TW201531460A - Cyanopyridine manufacturing method, benzonitrile manufacturing method, carbonate ester manufacturing method, and carbonate ester manufacturing apparatus - Google Patents

Cyanopyridine manufacturing method, benzonitrile manufacturing method, carbonate ester manufacturing method, and carbonate ester manufacturing apparatus Download PDF

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TW201531460A
TW201531460A TW103145480A TW103145480A TW201531460A TW 201531460 A TW201531460 A TW 201531460A TW 103145480 A TW103145480 A TW 103145480A TW 103145480 A TW103145480 A TW 103145480A TW 201531460 A TW201531460 A TW 201531460A
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catalyst
reaction
carbonate
solid
producing
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TWI562988B (en
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Kenji Nakao
Kimihito Suzuki
Kenichiro Fujimoto
Keiichi Tomishige
Yoshinao Nakagawa
Hitoshi Donomae
Masazumi Tamura
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Nippon Steel & Sumitomo Metal Corp
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Priority claimed from JP2014042007A external-priority patent/JP6349787B2/en
Priority claimed from JP2014183657A external-priority patent/JP6435728B2/en
Priority claimed from JP2014183655A external-priority patent/JP6435727B2/en
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Abstract

To provide a method for performing regeneration from picolinamide or benzamide to cyanopyridine or benzonitrile without using strong reagents and while also limiting generation of by-products. To solve said problem, one embodiment of the present invention provides a cyanopyridine manufacturing method characterized in that the cyanopyridine is manufactured by heating picolinamide in the presence of a catalyst loaded with an alkali metal oxide and in the presence of an organic solvent to cause a dehydration reaction. Another embodiment of the present invention provides a benzonitrile manufacturing method characterized in that the benzonitrile is manufactured by heating benzamide in the presence of a catalyst in which a metal oxide of a metal species such as molybdenum is loaded on a catalyst support obtained from SiO2, etc. and in the presence of an organic solvent to cause a dehydration reaction.

Description

氰吡啶之製造方法、苯甲腈之製造方法、碳酸酯之製造方法及碳酸酯之製造裝置 Method for producing cyanide pyridine, method for producing benzonitrile, method for producing carbonate, and device for producing carbonate

本發明有關一種氰吡啶之製造方法、苯甲腈之製造方法、碳酸酯之製造方法及碳酸酯之製造裝置。 The present invention relates to a method for producing cyanopyridine, a method for producing benzonitrile, a method for producing a carbonate, and a device for producing a carbonate.

背景技術 Background technique

所謂碳酸酯係指碳酸CO(OH)2之2個氫原子中有1個或2個原子業經烷基或芳基取代之化合物的總稱,其具有RO-C(=O)-OR’(R、R’表示飽和烴基或不飽和烴基)之結構。 The term "carbonate" refers to a general term for a compound in which one or two of the two hydrogen atoms of CO(OH) 2 are replaced by an alkyl group or an aryl group, and has RO-C(=O)-OR' (R). And R' represents a structure of a saturated hydrocarbon group or an unsaturated hydrocarbon group.

碳酸酯除了可作為用以提高辛烷值之汽油添加劑、及用以減少廢氣中之粒子的柴油機燃料添加劑之添加劑來使用之外,亦可用作合成聚碳酸酯或胺甲酸酯、醫藥品/農藥等樹脂及有機化合物時之烷化劑、羰化劑及溶劑等,或是用作鋰離子電池之電解液、潤滑油原料、鍋爐配管之防鏽用脫氧劑之原料等,實為非常有用之化合物。 In addition to being used as a gasoline additive for increasing the octane number and a diesel fuel additive for reducing particles in the exhaust gas, the carbonate can also be used as a synthetic polycarbonate or a urethane or a pharmaceutical product. /Alkylating agent, carbonylating agent, solvent, etc. in the case of resins and organic compounds such as pesticides, or as a raw material for electrolytes and lubricating oils for lithium ion batteries, and as a deoxidizer for rust prevention of boiler piping. Useful compounds.

習知之碳酸酯製造方法係以令光氣與作為羰基源之醇類直接反應的方法為主流。此種方法由於使用極為有害且具高腐蝕性之光氣,其輸送或貯藏等之處置上必須細心注意,為了維持管理製造設備及確保安全性而極耗成 本。此外,以本法進行製造時,原料及催化劑中含有氯等之鹵素,所得碳酸酯中含有無法以簡單之純化步驟予以去除的微量鹵素。在汽油添加劑、輕油添加劑及供用於電子材料之用途上,由於其也有成為腐蝕成因之疑慮存在,令微量存在之鹵素變得極微量之徹底純化步驟就變得必須。再者,由於此法需利用對人體極為有害之光氣,近來,行政指導(諸如,不許可新建本製造方法之製造設備等)逐漸變得嚴格,而強烈待望著無須使用光氣之新穎製造方法。 The conventional method for producing carbonates is mainly directed to a method in which phosgene is directly reacted with an alcohol as a carbonyl source. Due to the extremely harmful and highly corrosive phosgene, such methods must be carefully handled in terms of handling or storage, and are extremely consumable in order to maintain management equipment and ensure safety. this. Further, in the production by this method, a halogen such as chlorine is contained in the raw material and the catalyst, and the obtained carbonate contains a trace amount of halogen which cannot be removed by a simple purification step. In the case of gasoline additives, light oil additives, and applications for electronic materials, since there are also doubts about the cause of corrosion, it is necessary to thoroughly clean the halogen in a trace amount. Furthermore, since this method requires the use of phosgene which is extremely harmful to the human body, recent administrative guidance (such as manufacturing equipment that does not permit the creation of this manufacturing method) has gradually become stricter, and it is strongly desired to use novel manufacturing without using phosgene. method.

在此種情況下,如非專利文獻1所載,目前已有下述方法被視為不使用光氣之碳酸酯之製造法而趨於實用化:使二氧化碳與環氧乙烷等反應而合成出環狀碳酸酯,之後更與甲醇反應而獲得碳酸二甲酯。此種方法幾乎不使用或發生鹽酸等之腐蝕性物質,且將被視為地球暖化氣體而探求削減其量之二氧化碳納入架構中,可藉此期待削減效果,實為一種對環境友善之優異方法。然而,如專利文獻1所載,其極大課題在於副生成之乙二醇等的有效利用。此外,由於難以安全輸送環氧乙烷原料之乙烯或環氧乙烷,也有必須將碳酸酯製程用廠房與乙烯/環氧乙烷製程用廠房鄰接建造的限制。 In this case, as disclosed in Non-Patent Document 1, the following method has been considered to be practical as a method of producing a carbonate without using phosgene: synthesis of carbon dioxide and ethylene oxide The cyclic carbonate is removed and then reacted with methanol to obtain dimethyl carbonate. This method uses almost no corrosive substances such as hydrochloric acid, and it is considered to be a global warming gas, and it is considered to reduce the amount of carbon dioxide into the structure. Therefore, it is expected to reduce the effect, which is an excellent environmental friendliness. method. However, as disclosed in Patent Document 1, a great problem is the effective use of ethylene glycol or the like which is produced by-product. In addition, since it is difficult to safely transport ethylene or ethylene oxide of the ethylene oxide raw material, it is also necessary to construct a carbonate process plant adjacent to the ethylene/ethylene oxide process plant.

此外,如專利文獻2所載,目前也已揭示了一種使甲醇與一氧化碳在氯化亞銅催化劑存在下以液相進行氧氣氧化(oxygen oxidation)藉此製出碳酸二甲酯的方法。然而,本方法被指出有下述問題:需運用對人體有害之一氧化碳;與使用光氣之製造法相同,因催化劑中含有鹵素, 必須從所得碳酸酯進行鹵素之純化步驟;及,會副生成出不少的二氧化碳。 Further, as disclosed in Patent Document 2, a method of producing dimethyl carbonate by subjecting methanol and carbon monoxide to oxygen oxidation in the liquid phase in the presence of a cuprous chloride catalyst has been disclosed. However, this method has been pointed out to have the problem that it is necessary to use a carbon monoxide which is harmful to the human body; it is the same as the production method using phosgene, because the catalyst contains halogen, The halogen purification step must be carried out from the obtained carbonate; and, a considerable amount of carbon dioxide is formed by the side.

再者,如非專利文獻2所載,在Pd-Cu系催化劑存在下從亞硝酸甲酯與一氧化碳製出碳酸二甲酯之方法亦已實用化。本方法係使甲醇及氧與製造碳酸二甲酯時所副生成之一氧化氮反應而生成亞硝酸甲酯,藉此方法來供給原料之亞硝酸甲酯,如此仍有製程複雜及需運用對人體有害之一氧化碳等之課題。 Further, as disclosed in Non-Patent Document 2, a method of producing dimethyl carbonate from methyl nitrite and carbon monoxide in the presence of a Pd-Cu-based catalyst has also been put into practical use. The method comprises the steps of: reacting methanol and oxygen with one of nitrogen oxides produced by the production of dimethyl carbonate to form methyl nitrite, thereby supplying the raw material of methyl nitrite, so that the process is complicated and needs to be applied. The human body is harmful to carbon monoxide and other issues.

相對於此,目前正嘗試著使甲醇與二氧化碳在固體催化劑存在下反應以直接合成出碳酸酯(非專利文獻3)。然而,本反應雖屬平衡反應,平衡卻大幅偏向原料系統,因此甲醇轉化率最高也僅止於1%程度,而有反應率及生產性甚低此一應予克服之極大課題。 On the other hand, attempts have been made to directly synthesize a carbonate by reacting methanol with carbon dioxide in the presence of a solid catalyst (Non-Patent Document 3). However, although this reaction is an equilibrium reaction, the balance is largely biased toward the raw material system. Therefore, the highest methanol conversion rate is only about 1%, and the reaction rate and productivity are very low, which should be overcome.

為解決上述課題,現已嘗試將與碳酸酯(碳酸二甲酯)一起副生成之水去除至系統外以解除反應制約,例如,已有下述研究被報導:將縮醛(非專利文獻4)、2,2-二甲氧基丙烷(非專利文獻5)作為水合劑而與催化劑一起使用。然而,此種方法具有反應會隨著反應壓力提高而進行的特性,在低壓下反應產率極低,若非極高壓則無法獲得高生產性。這被推測是因為,可預想縮醛、2,2-二甲基丙烷之水合反應在液相下不受催化劑作用即會進行,因此與CO2壓力無關,碳酸二甲酯之直接合成反應的反應速度會決定整體的反應速度;但,在反應壓力分別為300氣壓(30MPa)、60氣壓(6MPa)之高壓下,甲醇轉化率會提高,昇壓所必須之動 能因此變得極大,而有能量效率變差等之問題。 In order to solve the above problems, it has been attempted to remove the water produced by the carbonic acid ester (dimethyl carbonate) to the outside of the system to release the reaction restriction. For example, the following studies have been reported: acetal (Non-Patent Document 4) 2,2-dimethoxypropane (Non-Patent Document 5) is used as a hydrating agent together with a catalyst. However, this method has a characteristic that the reaction proceeds as the reaction pressure is increased, and the reaction yield is extremely low at a low pressure, and high productivity cannot be obtained if it is not extremely high. This is presumed to be because it is expected that the hydration reaction of acetal and 2,2-dimethylpropane will proceed without being affected by the catalyst in the liquid phase, so that the direct synthesis reaction of dimethyl carbonate is independent of the pressure of CO 2 . The reaction rate determines the overall reaction rate; however, at a high pressure of 300 MPa (30 MPa) and 60 MPa (6 MPa), the methanol conversion rate will increase, and the kinetic energy necessary for the pressure increase will become extremely large. Problems such as poor energy efficiency.

此外,雖有使用分子篩(固體脫水劑)之研究(非專利文獻6)已獲報導,但其會成為使反應部(高壓)與脫水部(常壓)分離循環之製程,因此而有能量消費甚大且需要大量固體脫水劑之問題點。 In addition, although research using a molecular sieve (solid dehydrating agent) (Non-Patent Document 6) has been reported, it is a process for separating the reaction portion (high pressure) from the dehydration portion (normal pressure), and thus energy consumption. Very large and requires a large number of solid dehydrating agents.

另外,迄今為止,可用於碳酸酯之直接合成反應的固體催化劑已探討了:二甲氧基二丁基錫等之錫化合物;甲氧基鉈等之鉈化合物;乙酸鎳等之鎳化合物;五氧化釩;碳酸鉀等之鹼金屬碳酸鹽;及,Cu/SiO2等各種化合物。 Further, hitherto, solid catalysts which can be used for the direct synthesis reaction of carbonates have been studied: tin compounds such as dibutyltin dimethoxide; antimony compounds such as methoxyquinone; nickel compounds such as nickel acetate; vanadium pentoxide An alkali metal carbonate such as potassium carbonate; and various compounds such as Cu/SiO 2 .

另一方面,就將乙腈用作水合劑之反應而言,已有在固體催化劑存在下從二元醇之丙二醇與二氧化碳直接合成出環狀碳酸酯(碳酸丙烯酯)之反應系統的相關研究獲得報導(非專利文獻7)。然而,即使是本反應系統,反應壓力之影響仍是顯著,而有反應會隨著反應壓力提高而進行的特性,低壓下之反應產率極低,但在有利於環狀碳酸酯之直接合成反應平衡的高壓下則產率上昇,已確認反應壓力宜在100氣壓以上,而與上述者相同地具有能量效率變差等之問題。 On the other hand, in the reaction of using acetonitrile as a hydrating agent, a related research on a reaction system for directly synthesizing a cyclic carbonate (propylene carbonate) from a diol of a glycol and a carbon dioxide in the presence of a solid catalyst has been obtained. Report (Non-Patent Document 7). However, even in this reaction system, the influence of the reaction pressure is remarkable, and the reaction proceeds with the increase of the reaction pressure, and the reaction yield under low pressure is extremely low, but it is advantageous for the direct synthesis of the cyclic carbonate. When the reaction equilibrium is high, the yield is increased, and it is confirmed that the reaction pressure is preferably 100 or more, and the same as the above, there is a problem that the energy efficiency is deteriorated.

本案發明人在製造碳酸酯之際,著眼於使用不勻相催化劑而從一元醇與二氧化碳直接合成出碳酸酯之方法,並藉由使用乙腈來作為將與碳酸酯一起副生成之水排除到系統外之水合劑,終而發現了下述效果:毋須諸如非專利文獻4、5所載300氣壓或60氣壓般之高壓,而可在接近常壓之壓力下使反應獲得促進(參照專利文獻3)。 The inventors of the present invention focused on the direct synthesis of carbonates from monohydric alcohols and carbon dioxide using heterogeneous catalysts in the production of carbonates, and by using acetonitrile as a water to be produced as a by-product with carbonates. In the case of the external hydrating agent, the following effects are found: it is not necessary to carry out the reaction at a pressure close to the normal pressure, such as the pressure of 300 or 60 atmospheres as shown in Non-Patent Documents 4 and 5 (refer to Patent Document 3). ).

先行技術文献 Advanced technical literature 專利文獻 Patent literature

【專利文獻1】WO2004/014840號公報 [Patent Document 1] WO2004/014840

【專利文獻2】EP365,083號公報 [Patent Document 2] Publication No. EP365,083

【專利文獻3】日本特開2009-132673號公報 [Patent Document 3] Japanese Patent Laid-Open Publication No. 2009-132673

【專利文獻4】日本特開2010-77113號公報 [Patent Document 4] Japanese Patent Laid-Open Publication No. 2010-77113

【專利文獻5】日本特開2012-162523號公報 [Patent Document 5] Japanese Patent Laid-Open Publication No. 2012-162523

【專利文獻6】日本特開2009-213975號公報 [Patent Document 6] Japanese Patent Laid-Open Publication No. 2009-213975

【專利文獻7】日本特開2005-194224號公報 [Patent Document 7] Japanese Patent Laid-Open Publication No. 2005-194224

【專利文獻8】日本特開平11-35564號公報 [Patent Document 8] Japanese Patent Laid-Open No. Hei 11-35564

非專利文獻 Non-patent literature

【非專利文獻1】化學工學,68(1) (2004)41 [Non-Patent Document 1] Chemical Engineering, 68(1) (2004) 41

【非專利文獻2】催化劑,36 (1994) 127 [Non-Patent Document 2] Catalyst, 36 (1994) 127

【非專利文獻3】Catal. Lett., 58(1999) [Non-Patent Document 3] Catal. Lett., 58 (1999)

【非專利文獻4】Polyhedron, 19 (2000) 573 [Non-Patent Document 4] Polyhedron, 19 (2000) 573

【非專利文獻5】Appl. Catal. A Gen, 237(2002) 103 [Non-Patent Document 5] Appl. Catal. A Gen, 237 (2002) 103

【非專利文獻6】Eco Industry, 6(2001) 11 [Non-Patent Document 6] Eco Industry, 6 (2001) 11

【非專利文獻7】Catal. Lett., 112, (2006) 187 [Non-Patent Document 7] Catal. Lett., 112, (2006) 187

【非專利文獻8】M. B. Smith, J. March, Adv. Org. Chem.: Reactions, Mechanism, and Structure 5th ed., John Wiley & Sons, New York, (2001) [Patent Document 8] MB Smith, J. March, Adv. Org. Chem .: Reactions, Mechanism, and Structure 5 th ed., John Wiley & Sons, New York, (2001)

【非專利文獻9】御園生誠、齊藤泰和,催化劑化學,丸善(1999) [Non-Patent Document 9] Yuyuan Shengcheng, Saito Taihe, Catalyst Chemistry, Maruzen (1999)

【非專利文獻10】C. W. Kuo, et al., Chem. Commun., (2007) 301 [Non-Patent Document 10] C. W. Kuo, et al., Chem. Commun., (2007) 301

【非專利文獻11】S. Enthaler, Chem. Eur. J., 17(2011) 9316 [Non-Patent Document 11] S. Enthaler, Chem. Eur. J., 17 (2011) 9316

【非專利文獻12】K. Ishihara, et al., Angew. Chem. Int. Ed., 41(2002) 2983 [Non-Patent Document 12] K. Ishihara, et al., Angew. Chem. Int. Ed., 41 (2002) 2983

【非專利文獻13】S. Sueoka, et al., Chem. Commun., 46(2010) 8243 [Non-Patent Document 13] S. Sueoka, et al., Chem. Commun., 46 (2010) 8243

發明概要 Summary of invention

本案發明人為了更進一步提高碳酸酯之生成量,經精心探討水合劑之種類後發現,與乙腈相較下,藉由使用2-氰吡啶或苯甲腈更可大幅改善碳酸酯之生成量及生成速度,在接近常壓之相對較低壓力下容易進行反應,並且反應速度極為快速(參照專利文獻4、5)。然而,副生成之2-吡啶甲醯胺及苯甲醯胺之處理方法及利用方法則未獲探究。 In order to further increase the amount of carbonate formed, the inventors of the present invention have carefully studied the types of hydrating agents and found that the production of carbonates can be greatly improved by using 2-cyanopyridine or benzonitrile as compared with acetonitrile. The production rate is easy to carry out at a relatively low pressure close to normal pressure, and the reaction rate is extremely fast (see Patent Documents 4 and 5). However, the treatment methods and utilization methods of the by-produced 2-pyridinecarboxamide and benzamide have not been explored.

在本發明中用作水合劑且以2-氰吡啶及苯甲腈為首之腈類,一般被利用在溶劑、合成樹脂、染料及藥品中間產物等諸多用途上。其中,尤以2-氰吡啶為醫藥品或農藥之原料物質,其係一在合成2位之吡啶、哌啶衍生物時被用為起始原料之物質。此外,苯甲腈為醫藥品或農藥之原料物質,其係一在合成各種衍生物時被用為起始原料之物質。 The nitriles used as the hydrating agent in the present invention and including 2-cyanopyridine and benzonitrile are generally used in many applications such as solvents, synthetic resins, dyes, and pharmaceutical intermediates. Among them, 2-cyanopyridine is a raw material of a pharmaceutical or a pesticide, and is used as a starting material in the synthesis of a pyridine or piperidine derivative at the 2-position. Further, benzonitrile is a raw material of a pharmaceutical or a pesticide, and is a substance which is used as a starting material in the synthesis of various derivatives.

然而,藉由2-氰吡啶與水之反應而生成之2-吡啶甲醯胺的用途則侷限於一部分之醫農藥中間產物。同樣地,藉由苯甲腈與水之反應而生成之苯甲醯胺的用途也侷限在一部分之醫農藥中間產物。因此,在將2-氰吡啶或苯甲腈用作水合劑之碳酸酯製造過程中,期望能使副生成之2-吡啶甲醯胺或苯甲醯胺再生為2-氰吡啶或苯甲腈並予以再利用,爰此,使該再生反應以高選擇率(這是由於一旦生成副產物則變得難以作為水合劑再次利用)且高產率(這是由於一旦產率降低則2-吡啶甲醯胺或苯甲醯胺之殘留量會增多,2-氰吡啶或苯甲腈之分離處理量增多而使負荷提高)方式進行乃明確地成為產業課題。 However, the use of 2-pyridinecarbachamide formed by the reaction of 2-cyanopyridine with water is limited to a portion of the pharmaceutical pesticide intermediate. Similarly, the use of benzamide produced by the reaction of benzonitrile with water is also limited to a portion of the pharmaceutical pesticide intermediates. Therefore, in the production of a carbonate using 2-cyanopyridine or benzonitrile as a hydrating agent, it is desirable to regenerate the by-produced 2-pyridinecarboxamide or benzamidine to 2-cyanopyridine or benzonitrile. And reused, so that the regeneration reaction is made at a high selectivity (this is because it becomes difficult to reuse as a hydrating agent once a by-product is formed) and high yield (this is because once the yield is lowered, 2-pyridine A The residual amount of guanamine or benzamide is increased, and the amount of separation treatment of 2-cyanopyridine or benzonitrile is increased to increase the load. This is an industrial problem.

一般而言,就腈類合成方法之一而言,雖然可利用無機氰化物之求核取代反應,但卻有需使用有毒之氰化物及副生成鹵鹽之問題(非專利文獻8)。 In general, in the case of one of the nitrile synthesis methods, although the nuclear substitution reaction of the inorganic cyanide can be utilized, there is a problem that toxic cyanide and a by-product halogen salt are required (Non-Patent Document 8).

此外,以稱為氨氧化法(SOHIO法)之方法使用Mo-Bi系或Fe-Sn系之氧化物催化劑並在氨存在下以空氣作為氧化劑之氣相反應業已工業化,但其需要400℃以上之高反應溫度且限於丙醯腈等(非專利文獻9)。 Further, a gas phase reaction using a Mo-Bi-based or Fe-Sn-based oxide catalyst in the form of an ammonia oxidation method (SOHIO method) and using air as an oxidant in the presence of ammonia has been industrialized, but it requires 400 ° C or more. The high reaction temperature is limited to acrylonitrile or the like (Non-Patent Document 9).

另一方面,也有利用醯胺之脫水反應來進行的腈類合成,以2-吡啶甲醯胺或苯甲醯胺之脫水反應而言,雖已有2件之報告例,但皆是使用勻相催化劑,因此而造成了下述課題:合成後之純化及催化劑之分離等的後續步驟變得煩雜;以及,使用強烈試劑(強酸或強鹼)且發生多量副產物,因此環境負擔較大(非專利文獻10、11)。 On the other hand, there is also a nitrile synthesis by a dehydration reaction of decylamine. In the case of the dehydration reaction of 2-pyridinecarbamide or benzamide, although there are two reports, all are used uniformly. The phase catalyst causes a problem that the subsequent steps such as purification after synthesis and separation of the catalyst become complicated; and that a strong reagent (strong acid or strong base) is used and a large amount of by-products are generated, so that the environmental burden is large ( Non-patent literature 10, 11).

此外,就使用脫水劑之醯胺脫水反應而言,雖然在專利文獻7及8中已有在可使醯胺與水分液之脂肪族腈類或脂環式腈類所構成之溶劑中使用光氣、磷醯氯、亞硫醯氯、氯化硫醯基、五氯化磷等之腈類製造方法的相關記載,卻有需使用劇毒之氰化物或鹵化物之問題。 Further, in the case of the dehydration reaction of a guanamine using a dehydrating agent, in Patent Documents 7 and 8, light is used in a solvent which can form an aliphatic nitrile or an alicyclic nitrile which can be used for a guanamine and a water liquid. The related description of the method for producing nitriles such as gas, phosphonium chloride, sulfinium chloride, sulfonium chloride, and phosphorus pentachloride requires the use of highly toxic cyanide or halide.

又,就使用非勻相催化劑之醯胺脫水反應而言,在專利文獻3中已有第1級醯胺脫水反應用催化劑與使用其之腈類製造方法的相關記載。其中催化劑為在水滑石上載持有釩之固體催化劑,作為第1級醯胺,則是連同如苯甲醯胺般之芳香族醯胺、具雜環之醯胺及脂肪族醯胺均視為具有活性,但反應速度較慢而有所不足。這被認為是肇因於:一般而言,與腈類相較下醯胺屬於較安定之物質,醯胺脫水反應之反應速度較慢;此外,於醯胺分子內,醯胺基之氫原子與氮雜原子之間雖會發生分子內氫鍵,但醯胺之分子內氫鍵特別大而成為安定之物質,不易進行脫水反應。 Further, in the case of the decylamine dehydration reaction using a non-homogeneous catalyst, Patent Document 3 discloses a first-stage guanamine dehydration reaction catalyst and a nitrile production method using the same. The catalyst is a solid catalyst carrying vanadium on hydrotalcite, and as a first-grade guanamine, it is considered as an aromatic amide such as benzoguanamine, a decylamine having a heterocyclic ring, and an aliphatic decylamine. It is active, but the reaction rate is slow and insufficient. This is considered to be due to: in general, the decylamine is a relatively stable substance compared to the nitrile, and the reaction rate of the dehydration reaction of the guanamine is slow; in addition, in the molecule of the guanamine, the hydrogen atom of the guanamine group Although intramolecular hydrogen bonds occur between the nitrogen hetero atoms, the intermolecular hydrogen bonds of the indoleamine are particularly large and become stable substances, and it is difficult to carry out the dehydration reaction.

如上所述,迄今未止尚未有不需使用強烈試劑,且可在一併抑制副產物發生的同時,從吡啶甲醯胺或苯甲醯胺進行再生為氰吡啶或苯甲腈之方法的相關報告例。 As described above, there has been no correlation with the method of regenerating pyridine carboxamide or benzamide from pyridine carbenamide or benzamide while not inhibiting the occurrence of by-products. Report example.

有鑑於上述習知技術之問題點,本發明之目的即在於提供一種方法,其毋須使用強烈試劑且可在一併抑制副產物發生之同時,從吡啶甲醯胺或苯甲醯胺進行再生為氰吡啶或苯甲腈。 In view of the above problems of the prior art, it is an object of the present invention to provide a process which does not require the use of a strong reagent and which can inhibit the occurrence of by-products from being regenerated from pyridylguanamine or benzamide. Cyanide or benzonitrile.

雖然以往吡啶甲醯胺之脫水反應只會以勻相催 化劑來進行,但已探討了可抑制副產物且可容易分離之非勻相催化劑。 Although the dehydration reaction of pyridine carbenamide has only been used in the past The agent is used, but a heterogeneous catalyst which inhibits by-products and can be easily separated has been investigated.

於此,先嘗試以非勻相催化劑(其使用了被認為在製造苯甲醯胺上有效之釩)進行吡啶甲醯胺之脫水反應,得知如此幾乎不會生成氰吡啶。 Here, an attempt was made to carry out a dehydration reaction of pyridine carbenamide with a non-homogeneous catalyst which uses vanadium which is considered to be effective in producing benzamide, and it was found that cyanopyridine was hardly formed.

於是,本案發明人思及,因吡啶甲醯胺內之吡啶環顯示出弱鹼性,若使用酸性催化劑,有可能發生吡啶環吸附在催化劑之活性點而被毒化進而引起活性降低,爰此探討了以會呈現鹼性之金屬作為活性種的催化劑。 Therefore, the inventors of the present invention thought that since the pyridine ring in the pyridine carbenamide shows a weak basicity, if an acidic catalyst is used, there is a possibility that the pyridine ring is adsorbed at the active site of the catalyst and poisoned, thereby causing a decrease in activity. A catalyst which exhibits a basic metal as an active species.

結果發現,若使用使催化劑載體載持具鹼性性質之鹼金屬的催化劑,將會變得具有高活性,而終至完成本發明。 As a result, it has been found that if a catalyst which supports an alkali metal having a basic property in a catalyst carrier is used, it becomes highly active, and the present invention is completed.

本案發明人也針對苯甲腈之製造方法進一步探究。以往,苯甲醯胺之脫水反應係以非勻相催化劑進行,諸如單純之金屬氧化物粒子(非專利文獻12)、或者使金屬氧化物粒子載持於稱為水滑石之二維層狀無機化合物載體而成之物(非專利文獻13)等,但本案發明人推定該化合物中之金屬-氧之間的雙鍵係作為醯胺脫水反應之活性種發揮效用,而特別聚焦在具有相同雙鍵之金屬氧化物予以探討。 The inventors of the present invention have further explored the production method of benzonitrile. Conventionally, the dehydration reaction of benzamide is carried out by a heterogeneous catalyst such as a simple metal oxide particle (Non-Patent Document 12) or a metal oxide particle supported on a two-dimensional layered inorganic salt called hydrotalcite. The compound carrier (Non-Patent Document 13) or the like, but the inventors of the present invention presume that the double bond between the metal and oxygen in the compound functions as an active species of the indole dehydration reaction, and is particularly focused on having the same double The metal oxide of the bond is discussed.

本案發明人更就載體考量其表面結構及離子性、電子狀態,而從金屬氧化物於最佳存在狀態下被載持的觀點進行探究。 The inventors of the present invention have investigated the surface structure, the ionicity, and the electronic state of the carrier, and explored from the viewpoint that the metal oxide is carried in the optimal state of existence.

結果發現,針對特定之催化劑載體使其載持金屬-氧之間具有雙鍵之特定金屬,若使用此種催化劑,則在相 對較溫和之條件下仍會變得高活性,進而完成本發明。 As a result, it has been found that a specific catalyst carrier is used to carry a specific metal having a double bond between metal and oxygen, and if such a catalyst is used, the phase is The invention is still highly active under milder conditions, thereby completing the present invention.

本案發明人也進一步將上述見解應用於碳酸酯之製造方法並予以探究。亦即,本案發明人在製造碳酸酯之際,著眼於從一元醇與二氧化碳直接合成碳酸酯之方法,並藉由使用乙腈及苯甲腈作為水合劑而將與碳酸酯一起副生成之水去除到系統外,終而發現了下述效果並申請專利(專利文獻3、專利文獻4):可毋須非專利文獻4、5所記載之諸如30MPa(300氣壓)或6MPa(60氣壓)的高壓,而在接近於常壓之壓力下,使反應獲得促進。又更進一步發現,與使用乙腈或苯甲腈時相較,可藉由使用2-氰吡啶而大幅改善碳酸酯之生成量及生成速度,且在接近常壓之相對較低之壓力下反應容易進行並且反應速度極快,此一發現已被專利公開在專利文獻5。但無論是使用任一水合劑的情況,均未探究副產物醯胺之分離或再利用等之處理方法,而成為了產業課題。 The inventors of the present invention have further applied the above findings to the method of producing carbonates and have explored them. That is, the inventors of the present invention focused on the direct synthesis of carbonate from monohydric alcohol and carbon dioxide in the production of carbonate, and removed the water formed by the carbonic acid ester by using acetonitrile and benzonitrile as a hydrating agent. In addition to the system, the following effects have been found and patents have been found (Patent Document 3, Patent Document 4): high pressure such as 30 MPa (300 atmospheres) or 6 MPa (60 atmospheres) described in Non-Patent Documents 4 and 5 is not required. The reaction is promoted under pressure close to atmospheric pressure. It has further been found that the amount of carbonate formation and the rate of formation can be greatly improved by using 2-cyanopyridine as compared with the case of using acetonitrile or benzonitrile, and it is easy to react at a relatively low pressure close to normal pressure. This is carried out and the reaction rate is extremely fast, and this finding has been disclosed in Patent Document 5 by the patent. However, in the case of using any of the hydrating agents, the treatment methods such as the separation or reuse of the by-product guanamine have not been investigated, and it has become an industrial issue.

本案發明人以上述知識見解為基礎,針對包含副產物之利用在內的碳酸酯製造方法進行探討,而思及將用作水合劑時具有優異特性之氰吡啶或苯甲腈用於本製造方法中,該優異特性包含:在接近常壓之相對低壓下反應容易進行、反應速度非常快且副產物之種類亦少。 Based on the above knowledge, the inventors of the present invention have studied the method for producing a carbonate containing the use of by-products, and considered the use of cyanide or benzonitrile having excellent properties as a hydrating agent in the present production method. Among them, the excellent characteristics include that the reaction proceeds easily at a relatively low pressure close to normal pressure, the reaction rate is very fast, and the kinds of by-products are also small.

於是,針對固體催化劑,著眼於構成催化劑之元素及組成予以精心探討,結果發現,特定之固體催化劑在水合劑使用氰吡啶或苯甲腈時,於固體催化劑存在下因水合反應而生成吡啶甲醯胺或苯甲醯胺之反應會受到促進, 而有效率地進行源自反應系統之脫水,即使在相對低壓之溫和條件下,也不會受到反應平衡制約,而可高產率地獲得碳酸酯。 Then, in view of the solid catalyst, attention was paid to the elements and compositions constituting the catalyst. As a result, it was found that a specific solid catalyst produced pyridine formazan in the presence of a solid catalyst in the presence of a solid catalyst in the case of using a cyanopyridine or benzonitrile as a hydrating agent. The reaction of amine or benzamide is promoted, The dehydration from the reaction system is efficiently carried out, and even under mild conditions of relatively low pressure, it is not restricted by the reaction equilibrium, and the carbonate can be obtained in high yield.

更進一步發現,於此等催化劑之中,使用特定催化劑載體之物極為有效。 It has further been found that among these catalysts, the use of a specific catalyst carrier is extremely effective.

又,水合劑使用氰吡啶或苯甲腈時,會副生成吡啶甲醯胺或苯甲醯胺。此等吡啶甲醯胺或苯甲醯胺之用途受限而有難以有效活用之問題。於此,本案發明人將上述知識見解應用到碳酸酯之製造方法中,藉此令吡啶甲醯胺或苯甲醯胺再生為氰吡啶或苯甲腈。本發明之要旨如下。 Further, when cyanopyridine or benzonitrile is used as the hydrating agent, pyridine carbenamide or benzamide is produced as a by-product. The use of such pyridine carbenamide or benzamide is limited and there is a problem that it is difficult to use it effectively. Here, the inventors of the present invention applied the above knowledge to the method for producing a carbonate, whereby pyridine carbenamide or benzamide was regenerated into cyanopyridine or benzonitrile. The gist of the present invention is as follows.

(1)一種氰吡啶之製造方法,其特徵在於:在載持有鹼金屬氧化物之催化劑存在下且在有機溶劑存在下,將吡啶甲醯胺加熱使其進行脫水反應,藉以製出氰吡啶。 (1) A method for producing cyanopyridine, which comprises heating a pyridine carbenamide in the presence of an organic metal-containing catalyst in the presence of an organic solvent to carry out a dehydration reaction, thereby producing a cyanopyridine .

(2)如前述(1)記載之氰吡啶之製造方法,其中前述氰吡啶為2-氰吡啶,且前述吡啶甲醯胺為2-吡啶甲醯胺。 (2) The method for producing cyanide according to the above (1), wherein the cyanopyridine is 2-cyanopyridine, and the pyridine carbenamide is 2-pyridinecarboxamide.

(3)如前述(1)或(2)之氰吡啶之製造方法,其中前述載持有鹼金屬氧化物之催化劑係一在由SiO2、CeO2及ZrO2中任1種或2種以上所構成之催化劑載體上載持有1種或2種以上鹼金屬氧化物的催化劑。 (3) The method for producing a cyanopyridine according to the above (1) or (2), wherein the catalyst supporting the alkali metal oxide is one or more selected from the group consisting of SiO 2 , CeO 2 and ZrO 2 . The catalyst carrier is configured to carry a catalyst containing one or two or more kinds of alkali metal oxides.

(4)如前述(3)之氰吡啶之製造方法,其中前述催化劑載體為SiO2(4) The method for producing cyanide according to the above (3), wherein the catalyst carrier is SiO 2 .

(5)如前述(1)至(4)中任一項之氰吡啶之製造方法,其中前述鹼金屬氧化物為Li、K、Na、Rb及Cs中任一者之氧化物。 (5) The method for producing a cyanopyridine according to any one of the above (1) to (4) wherein the alkali metal oxide is an oxide of any one of Li, K, Na, Rb and Cs.

(6)如前述(1)至(5)中任一項之氰吡啶之製造方法,其中前述有機溶劑為對稱三甲苯(mesitylene) (6) The method for producing cyanide pyridine according to any one of the above (1) to (5) wherein the organic solvent is mesitylene

(7)如前述(1)至(6)中任一項之氰吡啶之製造方法,其在前述脫水反應之際使用脫水劑。 (7) The method for producing cyanopyridine according to any one of the above (1) to (6), wherein a dehydrating agent is used in the dehydration reaction.

(8)一種碳酸酯之製造方法,其特徵在於具有:第1反應步驟,其在CeO2及ZrO2中任一方或雙方之固體催化劑與氰吡啶存在下,使一元醇與二氧化碳反應而生成碳酸酯與水,在此同時,藉由前述氰吡啶與前述已生成之水的水合反應使吡啶甲醯胺生成;及第2反應步驟,其在經由前述第1反應步驟分離出前述吡啶甲醯胺後,在載持有鹼金屬氧化物之催化劑存在下且在有機溶劑存在下,將該吡啶甲醯胺加熱並進行脫水反應,藉此而再生為氰吡啶;並且,將前述第2反應步驟所再生之氰吡啶使用於前述第1反應步驟中。 (8) A method for producing a carbonate, characterized by comprising: a first reaction step of reacting a monohydric alcohol with carbon dioxide to form a carbonic acid in the presence of a solid catalyst of either or both of CeO 2 and ZrO 2 and cyanide And an ester, wherein at the same time, pyridine carbenamide is formed by hydration of the cyanopyridine with the water formed; and a second reaction step of separating the pyridine carbenamide by the first reaction step Thereafter, the pyridine carbenamide is heated and dehydrated in the presence of a catalyst carrying an alkali metal oxide in the presence of an organic solvent, thereby being regenerated into cyanide; and the second reaction step is The regenerated cyanide is used in the first reaction step described above.

(9)如前述(8)之碳酸酯之製造方法,其具有:第1反應步驟,其將CeO2及ZrO2中任一方或雙方之固體催化劑與一元醇、二氧化碳及氰吡啶混合並使其反應,而生成碳酸酯與吡啶甲醯胺;第1分離步驟,其將自該第1反應步驟排出之碳酸酯、吡啶甲醯胺、未反應之氰吡啶及前述固體催化劑以烷烴實施溶劑萃取,之後施行固液分離而分離為:液相之碳酸酯、未反應之氰吡啶及烷烴、以及固相之前述固體催化劑及吡啶甲醯胺; 第2分離步驟,其使前述第1分離步驟之固液分離後之液相碳酸酯、未反應之氰吡啶及烷烴各自分離;第3分離步驟,其以親水性溶劑萃取前述第1分離步驟在固液分離後的固相,即固體催化劑及吡啶甲醯胺後,施行固液分離而分離為:液相之吡啶甲醯胺及親水性溶劑、以及固相之固體催化劑;第2反應步驟,其在載持有鹼金屬氧化物之催化劑存在下且在有機溶劑存在下,將該第3分離步驟所分離出之吡啶甲醯胺加熱使其進行脫水反應,而生成氰吡啶;第4分離步驟,其將自該第2反應步驟排出之氰吡啶、未反應之吡啶甲醯胺及載持有鹼金屬氧化物之催化劑予以過濾,而分離出固相之載持有鹼金屬氧化物之催化劑;及第5分離步驟,其使該第4分離步驟分離後殘存之氰吡啶、吡啶甲醯胺、有機溶劑及水各自分離;並且,將前述第5分離步驟所分離出之氰吡啶使用於前述第1反應步驟中。 (9) The method for producing a carbonate according to the above (8), comprising: a first reaction step of mixing a solid catalyst of either or both of CeO 2 and ZrO 2 with monohydric alcohol, carbon dioxide, and cyanopyridine; a reaction to form a carbonate and a pyridine carbenamide; a first separation step of subjecting the carbonate, pyridine carbenamide, unreacted cyanopyridine, and the solid catalyst discharged from the first reaction step to solvent extraction with an alkane, Thereafter, solid-liquid separation is carried out to separate into a liquid phase carbonate, an unreacted cyanopyridine and an alkane, and a solid phase of the solid catalyst and pyridine carbenamide; and a second separation step for solidifying the first separation step The liquid phase carbonate, the unreacted cyanopyridine and the alkane are separated after the liquid separation; the third separation step extracts the solid phase after the solid-liquid separation in the first separation step by a hydrophilic solvent, that is, the solid catalyst and the pyridine group After the guanamine is subjected to solid-liquid separation, it is separated into: a liquid phase pyridine carbenamide and a hydrophilic solvent, and a solid phase solid catalyst; and a second reaction step in which a catalyst carrying an alkali metal oxide is present And the pyridine carbenamide separated by the third separation step is heated to be subjected to a dehydration reaction in the presence of an organic solvent to form a cyanide pyridine; and a fourth separation step of discharging cyanide from the second reaction step Pyridine, unreacted pyridine carbenamide and a catalyst carrying an alkali metal oxide are filtered to separate a solid phase catalyst carrying an alkali metal oxide; and a fifth separation step which causes the fourth separation The cyanopyridine, the pyridine carbenamide, the organic solvent and the water remaining after the separation are separated, respectively; and the cyanopyridine separated in the above fifth separation step is used in the first reaction step.

(10)如前述(9)之碳酸酯之製造方法,其更具有一使前述第3分離步驟所分離出之固體催化劑再生的步驟,並且將再生後之催化劑使用於前述第1反應步驟中。 (10) The method for producing a carbonate according to the above (9), further comprising the step of regenerating the solid catalyst separated by the third separation step, and using the regenerated catalyst in the first reaction step.

(11)如前述(9)或(10)之碳酸酯之製造方法,其在前述第1反應步驟中有未反應之一元醇殘留,而在前述第1分離步驟中將自前述第1反應步驟排出之碳酸酯、吡啶甲醯胺、未反應之一元醇、未反應之氰吡啶及前述固體催化劑以烷烴實施溶劑萃取,之後施行固液分離而分離為:液相 之碳酸酯、未反應之一元醇、未反應之氰吡啶及烷烴以及固相之前述固體催化劑及吡啶甲醯胺。 (11) The method for producing a carbonate according to the above (9) or (10), wherein in the first reaction step, an unreacted monohydric alcohol remains, and in the first separating step, from the first reaction step The discharged carbonate, the pyridine carbenamide, the unreacted monohydric alcohol, the unreacted cyanide, and the aforementioned solid catalyst are subjected to solvent extraction with an alkane, followed by solid-liquid separation to be separated into a liquid phase. The above-mentioned solid catalyst of the carbonate, the unreacted monohydric alcohol, the unreacted cyanpyridine and the alkane, and the solid phase, and the pyridine carbenamide.

(12)如前述(9)至(11)中任一項之碳酸酯之製造方法,其在前述第1反應步驟中生成吡啶甲酸甲酯及胺甲酸甲酯中之至少任一者作為副產物,且在前述第1分離步驟中,將自前述第1反應步驟排出之碳酸酯、吡啶甲醯胺、未反應之氰吡啶、吡啶甲酸甲酯、胺甲酸甲酯及前述固體催化劑以烷烴實施溶劑萃取,之後施行固液分離而分離為:液相之碳酸酯、未反應之氰吡啶、吡啶甲酸甲酯、胺甲酸甲酯及烷烴以及固相之前述固體催化劑及吡啶甲醯胺。 (12) The method for producing a carbonate according to any one of the above (9) to (11), wherein at least one of methyl pyridinecarboxylate and methyl carbamate is produced as a by-product in the first reaction step In the first separation step, the carbonate, the pyridine carbenamide, the unreacted cyanide, the methyl pyridinecarboxylate, the methyl carbamate, and the solid catalyst discharged from the first reaction step are subjected to a solvent as an alkane. The extraction is followed by solid-liquid separation and separation into a liquid phase carbonate, an unreacted cyanide, a methyl pyridinecarboxylate, a methyl carbamate and an alkane, and a solid phase of the above solid catalyst and pyridine carbenamide.

(13)如前述(9)至(12)中任一項之碳酸酯之製造方法,其在前述第1反應步驟中有未反應之一元醇殘留,且生成吡啶甲酸甲酯及胺甲酸甲酯中之至少任一者作為副產物,而在前述第1分離步驟中將自前述第1反應步驟排出之碳酸酯、吡啶甲醯胺、未反應之一元醇、未反應之氰吡啶、吡啶甲酸甲酯、胺甲酸甲酯及前述固體催化劑以烷烴實施溶劑萃取,之後施行固液分離而分離為:液相之碳酸酯、未反應之一元醇、未反應之氰吡啶、吡啶甲酸甲酯、胺甲酸甲酯及烷烴,以及固相之前述固體催化劑及吡啶甲醯胺。 (13) A method for producing a carbonate according to any one of the above (9) to (12), wherein in the first reaction step, an unreacted monohydric alcohol remains, and methyl pyridinecarboxylate and methyl carbamate are formed. At least one of them is a by-product, and in the first separation step, the carbonate, the pyridylcarbamide, the unreacted monohydric alcohol, the unreacted cyanide, and the picolinic acid are discharged from the first reaction step. The ester, methyl carbamate and the above solid catalyst are subjected to solvent extraction with an alkane, followed by solid-liquid separation to be separated into: a liquid phase carbonate, an unreacted monohydric alcohol, an unreacted cyanide, a methyl pyridinecarboxylate, a uric acid. A methyl ester and an alkane, and a solid phase of the foregoing solid catalyst and pyridine carbenamide.

(14)如前述(9)至(13)中任一項之碳酸酯之製造方法,其在前述溶劑萃取之際所使用之烷烴為己烷。 (14) The method for producing a carbonate according to any one of the above (9) to (13), wherein the alkane used in the solvent extraction is hexane.

(15)如前述(9)至(14)中任一項之碳酸酯之製造方法,其中前述親水性溶劑為丙酮。 (15) The method for producing a carbonate according to any one of the above (9) to (14) wherein the hydrophilic solvent is acetone.

(16)如前述(8)至(15)中任一項之碳酸酯之製造方 法,其中前述氰吡啶為2-氰吡啶,且前述吡啶甲醯胺為2-吡啶甲醯胺。 (16) A producer of a carbonate according to any one of the above (8) to (15) The method wherein the cyanopyridine is 2-cyanopyridine, and the pyridine carbenamide is 2-pyridinecarbamide.

(17)如前述(8)至(16)中任一項之碳酸酯之製造方法,其中前述載持有鹼金屬氧化物之催化劑係一在SiO2、CeO2及ZrO2中任1種或2種以上所構成之催化劑載體上載持有1種或2種以上鹼金屬氧化物的催化劑。 (17) The method for producing a carbonate according to any one of the above (8), wherein the catalyst supporting the alkali metal oxide is one of SiO 2 , CeO 2 and ZrO 2 or A catalyst in which two or more kinds of alkali metal oxides are supported by a catalyst carrier having two or more kinds of catalyst carriers.

(18)如前述(17)之碳酸酯之製造方法,其中前述催化劑載體為SiO2(18) A method for producing a carbonate according to the above (17), wherein the catalyst carrier is SiO 2 .

(19)如前述(8)至(18)中任一項之碳酸酯之製造方法,其中前述鹼金屬氧化物為Li、K、Na、Rb及Cs中任一者之氧化物。 (19) The method for producing a carbonate according to any one of the above (8), wherein the alkali metal oxide is an oxide of any one of Li, K, Na, Rb and Cs.

(20)如前述(8)至(19)中任一項之碳酸酯之製造方法,其中前述有機溶劑為對稱三甲苯。 (20) The method for producing a carbonate according to any one of the above (8) to (19) wherein the organic solvent is symmetrical trimethylbenzene.

(21)如前述(8)至(20)中任一項之碳酸酯之製造方法,其係於前述脫水反應之際使用脫水劑。 (21) A method for producing a carbonate according to any one of the above (8) to (20), wherein a dehydrating agent is used in the dehydration reaction.

(22)如前述(8)至(21)中任一項之碳酸酯之製造方法,其中前述一元醇為甲醇,且該方法製造碳酸二甲酯作為碳酸酯。 (22) The method for producing a carbonate according to any one of the above (8) to (21) wherein the monohydric alcohol is methanol, and the method produces dimethyl carbonate as a carbonate.

(23)如前述(8)至(22)中任一項之碳酸酯之製造方法,其中前述一元醇為乙醇,且該方法製造碳酸二乙酯作為碳酸酯。 (23) The method for producing a carbonate according to any one of the above (8) to (22) wherein the monohydric alcohol is ethanol, and the method produces diethyl carbonate as a carbonate.

(24)一種碳酸酯之製造裝置,用於如前述(8)至(23)中任一項之碳酸酯之製造方法,其特徵在於具有:加壓部,其加壓二氧化碳; 第1反應部,其在CeO2及ZrO2中任一方或雙方之固體催化劑與氰吡啶存在下,使一元醇與二氧化碳反應而生成碳酸酯與水,在此同時,藉由前述氰吡啶與前述已生成之水的水合反應,使吡啶甲醯胺生成;第1分離部,其將自該第1反應步驟排出之碳酸酯、吡啶甲醯胺、未反應之氰吡啶及前述固體催化劑以烷烴實施溶劑萃取,之後施行固液分離而分離為:液相之碳酸酯、未反應之氰吡啶及烷烴以及固相之前述固體催化劑及吡啶甲醯胺;第2分離部,其使前述第1分離部施行固液分離後之液相碳酸酯、未反應之氰吡啶及烷烴各自分離;第3分離部,其以親水性溶劑萃取前述第1分離步驟施行固液分離後的固體催化劑及吡啶甲醯胺,之後施行固液分離而分離為:液相之吡啶甲醯胺及親水性溶劑以及固相之固體催化劑第2反應部,其在載持有鹼金屬氧化物之催化劑存在下且在有機溶劑存在下,將以前述第3分離部分離之前述吡啶甲醯胺加熱並使其進行脫水反應,而生成氰吡啶;第4分離部,其將自該第2反應部排出之氰吡啶、未反應之吡啶甲醯胺及載持有鹼金屬氧化物之催化劑予以過濾,而分離出固相之載持有鹼金屬氧化物之催化劑;第5分離部,其使該第4分離部施行分離後所殘存之氰吡啶、吡啶甲醯胺、有機溶劑及水各自分離;及輸送部,其將前述第5分離部所分離出之氰吡啶朝前述 第1反應部輸送。 (24) A method for producing a carbonate according to any one of the above (8) to (23), characterized by comprising: a pressurizing portion for pressurizing carbon dioxide; and a first reaction portion And reacting a monohydric alcohol with carbon dioxide in the presence of a solid catalyst of either or both of CeO 2 and ZrO 2 in the presence of cyanopyridine to form a carbonate and water, and at the same time, by the aforementioned cyanopyridine and the aforementioned water a hydration reaction to produce pyridine carbenamide; a first separation unit that extracts carbonate, pyridine carbenamide, unreacted cyanopyridine, and the aforementioned solid catalyst discharged from the first reaction step by solvent extraction with an alkane, and then Separating into a liquid phase carbonate, an unreacted cyanopyridine and an alkane, and a solid phase of the solid catalyst and pyridine carbenamide, and a second separation unit for performing solid-liquid separation on the first separation unit The liquid phase carbonate, the unreacted cyanopyridine, and the alkane are separated, and the third separation unit extracts the solid catalyst and the pyridine carbenamide after the solid-liquid separation in the first separation step by a hydrophilic solvent, and then performs the same. Separating and separating into liquid phase pyridine carbenamide and a hydrophilic solvent and a solid phase solid catalyst second reaction portion, which is in the presence of a catalyst carrying an alkali metal oxide and in the presence of an organic solvent, The pyridine carbenamide separated by the third separation unit is heated and subjected to a dehydration reaction to form cyanide pyridine, and a fourth separation unit is obtained by discharging cyanide from the second reaction portion, unreacted pyridine carbenamide And a catalyst carrying an alkali metal oxide, and separating the solid phase carrier carrying the alkali metal oxide; and a fifth separation unit for separating the cyanide remaining after the separation of the fourth separation portion, The pyridine carbenamide, the organic solvent and the water are separated from each other; and the transport unit that transports the cyanopyridine separated by the fifth separation unit toward the first reaction unit.

(25)一種苯甲腈之製造方法,其特徵在於:在催化劑存在下且在有機溶劑存在下,將苯甲醯胺加熱使其進行脫水反應,藉以製造苯甲腈,並且,該催化劑係在由SiO2、TiO2、CeO2、ZrO2、Al2O3及C中任1種或2種以上所構成之催化劑載體上載持有鉬、鎢、錸、鈦及鈮中任1種或2種以上金屬種之金屬氧化物。 (25) A process for producing benzonitrile, characterized in that benzonitrile is heated in the presence of a catalyst in the presence of an organic solvent to carry out a dehydration reaction, whereby benzonitrile is produced, and the catalyst is A catalyst carrier composed of one or more of SiO 2 , TiO 2 , CeO 2 , ZrO 2 , Al 2 O 3 and C is loaded with one or two of molybdenum, tungsten, rhenium, titanium and lanthanum. A metal oxide of the above metal species.

(26)如前述(25)之苯甲腈之製造方法,其將前述苯甲醯胺加熱並使其在液相狀態下進行脫水反應,藉以製出苯甲腈。 (26) A process for producing benzonitrile according to the above (25), wherein the benzamide is heated and subjected to a dehydration reaction in a liquid phase to produce benzonitrile.

(27)如前述(25)或(26)之苯甲腈之製造方法,其中前述催化劑載體為SiO2(27) A process for producing benzonitrile according to the above (25) or (26), wherein the catalyst carrier is SiO 2 .

(28)如前述(25)至(27)中任一項之苯甲腈之製造方法,其中前述催化劑係在SiO2之載體上載持有鉬氧化物。 (28) The method for producing benzonitrile according to any one of the above (25), wherein the catalyst is a molybdenum oxide supported on a carrier of SiO 2 .

(29)如前述(25)至(28)中任一項之苯甲腈之製造方法,其中前述有機溶劑係由氯苯、二甲苯及對稱三甲苯中任1種或2種以上構成。 The method for producing benzonitrile according to any one of the above-mentioned (25), wherein the organic solvent is one or more selected from the group consisting of chlorobenzene, xylene and symmetrical trimethylbenzene.

(30)如前述(25)至(29)中任一項之苯甲腈之製造方法,其在前述脫水反應之際使用脫水劑。 (30) A method for producing benzonitrile according to any one of (25) to (29), wherein a dehydrating agent is used in the dehydration reaction.

(31)一種碳酸酯之製造方法,其特徵在於具有:第1反應步驟,其在CeO2及ZrO2中任一方或雙方之固體催化劑與苯甲腈存在下,使一元醇與二氧化碳反應而生成碳酸酯與水,在此同時,藉由前述苯甲腈與前述已生成之 水的水合反應,使苯甲醯胺生成;及第2反應步驟,其在經由前述第1反應步驟分離出前述苯甲醯胺後,在催化劑存在下且在有機溶劑存在下,將該苯甲醯胺加熱並進行脫水反應,藉此而再生為苯甲腈,且,該催化劑係於SiO2、TiO2、CeO2、ZrO2、Al2O3及C中任1種或2種以上之催化劑載體上載持有鉬、鎢、錸、鈦及鈮中任1種或2種以上金屬種之金屬氧化物;並且,將前述第2反應步驟所再生之苯甲腈使用於前述第1反應步驟中。 (31) A method for producing a carbonate, comprising: a first reaction step of reacting a monohydric alcohol with carbon dioxide in the presence of a solid catalyst of either or both of CeO 2 and ZrO 2 in the presence of benzonitrile; a carbonate and water, at the same time, by the hydration reaction of the benzonitrile with the water formed, to form benzamide; and a second reaction step of separating the benzene by the first reaction step After the formamide, the benzamide is heated and dehydrated in the presence of a catalyst in the presence of an organic solvent, thereby regenerating to benzonitrile, and the catalyst is based on SiO 2 , TiO 2 , CeO. (2) a catalyst carrier of one or more of ZrO 2 , Al 2 O 3 and C, and a metal oxide of one or more metal species of molybdenum, tungsten, niobium, titanium and niobium; The benzonitrile regenerated in the second reaction step is used in the first reaction step.

(32)如前述(31)之碳酸酯之製造方法,其具有:第1反應步驟,其在CeO2及ZrO2中任一方或雙方之固體催化劑與苯甲腈存在下,使一元醇與二氧化碳反應而生成碳酸酯與水,在此同時,藉由前述苯甲腈與前述已生成之水的水合反應,使苯甲醯胺生成;第1分離步驟,其將自前述第1反應步驟排出之碳酸酯、苯甲醯胺、未反應之苯甲腈及前述固體催化劑以烷烴實施溶劑萃取,之後施行固液分離而分離為:液相之碳酸酯、未反應之苯甲腈及烷烴以及固相之前述固體催化劑及苯甲醯胺;第2分離步驟,其使前述固液分離後液相之碳酸酯、未反應苯甲腈及烷烴各自分離;第3分離步驟,其以親水性溶劑萃取前述固液分離後之固體催化劑及苯甲醯胺,並施行固液分離而分離為:液相之苯甲醯胺及親水性溶劑以及固相之固體催化劑; 第2反應步驟,其在催化劑存在下且在有機溶劑存在下將該第3分離步驟分離出之苯甲醯胺加熱並進行脫水反應,藉此而再生為苯甲腈,且該催化劑係在SiO2、TiO2、CeO2、ZrO2、Al2O3及C中任1種或2種以上之催化劑載體上載持有鉬、鎢、錸、鈦及鈮中任1種或2種以上金屬種之金屬氧化物;第4分離步驟,其將自第2反應步驟排出之苯甲腈、未反應之苯甲醯胺及在催化劑載體上載持有金屬氧化物之催化劑予以過濾,而分離出在催化劑載體上載持有金屬氧化物之固相催化劑;及第5分離步驟,其使該分離後殘存之苯甲腈、苯甲醯胺、有機溶劑及水各自分離;並且,將前述分離出之苯甲腈使用於前述第1反應步驟中。 (32) A method for producing a carbonate according to the above (31), comprising: a first reaction step of monohydric alcohol and carbon dioxide in the presence of one or both of a solid catalyst of CeO 2 and ZrO 2 and benzonitrile; The reaction produces a carbonate and water, and at the same time, the benzamide is formed by the hydration reaction of the benzonitrile with the water formed, and the first separation step is discharged from the first reaction step. The carbonate, benzamide, unreacted benzonitrile and the aforementioned solid catalyst are subjected to solvent extraction with an alkane, followed by solid-liquid separation to be separated into a liquid phase carbonate, unreacted benzonitrile and an alkane, and a solid phase. The solid catalyst and benzamide; a second separation step of separating the liquid phase carbonate, unreacted benzonitrile and an alkane after the solid-liquid separation; and a third separation step of extracting the aforementioned with a hydrophilic solvent The solid catalyst and the benzamide after solid-liquid separation are separated into a liquid phase of benzamide and a hydrophilic solvent and a solid phase solid catalyst by solid-liquid separation; a second reaction step in the presence of a catalyst And there is The benzamide separated in the third separation step is heated and dehydrated in the presence of an organic solvent, thereby being regenerated into benzonitrile, and the catalyst is in SiO 2 , TiO 2 , CeO 2 , ZrO 2 , Al. a catalyst carrier in which one or two or more kinds of 2 O 3 and C are supported, and a metal oxide of one or more metal species of molybdenum, tungsten, niobium, titanium, and niobium; and a fourth separation step, which will The benzonitrile discharged from the second reaction step, the unreacted benzamide and the catalyst carrying the metal oxide on the catalyst carrier are filtered, and the solid phase catalyst carrying the metal oxide on the catalyst carrier is separated; And a fifth separation step of separating benzonitrile, benzamide, an organic solvent and water remaining after the separation; and using the isolated benzonitrile in the first reaction step.

(33)如前述(32)之碳酸酯之製造方法,其更具有使前述已分離之固體催化劑再生的步驟,且將再生後之催化劑使用於前述第1反應步驟中。 (33) The method for producing a carbonate according to the above (32), further comprising the step of regenerating the separated solid catalyst, and using the regenerated catalyst in the first reaction step.

(34)如前述(32)或(33)之碳酸酯之製造方法,其在前述溶劑萃取之際所使用的烷烴為己烷。 (34) A method for producing a carbonate according to the above (32) or (33), wherein the alkane used in the solvent extraction is hexane.

(35)如前述(32)至(34)中任一項之碳酸酯之製造方法,其中前述親水性溶劑為丙酮。 The method for producing a carbonate according to any one of the above (32) to (34) wherein the hydrophilic solvent is acetone.

(36)如前述(31)至(35)中任一項之碳酸酯之製造方法,其中前述載持有金屬氧化物之催化劑載體為SiO2、TiO2、CeO2及ZrO2中之任1種或2種以上。 The method for producing a carbonate according to any one of the above (31) to (35), wherein the catalyst carrier carrying the metal oxide is any one of SiO 2 , TiO 2 , CeO 2 and ZrO 2 . Kind or more than two.

(37)如前述(36)之碳酸酯之製造方法,其中前述催化劑載體為SiO2(37) A method for producing a carbonate according to the above (36), wherein the catalyst carrier is SiO 2 .

(38)如前述(31)至(37)中任一項之碳酸酯之製造方法,其中前述金屬氧化物為鉬氧化物。 The method for producing a carbonate according to any one of the above (31) to (37) wherein the metal oxide is a molybdenum oxide.

(39)如前述(31)至(38)中任一項之碳酸酯之製造方法,其中前述有機溶劑係由氯苯、二甲苯及對稱三甲苯中之任1種或2種以上構成。 The method for producing a carbonate according to any one of the above-mentioned (31), wherein the organic solvent is one or more selected from the group consisting of chlorobenzene, xylene and symmetrical trimethylbenzene.

(40)如前述(31)至(39)中任一項之碳酸酯之製造方法,其在前述第2反應步驟中使用脫水劑。 (40) A method for producing a carbonate according to any one of the above (31) to (39), wherein a dehydrating agent is used in the second reaction step.

(41)如前述(31)至(40)中任一項之碳酸酯之製造方法,其中前述一元醇為甲醇,且該製造方法係製造碳酸二甲酯作為碳酸酯。 The method for producing a carbonate according to any one of the above (31) to (40) wherein the monohydric alcohol is methanol, and the production method is to produce dimethyl carbonate as a carbonate.

(42)如前述(31)至(41)中任一項之碳酸酯之製造方法,其中前述一元醇為乙醇,且該製造方法係製造碳酸二乙酯作為碳酸酯。 The method for producing a carbonate according to any one of the above (31) to (41) wherein the monohydric alcohol is ethanol, and the production method is to produce diethyl carbonate as a carbonate.

(43)一種碳酸酯之製造裝置,用於如前述(31)至(42)中任一項之製造方法,其特徵在於具有:加壓部,其加壓二氧化碳;第1反應部,其在CeO2及ZrO2中任一方或雙方之固體催化劑與苯甲腈存在下,使一元醇與二氧化碳反應而生成碳酸酯與水,在此同時,藉由前述苯甲腈與前述已生成之水的水合反應,使苯甲醯胺生成;第1分離部,其將自該第1反應部排出之碳酸酯、苯甲醯胺、未反應之苯甲腈及前述固體催化劑以烷烴實施溶劑 萃取,之後施行固液分離而分離為:液相之碳酸酯、未反應之苯甲腈及烷烴以及固相之前述固體催化劑及苯甲醯胺;第2分離部,其使前述固液分離後液相之碳酸酯、未反應之苯甲腈及烷烴各自分離;第3分離部,其以親水性溶劑萃取前述固液分離後之固體催化劑及苯甲醯胺,之後施行固液分離而分離為:液相之苯甲醯胺及親水性溶劑以及固相之固體催化劑;第2反應部,其在催化劑存在下且在有機溶劑存在下,將該已分離之苯甲醯胺加熱而使其脫水反應並生成苯甲腈,且,該催化劑係於SiO2、TiO2、CeO2、ZrO2、Al2O3及C中任1種或2種以上之催化劑載體上載持有鉬、鎢、錸、釩及鈮中任1種或2種以上金屬種之金屬氧化物;第4分離部,其將該第2反應部所排出之苯甲腈、未反應之苯甲醯胺及在催化劑載體上載持有金屬氧化物之催化劑予以過濾,而分離出固相之載持有金屬氧化物之催化劑;第5分離部,其使該分離後殘存之苯甲腈、苯甲醯胺、有機溶劑及水各自分離;及輸送部,其將前述已分離之苯甲腈朝前述第1反應部輸送。 (43) A method for producing a carbonate according to any one of the above (31) to (42), characterized by comprising: a pressurizing portion that pressurizes carbon dioxide; and a first reaction portion in which In the presence of a solid catalyst of either or both of CeO 2 and ZrO 2 in the presence of benzonitrile, the monohydric alcohol is reacted with carbon dioxide to form a carbonate and water, and at the same time, the benzonitrile and the previously formed water are used. a hydration reaction to form benzamide; a first separation unit that extracts carbonate, benzoguanamine, unreacted benzonitrile, and the solid catalyst discharged from the first reaction unit by solvent extraction with an alkane, and then Separating into a liquid phase carbonate, an unreacted benzonitrile and an alkane, and a solid phase of the solid catalyst and benzamide; and a second separation unit that separates the liquid phase after the solid-liquid separation The carbonate, the unreacted benzonitrile and the alkane are each separated; and the third separation unit extracts the solid catalyst and the benzamide after the solid-liquid separation by a hydrophilic solvent, and then performs solid-liquid separation to separate into a liquid phase. Benzoylamine and a hydrophilic solvent a solid phase solid catalyst; a second reaction portion which, in the presence of a catalyst and in the presence of an organic solvent, heats the separated benzamide to cause dehydration reaction to form benzonitrile, and the catalyst is based on The catalyst carrier of one or more of SiO 2 , TiO 2 , CeO 2 , ZrO 2 , Al 2 O 3 and C is supported on one or more of molybdenum, tungsten, rhenium, vanadium and niobium. a metal oxide; a fourth separation unit that separates benzonitrile, unreacted benzamide, and a catalyst that carries a metal oxide on a catalyst carrier by the second reaction unit a catalyst for holding a metal oxide in a solid phase; a fifth separation portion that separates benzonitrile, benzamide, an organic solvent, and water remaining after the separation; and a transport portion that separates the foregoing The benzonitrile is transported to the first reaction unit.

如以上說明,若依本發明,則可不使用強烈試劑且可在抑制副產物發生之同時,從吡啶甲醯胺或苯甲醯胺 進行再生為氰吡啶或苯甲腈。 As described above, according to the present invention, it is possible to use no pyridine reagent or benzoguanamine while suppressing the occurrence of by-products without using a strong reagent. Regeneration is carried out as cyanopyridine or benzonitrile.

1‧‧‧第1反應塔 1‧‧‧1st reaction tower

2‧‧‧第1萃取塔 2‧‧‧1st extraction tower

3‧‧‧第1蒸餾塔 3‧‧‧1st distillation tower

4‧‧‧第2萃取塔 4‧‧‧2nd extraction tower

5‧‧‧第2蒸餾塔 5‧‧‧2nd distillation tower

6‧‧‧催化劑再生塔 6‧‧‧ Catalyst Regeneration Tower

7‧‧‧第2反應塔 7‧‧‧2nd reaction tower

8‧‧‧催化劑分離塔 8‧‧‧ Catalyst separation tower

9‧‧‧第3蒸餾塔 9‧‧‧3rd distillation tower

10‧‧‧CO2昇壓鼓風機 10‧‧‧CO 2 booster blower

11‧‧‧CO2 11‧‧‧CO 2

12‧‧‧一元醇 12‧‧‧ monohydric alcohol

13‧‧‧2-氰吡啶、苯甲腈 13‧‧‧2-Cyanopyridine, benzonitrile

14‧‧‧固體催化劑 14‧‧‧Solid catalyst

15‧‧‧反應液 15‧‧‧Reaction solution

16‧‧‧烷烴 16‧‧‧alkanes

17、21‧‧‧萃取液 17, 21‧‧ ‧ extract

18‧‧‧固相物質 18‧‧‧ Solid phase materials

19‧‧‧碳酸酯 19‧‧‧carbonate

20‧‧‧未反應之2-氰吡啶、未反應之苯甲腈 20‧‧‧Unreacted 2-cyanopyridine, unreacted benzonitrile

22‧‧‧用畢之固體催化劑 22‧‧‧Complete solid catalyst

23‧‧‧2-吡啶甲醯胺、苯甲醯胺 23‧‧‧2-pyridinecarboxamide, benzamide

24‧‧‧親水性溶劑 24‧‧‧Hydrophilic solvent

25‧‧‧固體催化劑 25‧‧‧Solid catalyst

26‧‧‧用畢之固體催化劑 26‧‧‧Complete solid catalyst

27‧‧‧有機溶劑 27‧‧‧Organic solvents

28‧‧‧未反應之2-吡啶甲醯胺、未反應之苯甲醯胺 28‧‧‧Unreacted 2-pyridinecarbamamine, unreacted benzamide

29‧‧‧水 29‧‧‧Water

30‧‧‧過濾塔 30‧‧‧Filter tower

31‧‧‧吡啶甲酸甲酯、苯甲酸甲酯 31‧‧‧Methyl pyridinecarboxylate, methyl benzoate

32‧‧‧胺甲酸甲酯 32‧‧‧Methyl methacrylate

33‧‧‧烷烴及未反應之一元醇 33‧‧‧alkanes and unreacted monohydric alcohol

圖1為本發明之碳酸酯製造裝置之一例。 Fig. 1 shows an example of a carbonate production apparatus of the present invention.

圖2為圖表,其顯示圖1之製造裝置之各步驟中的各物質狀態。 Fig. 2 is a graph showing the state of each substance in each step of the manufacturing apparatus of Fig. 1.

圖3為本發明之碳酸酯製造裝置之另一例。 Fig. 3 is another example of the carbonate production apparatus of the present invention.

圖4為圖表,其顯示圖3之製造裝置之各步驟中的各物質狀態。 Fig. 4 is a graph showing the state of each substance in each step of the manufacturing apparatus of Fig. 3.

本發明之實施形態 Embodiment of the present invention

以下,一邊參照圖式一邊就本發明之較佳實施形態予以詳細說明。此外,於本說明書及圖式中,實質上具有相同機能結構之構成要素係藉由賦予相同之元件符號俾省略重複說明。 Hereinafter, preferred embodiments of the present invention will be described in detail with reference to the drawings. In the present specification and the drawings, constituent elements that have substantially the same functional structure are denoted by the same reference numerals, and the repeated description is omitted.

<1. 2-氰吡啶之製造方法> <1. Method for producing 2-cyanopyridine>

本發明中利用2-吡啶甲醯胺之脫水反應的2-氰吡啶製造方法是在載持有鹼性金屬氧化物之催化劑與有機溶劑存在下使2-吡啶甲醯胺進行脫水反應而生成2-氰吡啶。 In the present invention, a 2-cyanopyridine produced by a dehydration reaction of 2-pyridinecarbamamine is produced by dehydrating 2-pyridinecarboxamide in the presence of a catalyst carrying a basic metal oxide and an organic solvent to form 2 - cyanide.

於此,本發明所使用之催化劑是使用會成為鹼性之鹼金屬(K、Li、Na、Rb、Cs)氧化物,載體則可使用一般而言可成為催化劑載體之物質,但經探討各種載體之結果, 明確得知在使用下述催化劑時會格外顯示出高性能,即:載持在SiO2、CeO2、ZrO2及其等之2種以上(例如CeO2-ZrO2等)之物。 Here, the catalyst used in the present invention is an alkali metal (K, Li, Na, Rb, Cs) oxide which is basic, and the carrier can be used as a catalyst carrier in general, but various materials have been studied. As a result of the carrier, it has been found that when the following catalyst is used, it exhibits high performance, that is, it is supported by two or more kinds of SiO 2 , CeO 2 , ZrO 2 and the like (for example, CeO 2 -ZrO 2 , etc.). Things.

這是由於,因2-吡啶甲醯胺內之吡啶環顯示弱鹼性,一旦使用酸性之催化劑,吡啶有可能會吸附於催化劑之活性點而被毒化進而引起活性降低,因此,以具有鹼性性質之金屬氧化物為宜。此外,經本案發明人精心探討之結果,以使用令鹼金屬氧化物高分散地載持於SiO2而成之催化劑尤佳,且鹼金屬氧化物可載持1種或2種以上。 This is because the pyridine ring in the 2-pyridine formamide exhibits a weak basicity. Once an acidic catalyst is used, pyridine may adsorb to the active site of the catalyst and be poisoned to cause a decrease in activity, so that it is alkaline. Metal oxides of the nature are preferred. In addition, as a result of careful study by the inventors of the present invention, it is preferable to use a catalyst in which an alkali metal oxide is highly dispersed and supported on SiO 2 , and the alkali metal oxide may be carried by one type or two or more types.

有關此處所用之載體的製造方法,若於下述舉例言之,以SiO2之一般製造方法而言,可大致分為乾式法與溼式法。乾式法有燃燒法、電弧法等,濕式法則有沉澱法、凝膠法等,無論以任一方法皆可製造出催化劑載體,但若以凝膠法以外之上述方法,則在技術上及經濟上難以成形為球狀,因此,仍以可使二氧化矽熔膠在氣體介質或液體介質中噴霧而容易地成形為球狀之凝膠法為宜。 The method for producing the carrier used herein can be roughly classified into a dry method and a wet method in the general production method of SiO 2 as exemplified below. The dry method includes a combustion method, an arc method, etc., and the wet method includes a precipitation method, a gel method, etc., and the catalyst carrier can be produced by any method. However, if the above method other than the gel method is used, it is technically Since it is economically difficult to form a spherical shape, it is preferable to use a gel method in which the cerium oxide melt can be easily formed into a spherical shape by spraying in a gaseous medium or a liquid medium.

再者,以CeO2之情況而言,可藉由在空氣環境下燒成乙醯丙酮鈰水合物或氫氧化鈰、硫酸鈰、乙酸鈰、硝酸鈰、硝酸鈰銨、碳酸鈰、草酸鈰、過氯酸鈰、磷酸鈰、硬脂酸鈰等各種鈰化合物來調製。此外,使用試劑之氧化鈰時,可直接使用或是在空氣環境下將其乾燥或燒成後作使用。進一步來說,也可從已溶有鈰之溶液沉澱後,藉由進行過濾、乾燥及燒成後作使用。 Further, in the case of CeO 2 , it can be calcined in an air atmosphere to form acetamidine oxime hydrate or barium hydroxide, barium sulfate, barium acetate, barium nitrate, barium ammonium nitrate, barium carbonate, barium oxalate, It is prepared by various hydrazine compounds such as bismuth perchlorate, strontium phosphate, and strontium stearate. In addition, when the cerium oxide of the reagent is used, it can be used as it is or dried or fired in an air environment. Further, it may be used after being precipitated from the solution in which the cerium has been dissolved, followed by filtration, drying, and baking.

另一方面,以ZrO2之情況而言,可藉由在空氣環 境下燒成乙氧基鋯、丁氧基鋯、碳酸鋯、氫氧化鋯、磷酸鋯、乙酸鋯、氯氧化鋯、氧化二硝酸鋯、硫酸鋯等各種鋯化合物來調製。又,使用試劑之氧化鋯時,可直接使用或是於空氣環境下將其乾燥或燒成後作使用。進一步來說,也可從已溶有鋯之溶液沉澱後,藉由進行過濾、乾燥及燒成後作使用。 On the other hand, in the case of ZrO 2 , ethoxy zirconium, zirconium butoxide, zirconium carbonate, zirconium hydroxide, zirconium phosphate, zirconium acetate, zirconium oxychloride, oxidized two can be fired in an air atmosphere. Various zirconium compounds such as zirconium nitrate and zirconium sulfate are prepared. Further, when the zirconia of the reagent is used, it can be used as it is, or dried or fired in an air atmosphere. Further, it may be used after being precipitated from a solution in which zirconium has been dissolved, followed by filtration, drying, and baking.

再者,以CeO2與ZrO2之化合物的情況而言,可在含有鈰與鋯之溶液中添加鹼,藉由共沉澱形成氫氧化物後,將業經過濾及水洗之物置於空氣環境下予以乾燥、燒成以進行調製。又,雖也可藉由將CeO2與ZrO2之粉末互為物理混合並予以燒成來進行調製,但最終調製品之比表面積不會增高,因此仍以容易進行反應之共沉澱法為宜。 Further, in the case of a compound of CeO 2 and ZrO 2 , a base may be added to a solution containing cerium and zirconium, and a hydroxide may be formed by coprecipitation, and then the filtered and washed product is placed in an air atmosphere. Dry and fire to prepare. Further, although the powders of CeO 2 and ZrO 2 can be physically mixed with each other and fired, the specific surface area of the final preparation is not increased, so that the coprecipitation method which is easy to carry out the reaction is suitable. .

藉由此等方法,可獲得由氧化鈰與氧化鋯之化合物(具體來說,諸如CeO2-ZrO2)所構成之固體催化劑載體。另,包含調製氧化鈰所構成之催化劑載體及氧化鋯所構成之催化劑載體的情況在內,調製此等各催化劑載體時之燒成溫度宜選擇可使最終調製品之比表面積提高的溫度,雖然也依起始原料而異,舉例來說以300℃至1100℃為宜。又,就本發明之固體催化劑載體而言,雖然含有上述元素以外在催化劑製程等中混入之不可避免的雜質也無妨,但仍以儘可能不混入雜質為宜。 By such a method, a solid catalyst carrier composed of a compound of cerium oxide and zirconium oxide (specifically, such as CeO 2 -ZrO 2 ) can be obtained. Further, in the case of including a catalyst carrier composed of cerium oxide and a catalyst carrier composed of zirconia, the firing temperature at the time of preparing each of the catalyst carriers is preferably selected such that the specific surface area of the final preparation is increased. It also varies depending on the starting materials, and is preferably, for example, 300 ° C to 1100 ° C. Further, the solid catalyst carrier of the present invention may contain unavoidable impurities which are mixed in a catalyst process or the like other than the above-mentioned elements, but it is preferred that impurities are not mixed as much as possible.

就本發明之催化劑製造法而言,若於下述中舉例,當載體為SiO2時可使用市售之粉末或球狀SiO2,為求可均勻載持活性金屬,需整粒到100mesh(0.15mm)以下,且為去 除水分,宜在空氣中以700℃進行1小時之預備燒成。此外,雖然SiO2包含了各種性狀之物,但表面積越大越可使活性金屬高度分散而使2-氰吡啶之生成量提高,因此較為理想。具體來說,以300m2/g以上之表面積為宜。但調製後之催化劑表面積有時會因為SiO2與活性金屬之相互作用等而僅較SiO2之表面積低。此時,宜令製造後之催化劑表面積在150m2/g以上。活性種之金屬氧化物的載持可藉由初溼含浸(Incipient wetness)法或蒸發乾涸法等之含浸法來進行載持。 In terms of catalyst production method of the present invention, if in the following example, when the carrier is SiO 2 usable time of commercially available spherical powder or SiO 2, for the sake of uniformly supported active metal, sieved to 100 mesh required ( 0.15 mm) or less, and in order to remove moisture, it is preferable to perform preliminary baking in air at 700 ° C for 1 hour. Further, although SiO 2 contains various properties, the larger the surface area, the higher the active metal concentration and the higher the amount of 2-cyanopyridine produced. Specifically, a surface area of 300 m 2 /g or more is preferred. However, the surface area of the catalyst after the preparation is sometimes lower than the surface area of SiO 2 due to the interaction of SiO 2 with the active metal or the like. At this time, it is preferred that the surface area of the catalyst after the production be 150 m 2 /g or more. The carrier of the metal oxide of the active species can be carried by an impregnation method such as an incipient wetness method or an evaporation dry method.

前驅物之金屬鹽僅需為水溶性即可,若為鹼金屬,則可使用諸如碳酸鹽、碳酸氫鹽、氯化物鹽、硝酸鹽、矽酸鹽等各種化合物。使鹼性金屬之前驅物水溶液含浸到載體後,藉由將其乾燥、燒成即可用作催化劑,燒成溫度雖也依所用前驅物而異,但以400~600℃為宜。 The metal salt of the precursor may only be water-soluble, and if it is an alkali metal, various compounds such as carbonate, hydrogencarbonate, chloride salt, nitrate, citrate may be used. After the alkaline metal precursor aqueous solution is impregnated into the carrier, it can be used as a catalyst by drying and baking, and the firing temperature varies depending on the precursor to be used, but it is preferably 400 to 600 °C.

再者,雖然催化劑之載持量僅需適當設定即可,但以全催化劑重量為基準,宜將鹼金屬氧化物之金屬換算載持量設定在0.1~1.5mmol/g程度,特別是0.1~1mmol/g程度。載持量若多於此量,活性有降低之虞。又,就反應時之催化劑使用量而言,也是適當設定即可。 In addition, although the catalyst loading amount only needs to be appropriately set, it is preferable to set the metal conversion amount of the alkali metal oxide to 0.1 to 1.5 mmol/g, especially 0.1 to the total catalyst weight. 1mmol/g degree. If the amount of the carrier is more than this amount, the activity is lowered. Further, the amount of the catalyst used in the reaction may be appropriately set.

進一步來說,本發明之催化劑雖是由在SiO2、CeO2、ZrO2中任1種或2種以上構成之載體上僅載持1種或2種以上之鹼金屬氧化物而成的催化劑所構成,但除了上述元素以外,包含在催化劑製程等中混入之不可避免的雜質亦無妨。但仍以儘可能不混入雜質為宜。 Further, the catalyst of the present invention is a catalyst obtained by supporting only one or two or more kinds of alkali metal oxides on a carrier composed of one or more of SiO 2 , CeO 2 and ZrO 2 . In addition to the above elements, it is also possible to include unavoidable impurities mixed in a catalyst process or the like. However, it is advisable to avoid impurities as much as possible.

於此,在載體上載持有將成為本發明之活性種的金屬氧化物之催化劑可為粉體或成型體中之任一形態,為成型體時,可為球狀、丸狀、圓柱狀、環狀、輪狀、顆粒狀等之任一者。 Here, the catalyst in which the metal oxide to be an active species of the present invention is supported on the carrier may be either a powder or a molded body, and in the case of a molded body, it may be spherical, pellet, or columnar. Any of a ring shape, a wheel shape, a pellet shape, and the like.

其次,本發明之使用催化劑的2-氰吡啶製造方法就反應形式而言並未特別受限,可使用批式反應器、半批式反應器以及連續槽型反應器或管型反應器等之流通式反應器中之任一者。此外,催化劑可應用固定床及漿態床等中之任一者。 Further, the method for producing 2-cyanopyridine using the catalyst of the present invention is not particularly limited in terms of the reaction form, and a batch reactor, a semi-batch reactor, a continuous tank reactor or a tubular reactor may be used. Any of the flow-through reactors. Further, the catalyst may be applied to any of a fixed bed and a slurry bed.

本發明之製造方法宜一邊去除脫水反應所生成之副產物之水一邊進行,舉例來說,宜在系統內部設置回流或蒸餾、沸石等之脫水劑而一邊去除副產物之水一邊進行反應。經本案發明人精心研討之結果,可由下述方式提高2-氰吡啶之生成量:使用索氏萃取管及冷卻器,在萃取管內設置沸石(分子篩)或氫化鈣作為脫水劑,於反應管中裝入催化劑、2-吡啶甲醯胺及有機溶劑後,使其回流並在常壓下反應。 The production method of the present invention is preferably carried out while removing water as a by-product produced by the dehydration reaction. For example, it is preferred to carry out a reaction while refluxing or distilling a dehydrating agent such as zeolite in the system while removing water of by-products. As a result of careful study by the inventors of the present invention, the amount of 2-cyanopyridine can be increased by using a Soxhlet extraction tube and a cooler, and a zeolite (molecular sieve) or calcium hydride is provided as a dehydrating agent in the extraction tube. After charging the catalyst, 2-pyridinecarboxamide and an organic solvent, it is refluxed and reacted under normal pressure.

有機溶劑以沸點為130℃以上之物質為佳,可舉例如氯苯、(鄰、間、對)二甲苯及對稱三甲苯等。 The organic solvent preferably has a boiling point of 130 ° C or higher, and examples thereof include chlorobenzene, (o-, m-, p-) xylene, and symmetrical trimethylbenzene.

反應條件宜在脫水反應速度與溶劑沸點、以及反應時所發生之CO2排出量及經濟性等之觀點下作選擇。 The reaction conditions are preferably selected from the viewpoints of the dehydration reaction rate and the boiling point of the solvent, and the amount of CO 2 emission and economy which occur during the reaction.

本發明之2-氰吡啶製造方法中,可將160~200℃之反應溫度、常壓之壓力、數小時~500小時之時間作為一般反應條件並在此條件下進行,但並不受此等條件所侷 限。 In the method for producing 2-cyanopyridine of the present invention, the reaction temperature of 160 to 200 ° C, the pressure of normal pressure, and the time of several hours to 500 hours can be used as general reaction conditions and under these conditions, but are not subject to such conditions. Condition bureau limit.

又,用作脫水劑之分子篩之種類、形狀並未特別受限,但舉例來說,可使用3A、4A、5A等一般吸水性較高且為球狀或丸狀之物。此外,宜在事前預先使其乾燥,且以在300~500℃下乾燥1小時左右為佳。 Further, the type and shape of the molecular sieve used as the dehydrating agent are not particularly limited, and for example, 3A, 4A, 5A or the like which is generally water-absorbent and spherical or pellet-shaped can be used. Further, it is preferred to dry it beforehand and preferably to dry at 300 to 500 ° C for about 1 hour.

2-吡啶甲醯胺之脫水反應係如上述,雖可想見會因2-吡啶甲醯胺之分解而副生成吡啶甲酸或吡啶,但本發明在使用催化劑之脫水反應後,僅有反應物之微量殘留的2-吡啶甲醯胺、生成物之2-氰吡啶及副產物之水、有機溶劑,而幾乎不會生成如上述般之副產物。 The dehydration reaction of 2-pyridinecarbamamine is as described above, although it is conceivable that pyridylcarboxylic acid or pyridine is formed by decomposition of 2-pyridinecarbamide, but the present invention has only a reactant after dehydration reaction using a catalyst. A small amount of residual 2-pyridylcarbamide, a product of 2-cyanopyridine and a by-product of water, an organic solvent, and almost no by-products as described above.

使用索氏萃取管及冷卻器回流時,將反應管周邊加熱到160~200℃。各物質之熔點為110℃(2-吡啶甲醯胺)、24℃(2-氰吡啶)、-45℃(有機溶劑,例如對稱三甲苯),此外,沸點為143℃(2-吡啶甲醯胺)、212℃(2-氰吡啶)、100℃(水)、165℃(有機溶劑,例如對稱三甲苯),因此,反應相除了催化劑為固體之外全部成為液體,一部分已氣化之2-吡啶甲醯胺、副產物之水、有機溶劑則在冷卻器中冷卻,副產物之水被脫水劑吸附,2-吡啶甲醯胺及有機溶劑則回到反應管而再次貢獻反應。 When using a Soxhlet extraction tube and a cooler to reflow, the periphery of the reaction tube is heated to 160 to 200 °C. The melting point of each substance is 110 ° C (2-pyridinecarbendazim), 24 ° C (2-cyanopyridine), -45 ° C (organic solvent, such as symmetrical trimethylbenzene), in addition, the boiling point is 143 ° C (2-pyridine formazan) Amine), 212 ° C (2-cyanopyridine), 100 ° C (water), 165 ° C (organic solvent, such as symmetrical trimethylbenzene), therefore, the reaction phase is all liquid except the catalyst is solid, part of which has been vaporized 2 - The pyridine carbenamide, the water of the by-product, and the organic solvent are cooled in a cooler, the water of the by-product is adsorbed by the dehydrating agent, and the 2-pyridine formamide and the organic solvent are returned to the reaction tube to contribute again.

反應後存在於系統內之各物質沸點係如上述般各自不同,因此可藉由蒸餾而輕易分離。又,由於催化劑 為固體,反應後可依需要加以分離、回收,且以通常之過濾等固液分離方法即可輕易回收。 The boiling points of the substances present in the system after the reaction are different as described above, and thus can be easily separated by distillation. Again, due to the catalyst It is a solid, and after the reaction, it can be separated and recovered as needed, and can be easily recovered by a solid-liquid separation method such as usual filtration.

<2. 3-氰吡啶及4-氰吡啶之製造方法> <2. Method for producing 3-cyanopyridine and 4-cyanopyridine>

將2-氰吡啶之起始物質即2-吡啶甲醯胺變更為菸鹼醯胺、異菸鹼醯胺並進行相同之處理,可藉此合成出3-氰吡啶及4-氰吡啶。 3-cyanopyridine and 4-cyanopyridine can be synthesized by changing 2-pyridine carbamide, which is a starting material of 2-cyanopyridine, to nicotinamide and isonicotinium amide and performing the same treatment.

<3. 苯甲腈之製造方法> <3. Method for producing benzonitrile>

苯甲腈之製造方法係以與氰吡啶製造方法相同之步驟構成。具體來說則如下所述。 The method for producing benzonitrile is constituted by the same steps as the method for producing cyanide. Specifically, it is as follows.

本發明之利用苯甲醯胺脫水反應之苯甲腈製造方法係在載持有鹼性金屬氧化物之催化劑與有機溶劑存在下使苯甲醯胺脫水反應來生成苯甲腈。 The benzonitrile production method using the benzamide dehydration reaction of the present invention dehydrates benzamide to form benzonitrile in the presence of a catalyst carrying a basic metal oxide and an organic solvent.

於此,本發明所使用之催化劑是使用會成為鹼性之鹼金屬(Mo、W、Re、Ti、Nb)氧化物,載體則可使用一般而言可成為催化劑載體之物質,但經探討各種載體之結果,明確得知使用下述催化劑時會格外顯示出高性能,即:在SiO2、TiO2、CeO2、ZrO2、Al2O3、C及其等中之2種以上的催化劑載體上,載持有活性金屬種之氧化物的催化劑。 Here, the catalyst used in the present invention is an alkali metal (Mo, W, Re, Ti, Nb) oxide which becomes alkaline, and the carrier can be used as a catalyst carrier in general, but various materials have been studied. As a result of the carrier, it was found that high performance is exhibited when the following catalyst is used, that is, two or more kinds of catalysts of SiO 2 , TiO 2 , CeO 2 , ZrO 2 , Al 2 O 3 , C, and the like. On the support, a catalyst carrying an oxide of the active metal species is carried.

這是由於一旦使用酸性之催化劑,催化劑之活性 點可能會吸附苯環而被毒化,進而引起活性降低,因此,以具有鹼性性質之金屬氧化物為宜。此外,經本案發明人精心探討之結果,得知於SiO2、TiO2、CeO2、ZrO2、Al2O3、及C之中,若使用SiO2、TiO2、CeO2、ZrO2中之1種或2種以上催化劑載體,則可顯示更高之性能,更為理想。這是因為,可以想見在與苯甲醯胺之反應中,金屬與氧之間的雙鍵部分有可能顯示出活性,因此以在金屬氧化物之中具有雙鍵之金屬元素為宜。更進一步而言,尤宜使用令上述金屬氧化物(特別是鉬)高分散在SiO2上而成之催化劑,金屬氧化物則可載持1種或2種以上。茲就金屬氧化物之製造方法說明於下。 This is because once an acidic catalyst is used, the active point of the catalyst may adsorb the benzene ring and be poisoned, thereby causing a decrease in activity. Therefore, it is preferred to use a metal oxide having a basic property. Further, as a result of intensive investigation by the inventors of the present invention, it is found that among SiO 2 , TiO 2 , CeO 2 , ZrO 2 , Al 2 O 3 , and C, SiO 2 , TiO 2 , CeO 2 , and ZrO 2 are used. One or two or more kinds of catalyst carriers can exhibit higher performance, and are more desirable. This is because it is conceivable that in the reaction with benzamide, the double bond portion between the metal and oxygen may exhibit activity, and therefore it is preferable to use a metal element having a double bond among the metal oxides. Furthermore, it is preferable to use a catalyst in which the metal oxide (particularly molybdenum) is highly dispersed on SiO 2 , and the metal oxide may be carried by one type or two or more types. The manufacturing method of the metal oxide is described below.

以SiO2之一般製造方法而言,可大致分為乾式法與溼式法。乾式法有燃燒法、電弧法等,濕式法則有沉澱法、凝膠法等,無論以任一方法皆可製造出催化劑載體,但若以凝膠法以外之上述方法,則在技術上及經濟上難以成形為球狀,因此,仍以可使二氧化矽熔膠在氣體介質或液體介質中噴霧而容易地成形為球狀之凝膠法為宜。 In the general production method of SiO 2 , it can be roughly classified into a dry method and a wet method. The dry method includes a combustion method, an arc method, etc., and the wet method includes a precipitation method, a gel method, etc., and the catalyst carrier can be produced by any method. However, if the above method other than the gel method is used, it is technically Since it is economically difficult to form a spherical shape, it is preferable to use a gel method in which the cerium oxide melt can be easily formed into a spherical shape by spraying in a gaseous medium or a liquid medium.

再者,以CeO2之情況而言,可藉由在空氣環境下燒成乙醯丙酮鈰水合物或氫氧化鈰、硫酸鈰、乙酸鈰、硝酸鈰、硝酸鈰銨、碳酸鈰、草酸鈰、過氯酸鈰、磷酸鈰、硬脂酸鈰等各種鈰化合物來調製。此外,使用試劑之氧化鈰時,可直接使用或是在空氣環境下將其乾燥或燒成後作使用。進一步來說,也可從已溶有鈰之溶液沉澱後,藉由進行過濾、乾燥及燒成後作使用。 Further, in the case of CeO 2 , it can be calcined in an air atmosphere to form acetamidine oxime hydrate or barium hydroxide, barium sulfate, barium acetate, barium nitrate, barium ammonium nitrate, barium carbonate, barium oxalate, It is prepared by various hydrazine compounds such as bismuth perchlorate, strontium phosphate, and strontium stearate. In addition, when the cerium oxide of the reagent is used, it can be used as it is or dried or fired in an air environment. Further, it may be used after being precipitated from the solution in which the cerium has been dissolved, followed by filtration, drying, and baking.

以ZrO2之情況而言,可藉由在空氣環境下燒成乙氧基鋯、丁氧基鋯、碳酸鋯、氫氧化鋯、磷酸鋯、乙酸鋯、氯氧化鋯、氧化二硝酸鋯、硫酸鋯等各種鋯化合物來調製。又,使用試劑之氧化鋯時,可直接使用或是於空氣環境下將其乾燥或燒成後作使用。進一步來說,也可從已溶有鋯之溶液沉澱後,藉由進行過濾、乾燥及燒成後作使用。 In the case of ZrO 2 , ethoxy zirconium, zirconium zirconate, zirconium carbonate, zirconium hydroxide, zirconium phosphate, zirconium acetate, zirconium oxychloride, zirconium oxynitrate, sulfuric acid can be fired in an air atmosphere. It is prepared by various zirconium compounds such as zirconium. Further, when the zirconia of the reagent is used, it can be used as it is, or dried or fired in an air atmosphere. Further, it may be used after being precipitated from a solution in which zirconium has been dissolved, followed by filtration, drying, and baking.

又,以TiO2或Al2O3的情況而言,可使用一般方法予以製造。C是以碳作為主體者,只要在本反應期間中不發生變質,呈任何形態皆可,舉例來說以活性碳等為宜,但並不限於此。 Further, in the case of TiO 2 or Al 2 O 3 , it can be produced by a general method. C is a carbon-based one, and it may be in any form as long as it does not deteriorate during the reaction period. For example, activated carbon or the like is preferable, but it is not limited thereto.

以含有2種以上金屬種之化合物的情況而言,可在含有2種以上金屬鹽之溶液中添加鹼,藉由共沉澱形成氫氧化物後,使業經過濾及水洗之物於空氣環境下乾燥、燒成來進行調製。此外,雖也可將2種以上之氧化物粉末互為物理混合並燒成來進行調製,但最終調製品之比表面積不會增高,因此仍以易進行反應之共沉澱法為宜。 In the case of a compound containing two or more kinds of metal species, a base may be added to a solution containing two or more metal salts, and a hydroxide may be formed by coprecipitation, and then the filtered and washed product may be dried in an air atmosphere. And firing to prepare. Further, although two or more kinds of oxide powders may be physically mixed and calcined to prepare each other, the specific surface area of the final preparation is not increased, so that a coprecipitation method which is easy to carry out the reaction is preferable.

舉例來說,在CeO2與ZrO2之化合物的情況下,可在含有鈰與鋯之溶液中添加鹼,藉由共沉澱形成氫氧化物後,將業經過濾、水洗之物置於空氣環境下乾燥、燒成以進行調製。 For example, in the case of a compound of CeO 2 and ZrO 2 , a base may be added to a solution containing cerium and zirconium, and after the hydroxide is formed by coprecipitation, the filtered and washed product is dried in an air atmosphere. , firing to make modulation.

藉由此等方法,可獲得由氧化鈰與氧化鋯之化合物(諸如CeO2-ZrO2)構成之固體催化劑載體。另,包含調製氧化鈰所構成之催化劑載體及氧化鋯所構成之催化劑載體的情況在內,調製此等各催化劑載體時之燒成溫度宜選擇 可使最終調製品之比表面積提高的溫度,雖然也依起始原料而異,舉例來說以300℃至1100℃為宜。又,就本發明之固體催化劑載體而言,雖然除了上述元素以外另含有在催化劑製程等中混入之不可避免的雜質也無妨,但仍以儘可能不混入雜質為宜。 By such a method, a solid catalyst carrier composed of a compound of cerium oxide and zirconium oxide such as CeO 2 -ZrO 2 can be obtained. Further, in the case of including a catalyst carrier composed of cerium oxide and a catalyst carrier composed of zirconia, the firing temperature at the time of preparing each of the catalyst carriers is preferably selected such that the specific surface area of the final preparation is increased. It also varies depending on the starting materials, and is preferably, for example, 300 ° C to 1100 ° C. Further, the solid catalyst carrier of the present invention may contain an unavoidable impurity mixed in a catalyst process or the like in addition to the above-mentioned elements, but it is preferable to avoid impurities as much as possible.

選自SiO2、TiO2、CeO2、ZrO2、Al2O3及C中任1種或2種以上之載體的表面積越大,越可高分散地載持活性金屬種而使苯甲腈之生成量提升,因而較為理想。具體來說,雖然表面積也會因載體之種類而異,但表面積以BET法測定宜在10m2/g以上。至於是否呈現高分散,可藉由電子顯微鏡(SEM、TEM等)等之影像來確認。 The larger the surface area of the carrier selected from one or more of SiO 2 , TiO 2 , CeO 2 , ZrO 2 , Al 2 O 3 and C, the higher the dispersion of the active metal species and the benzonitrile The increase in the amount of production is therefore ideal. Specifically, although the surface area varies depending on the type of the carrier, the surface area is preferably 10 m 2 /g or more as measured by the BET method. Whether or not high dispersion is exhibited can be confirmed by an image such as an electron microscope (SEM, TEM, etc.).

本發明催化劑之製造僅需以習知方法使將成為活性種之金屬氧化物載持於載體上即可。例如,可藉由初溼含浸(Incipient wetness)法或蒸發乾涸法等之含浸法來進行載持。 The production of the catalyst of the present invention requires only a metal oxide to be an active species to be supported on a carrier by a conventional method. For example, it can be carried by an impregnation method such as an incipient wetness method or an evaporation dry method.

若於下述中舉例,當載體為SiO2時可使用市售之粉末或球狀SiO2,為求可均勻載持活性金屬,需整粒到100mesh(0.15mm)以下,且為去除水分,宜在空氣中以700℃進行1小時之預備燒成。此外,雖然SiO2包含了各種性狀之物,但表面積越大越可使活性金屬高度分散進而使苯甲腈生成量提高,因此較為理想。具體來說,以300m2/g以上(BET法)之表面積為宜。但調製後之催化劑表面積有時會因為SiO2與活性金屬之相互作用等而僅較SiO2之表面積低。此時,宜令製造後之催化劑表面積在150m2/g以上(BET 法)。 As exemplified in the following, when the carrier is SiO 2 , a commercially available powder or spherical SiO 2 may be used. In order to uniformly carry the active metal, it is necessary to granulate to 100 mesh (0.15 mm) or less, and to remove moisture, It is preferred to carry out preliminary calcination at 700 ° C for 1 hour in the air. Further, although SiO 2 contains various properties, the larger the surface area, the higher the active metal can be dispersed and the amount of benzonitrile produced is increased. Specifically, a surface area of 300 m 2 /g or more (BET method) is preferred. However, the surface area of the catalyst after the preparation is sometimes lower than the surface area of SiO 2 due to the interaction of SiO 2 with the active metal or the like. At this time, it is preferred that the surface area of the catalyst after the production be 150 m 2 /g or more (BET method).

將成為活性種之金屬氧化物的前驅物之金屬鹽僅需為水溶性即可,可使用諸如碳酸鹽、碳酸氫鹽、氯化物鹽、硝酸鹽、矽酸鹽等各種化合物。使鹼性金屬之前驅物水溶液含浸到載體後,藉由將其乾燥、燒成即可用作催化劑,燒成溫度雖也依所用前驅物而異,但以400~600℃為宜。 The metal salt of the precursor of the metal oxide to be an active species need only be water-soluble, and various compounds such as carbonate, hydrogencarbonate, chloride salt, nitrate, and citrate can be used. After the alkaline metal precursor aqueous solution is impregnated into the carrier, it can be used as a catalyst by drying and baking, and the firing temperature varies depending on the precursor to be used, but it is preferably 400 to 600 °C.

此外,雖然金屬氧化物之載持量僅需適當設定即可,但舉例來說,以全催化劑重量為基準,宜使金屬氧化物之金屬換算載持量設定在0.1~1.5mmol/g程度,特別是0.1~1mmol/g程度,更宜0.2~0.8mmol/g程度。載持量若多於此量,則有金屬氧化物粗大化致使活性降低之虞。又,就反應時之催化劑使用量而言,也是適當設定即可。 In addition, although the amount of the metal oxide supported is only required to be appropriately set, for example, the metal conversion amount of the metal oxide is preferably set to be 0.1 to 1.5 mmol/g based on the total catalyst weight. In particular, it is about 0.1 to 1 mmol/g, more preferably about 0.2 to 0.8 mmol/g. When the amount of the support is more than this amount, there is a possibility that the metal oxide is coarsened to lower the activity. Further, the amount of the catalyst used in the reaction may be appropriately set.

進一步來說,本發明之催化劑雖是由在SiO2、TiO2、CeO2、ZrO2、Al2O3、C中任1種或2種以上構成之載體上僅載持1種或2種以上金屬氧化物而成的催化劑所構成,但除了上述元素以外,包含在催化劑製程等中混入之不可避免的雜質亦無妨。但仍以儘可能不混入雜質為宜。在一般情況下,雜質以小於催化劑全體之1質量%為宜。 Furthermore, the catalyst of the present invention contains only one or two kinds of carriers which are composed of one or two or more of SiO 2 , TiO 2 , CeO 2 , ZrO 2 , Al 2 O 3 and C. The catalyst composed of the above metal oxide may contain, in addition to the above-mentioned elements, impurities which are inevitably mixed in a catalyst process or the like. However, it is advisable to avoid impurities as much as possible. In general, the impurities are preferably less than 1% by mass of the entire catalyst.

於此,在載體上載持有將成為本發明之活性種之金屬氧化物的催化劑可為粉體或成型體中之任一形態,為成型體時,可為球狀、丸狀、圓柱狀、環狀、輪狀、顆粒狀等之任一者。 Here, the catalyst in which the metal oxide to be an active species of the present invention is supported on the carrier may be either a powder or a molded body, and in the case of a molded body, it may be spherical, pellet, or columnar. Any of a ring shape, a wheel shape, a pellet shape, and the like.

其次,本發明之使用催化劑的苯甲腈製造方法就 反應形式而言並未特別受限,可使用批式反應器、半批式反應器以及連續槽型反應器或管型反應器等之流通式反應器中之任一者。此外,催化劑可應用固定床及漿態床等中之任一者。 Next, the benzonitrile production method using the catalyst of the present invention is The reaction form is not particularly limited, and any of a batch reactor, a semi-batch reactor, and a flow reactor such as a continuous tank reactor or a tubular reactor may be used. Further, the catalyst may be applied to any of a fixed bed and a slurry bed.

有機溶劑以沸點為130℃以上之物質為佳,可舉例如氯苯、(鄰、間、對)二甲苯、對稱三甲苯、糠醛及十七烷等,但以氯苯、(鄰、間、對)二甲苯、對稱三甲苯為宜。 The organic solvent preferably has a boiling point of 130 ° C or higher, and examples thereof include chlorobenzene, (o-, m-, p-) xylene, symmetrical trimethylbenzene, furfural, and heptadecane, but chlorobenzene, (o-, m-, P-xylene and symmetrical trimethylbenzene are preferred.

反應條件宜在脫水反應速度與溶劑沸點、以及反應時所發生之CO2排出量及經濟性等之觀點下作選擇。 The reaction conditions are preferably selected from the viewpoints of the dehydration reaction rate and the boiling point of the solvent, and the amount of CO 2 emission and economy which occur during the reaction.

本發明之苯甲腈製造方法中,可將160~200℃之反應溫度、常壓之壓力、數小時~24小時之時間視為一般反應條件並在此條件下進行,但並不受此等條件所侷限。 In the method for producing benzonitrile of the present invention, the reaction temperature of 160 to 200 ° C, the pressure of normal pressure, and the time of several hours to 24 hours can be regarded as general reaction conditions and carried out under such conditions, but are not subject to such conditions. Conditions are limited.

在本發明之製造方法中,為了使反應長時間進行,宜一邊去除脫水反應所生成之副產物水一邊進行,例如,宜將沸石等之脫水劑設置於系統內,一邊去除副產物水一邊進行反應。經本案發明人精心探討之結果,得知可藉由使用索氏萃取管及冷卻器並在萃取管內設置沸石(分子篩)或氫化鈣作為脫水劑,於反應管內裝入催化劑、苯甲醯胺及有機溶劑後使其回流並於常壓下反應,而使苯甲腈生成量提升。 In the production method of the present invention, in order to carry out the reaction for a long period of time, it is preferred to remove the by-product water produced by the dehydration reaction. For example, it is preferred to carry out the dehydration agent such as zeolite in the system while removing the by-product water. reaction. As a result of careful study by the inventors of the present invention, it was found that the catalyst, benzamidine can be charged into the reaction tube by using a Soxhlet extraction tube and a cooler and disposing zeolite (molecular sieve) or calcium hydride as a dehydrating agent in the extraction tube. The amine and the organic solvent are refluxed and reacted under normal pressure to increase the amount of benzonitrile produced.

又,用作脫水劑之分子篩之種類、形狀並未特別受限,但舉例來說,可使用3A、4A、5A等一般吸水性較高且為球狀或丸狀之物。此外,宜在事前預先使其乾燥,且以在300~500℃下乾燥1小時左右為佳。 Further, the type and shape of the molecular sieve used as the dehydrating agent are not particularly limited, and for example, 3A, 4A, 5A or the like which is generally water-absorbent and spherical or pellet-shaped can be used. Further, it is preferred to dry it beforehand and preferably to dry at 300 to 500 ° C for about 1 hour.

苯甲醯胺之脫水反應係如上述,雖可想見會因苯甲醯胺之分解而副生成苯甲酸,但本發明使用催化劑之脫水反應後,僅餘反應物之微量殘留的苯甲醯胺、生成物之苯甲腈、副產物之水及有機溶劑,幾乎不會生成上述之副產物。又,即便生成了副產物亦僅為極少量,可藉蒸餾操作使其分離,而可使用在醫藥用途上。 The dehydration reaction of benzamidine is as described above, although it is conceivable that benzoic acid is formed by the decomposition of benzamide, but after the dehydration reaction of the catalyst of the present invention, only a small amount of residual benzamidine remains. The amine, the benzonitrile of the product, the water of the by-product, and the organic solvent hardly produce the by-products described above. Further, even if a by-product is formed, it is only a very small amount, and it can be separated by a distillation operation, and can be used for medical use.

使用索氏萃取管及冷卻器回流時,反應溫度宜為可使苯甲醯胺之脫水反應在液相下進行之條件。若慮及反應效率,則在液相條件下以更高溫為宜,在常壓下進行反應時,宜將反應管周邊加熱到160~200℃。在典型例之反應系統中,各物質之熔點為127℃(苯甲醯胺)、-13℃(苯甲腈)、-45℃(有機溶劑,例如對稱三甲苯),此外,沸點為288℃(苯甲醯胺)、188℃(苯甲腈)、100℃(水)、165℃(有機溶劑,例如對稱三甲苯),因此,若為上述溫度,反應相除了催化劑為固體之外幾乎全部成為液體,一部分已氣化之苯甲醯胺、副產物之水、有機溶劑則在冷卻器中冷卻,副產物之水被脫水劑吸附,苯甲醯胺及有機溶劑回到反應管而再次貢獻反應。 When refluxing using a Soxhlet extraction tube and a cooler, the reaction temperature is preferably a condition in which the dehydration reaction of benzamide is carried out in the liquid phase. When considering the reaction efficiency, it is preferable to use a higher temperature under liquid phase conditions, and when the reaction is carried out under normal pressure, the periphery of the reaction tube should be heated to 160 to 200 °C. In a typical reaction system, the melting point of each substance is 127 ° C (benzamide), -13 ° C (benzonitrile), -45 ° C (organic solvent, such as symmetrical trimethylbenzene), in addition, the boiling point is 288 ° C (benzamide), 188 ° C (benzonitrile), 100 ° C (water), 165 ° C (organic solvent, such as symmetrical trimethylbenzene), therefore, if the temperature is above, the reaction phase is almost all except the catalyst is solid As a liquid, a part of the vaporized benzamide, the by-product water, and the organic solvent are cooled in a cooler, the by-product water is adsorbed by the dehydrating agent, and the benzamide and the organic solvent are returned to the reaction tube to contribute again. reaction.

反應後存在於系統內之各物質沸點係如上述般各自不同,因此可藉由蒸餾而輕易分離。又,由於催化劑 為固體,反應後可依需要加以分離、回收,且以通常之過濾等固液分離方法即可輕易回收。 The boiling points of the substances present in the system after the reaction are different as described above, and thus can be easily separated by distillation. Again, due to the catalyst It is a solid, and after the reaction, it can be separated and recovered as needed, and can be easily recovered by a solid-liquid separation method such as usual filtration.

<4. 使用2-氰吡啶之碳酸酯製造方法> <4. Method for producing carbonate using 2-cyanopyridine>

如上所述,本案發明人已成功想出一種由2-吡啶甲醯胺進行再生為2-氰吡啶的方法,其無需使用強烈試劑且可同時一併抑制副產物之發生。而後,本案發明人更藉由將此一知識見解應用在碳酸酯之製造方法上而進一步思及下述說明之碳酸酯製造方法。 As described above, the inventors of the present invention have succeeded in conceiving a method of regenerating 2-cyanopyridine from 2-pyridinecarbendamine, which does not require the use of a strong reagent and can simultaneously suppress the occurrence of by-products. Then, the inventors of the present invention further conceived the carbonate production method described below by applying this knowledge knowledge to the method for producing a carbonate.

(第1反應步驟) (first reaction step)

本發明之碳酸酯製造方法中,第1反應步驟是在CeO2及ZrO2中任一方或雙方之固體催化劑與2-氰吡啶存在下,使一元醇與二氧化碳直接反應而生成碳酸酯之步驟。 In the method for producing a carbonate according to the present invention, the first reaction step is a step of directly reacting a monohydric alcohol with carbon dioxide in the presence of a solid catalyst of either or both of CeO 2 and ZrO 2 and 2-cyanopyridine to form a carbonate.

於本步驟中,一旦使一元醇與二氧化碳反應,除了碳酸酯之外,另外也會生成水,但藉由使2-氰吡啶存在並利用其與所生成之水之水合反應來生成2-吡啶甲醯胺,再從反應系統中去除或減少已生成之水,藉此即可促進碳酸酯之生成。 In this step, once the monohydric alcohol is reacted with carbon dioxide, water is additionally formed in addition to the carbonate, but 2-pyridine is formed by the presence of 2-cyanopyridine and hydration with the produced water. The formamide, which removes or reduces the water that has formed from the reaction system, thereby promoting the formation of carbonate.

(一元醇) (monohydric alcohol)

於此,一元醇可使用選自第一級醇、第二級醇及第三級醇中一種或二種以上之任一醇類,但使用甲醇、乙醇、1-丙醇、異丙醇、1-丁醇、1-戊醇、1-已醇、1-庚醇、1-辛醇、1-壬醇、烯丙醇、2-甲基-1-丙醇、環己甲醇、苄基醇時,生成物之產率較高且反應速度也快,較為理想。此時,所生成之碳酸酯分別為碳酸二甲酯、碳酸二乙酯、碳酸二丙酯、碳酸二異丙酯、碳酸二丁酯、碳酸二戊酯、碳酸二己酯、碳酸二庚酯、碳酸二辛酯、碳酸二壬酯、碳酸二烯丙酯、碳酸二2-甲基-丙酯、碳酸二環己甲酯、碳酸二苄酯。 Here, the monohydric alcohol may be one or more selected from the group consisting of a first alcohol, a second alcohol, and a third alcohol, but using methanol, ethanol, 1-propanol, isopropanol, 1-butanol, 1-pentanol, 1-hexanol, 1-heptanol, 1-octanol, 1-nonanol, allyl alcohol, 2-methyl-1-propanol, cyclohexylmethanol, benzyl In the case of an alcohol, the yield of the product is high and the reaction rate is also fast, which is preferable. At this time, the carbonates formed are respectively dimethyl carbonate, diethyl carbonate, dipropyl carbonate, diisopropyl carbonate, dibutyl carbonate, diamyl carbonate, dihexyl carbonate, diheptyl carbonate. , dioctyl carbonate, dinonyl carbonate, diallyl carbonate, di-2-methyl-propyl carbonate, dicyclohexyl carbonate, dibenzyl carbonate.

(碳酸酯製造用催化劑) (catalyst for carbonate production)

此外,CeO2及ZrO2中任一方或雙方之固體催化劑係指僅CeO2、僅ZrO2、CeO2與ZrO2之混合物或者CeO2與ZrO2之固溶體或複合氧化物,尤以僅CeO2為宜。此外,CeO2與ZrO2之固溶體或複合氧化物之CeO2與ZrO2混合比係以50:50為基本,但混合比可適當變更。 Further, either one of CeO 2 and ZrO 2 or both of the solid catalyst refers only CeO 2, ZrO 2 only, a mixture of CeO 2 and ZrO 2 or CeO 2 solid solution or a composite oxide of ZrO 2, especially only CeO 2 is preferred. Further, the mixing ratio of CeO 2 to ZrO 2 of the solid solution of CuO 2 and ZrO 2 or the composite oxide is 50:50, but the mixing ratio can be appropriately changed.

經本案發明人精心探究之結果,用於直接合成碳酸酯之催化劑必須具有酸鹼複合機能,且以具有酸性度相對較低且鹼性度相對較高之性質為佳。若酸性度過高,與其說是合成碳酸酯,毋寧是變成多量合成醚類,並不理想。就具有適度酸鹼複合機能之催化劑而言,可想見具有如下機制:醇類以R-O-M(M為催化劑)之形式解離吸附於鹼性點上而與CO2之間形成RO-C(=O)-O...M,另一方面,醇類以HO-R...M之形式吸附於酸性點上,而在兩吸附種之間生成RO-C(=O)-OR。 As a result of intensive investigation by the inventors of the present invention, the catalyst for direct synthesis of carbonate must have an acid-base composite function, and it is preferable to have a property of relatively low acidity and relatively high basicity. If the acidity is too high, it is not so much a synthetic carbonate, but it is a lot of synthetic ethers. In the case of a catalyst having a moderate acid-base complex function, it is conceivable to have a mechanism in which the alcohol is dissociated and adsorbed on the basic point in the form of ROM (M is a catalyst) to form RO-C (CO) with CO 2 . )-O...M, on the other hand, the alcohol is adsorbed to the acid sites in the form of HO-R...M, and RO-C(=O)-OR is formed between the two adsorbed species.

此外,該固體催化劑對於合成碳酸酯時所副生成之水與2-氰吡啶的水合反應也會顯示出催化劑活性。因此,本催化劑表面上雖會成為碳酸酯合成反應與水合反應兩者並進之狀態,即便在以反應平衡而言不利於碳酸酯合成反應之低壓條件下,2-氰吡啶之水合反應仍會受到催化劑作用而進行,而使碳酸酯合成反應所副生成之水迅速脫離催化劑表面,進而使碳酸酯合成反應之平衡朝向生成系統偏移,推測碳酸酯合成反應是如此而可在低反應壓力之溫和條件下仍不受平衡制約而獲得碳酸酯之高度反應率。反過來說,可想見的是,在高壓下催化劑表面會吸附多量CO2分子,在合成碳酸酯時難以與生成之水分子接觸,因此,其與2-氰吡啶間之水合反應變得不易進行,僅能在接***衡制約之狀態下生產碳酸酯,結果則是高壓下生產性不會提高。 Further, the solid catalyst also exhibits catalyst activity for the hydration reaction of water produced by the by-product of the synthesis of the carbonate with 2-cyanopyridine. Therefore, although the surface of the catalyst becomes a state in which both the carbonate synthesis reaction and the hydration reaction proceed together, the hydration reaction of 2-cyanopyridine is still subjected to low pressure conditions which are disadvantageous to the carbonate synthesis reaction in terms of reaction equilibrium. The catalyst acts to cause the water formed by the carbonate synthesis reaction to rapidly desorb from the catalyst surface, thereby shifting the balance of the carbonate synthesis reaction toward the generation system, and it is presumed that the carbonate synthesis reaction is so low and the reaction pressure is mild. Under the conditions, the high reaction rate of the carbonate is obtained without being restricted by the balance. Conversely, it is conceivable that a large amount of CO 2 molecules are adsorbed on the surface of the catalyst under high pressure, and it is difficult to contact the generated water molecules when synthesizing the carbonate, so that the hydration reaction with 2-cyanopyridine becomes difficult. When it is carried out, carbonate can be produced only in a state close to equilibrium, and as a result, productivity is not improved under high pressure.

有關上述推測,若從2-氰吡啶之反應的觀點來說明,則推測如下:2-氰吡啶在液相下會受到本發明固體催化劑之催化劑作用而使水合反應在其表面受到促進。因此,一旦成為高壓,固體催化劑表面會被CO2所包覆而成為與主反應所生成之水分子間之水合反應不易受到催化劑作用的狀態,因此水合反應速度降低。另一方面,非專利文獻4、非專利文獻5所記載之縮醛或2,2-二甲氧基丙烷在液相下完全不受催化劑作用,而與主反應生成之水分子引起水合反應。因此,主反應在高壓下會優先進行,故而推測水合反應是在高壓下開始。 The above speculation is explained from the viewpoint of the reaction of 2-cyanopyridine, and it is presumed that 2-cyanopyridine is subjected to the action of the catalyst of the solid catalyst of the present invention in the liquid phase to promote the hydration reaction on the surface thereof. Therefore, when the pressure is high, the surface of the solid catalyst is coated with CO 2 and the hydration reaction between the water molecules generated by the main reaction is less likely to be affected by the catalyst, so that the hydration reaction rate is lowered. On the other hand, the acetal or 2,2-dimethoxypropane described in Non-Patent Document 4 and Non-Patent Document 5 is completely free from the action of the catalyst in the liquid phase, and causes hydration reaction with the water molecules formed by the main reaction. Therefore, the main reaction is preferentially carried out under high pressure, so it is presumed that the hydration reaction starts under high pressure.

此外,就本發明之催化劑製造法而言,若於下述舉例來說,首先,以CeO2之情況而言,可藉由在空氣環境下燒成乙醯丙酮鈰水合物或氫氧化鈰、硫酸鈰、乙酸鈰、硝酸鈰、硝酸鈰銨、碳酸鈰、草酸鈰、過氯酸鈰、磷酸鈰、硬脂酸鈰等各種鈰化合物來調製。此外,使用試劑之氧化鈰時,可直接使用或是在空氣環境下將其乾燥或燒成後作使用。進一步來說,也可從已溶有鈰之溶液沉澱後,藉由進行過濾、乾燥及燒成後作使用。 Further, in the case of the catalyst production method of the present invention, as exemplified below, first, in the case of CeO 2 , acetonitrile acetone ruthenium hydrate or cesium hydroxide can be obtained by firing in an air atmosphere. It is prepared by various hydrazine compounds such as barium sulfate, barium acetate, barium nitrate, barium ammonium nitrate, barium carbonate, barium oxalate, barium perchlorate, barium phosphate, barium stearate. In addition, when the cerium oxide of the reagent is used, it can be used as it is or dried or fired in an air environment. Further, it may be used after being precipitated from the solution in which the cerium has been dissolved, followed by filtration, drying, and baking.

另一方面,以氧化鋯(ZrO2)之情況而言,可藉由在空氣環境下燒成乙氧基鋯、丁氧基鋯、碳酸鋯、氫氧化鋯、磷酸鋯、乙酸鋯、氯氧化鋯、氧化二硝酸鋯、硫酸鋯等各種鋯化合物來調製。又,使用試劑之氧化鋯時,可直接使用或是於空氣環境下將其乾燥或燒成後作使用。進一步來說,也可從已溶有鋯之溶液沉澱後,藉由進行過濾、乾燥及燒成後作使用。 On the other hand, in the case of zirconium oxide (ZrO 2 ), it can be calcined by zirconium ethoxide, zirconium butoxide, zirconium carbonate, zirconium hydroxide, zirconium phosphate, zirconium acetate, chlorine chloride by air. Various zirconium compounds such as zirconium, zirconium dinitrate, and zirconium sulfate are prepared. Further, when the zirconia of the reagent is used, it can be used as it is, or dried or fired in an air atmosphere. Further, it may be used after being precipitated from a solution in which zirconium has been dissolved, followed by filtration, drying, and baking.

再者,以CeO2與ZrO2之固溶體或複合氧化物般之化合物的情況而言,可在含有鈰與鋯之溶液中添加鹼,藉由共沉澱形成氫氧化物後,將業經過濾及水洗之物置於空氣環境下予以乾燥、燒成以進行調製。又,雖也可藉由將CeO2與ZrO2之粉末互為物理混合並予以燒成來進行調製,但最終調製品之比表面積不會增高,因此仍以容易進行反應之共沉澱法為宜。 Further, in the case of a solid solution of CeO 2 and ZrO 2 or a compound of a composite oxide, a base may be added to a solution containing cerium and zirconium, and a hydroxide may be formed by coprecipitation, and then filtered. The water-washed material is dried and fired in an air environment to prepare. Further, although the powders of CeO 2 and ZrO 2 can be physically mixed with each other and fired, the specific surface area of the final preparation is not increased, so that the coprecipitation method which is easy to carry out the reaction is suitable. .

藉由此等方法,可獲得由氧化鈰與氧化鋯之化合物(具體來說,諸如CeO2-ZrO2)構成之固體催化劑載體。另, 包含調製氧化鈰所構成之催化劑載體及氧化鋯所構成之催化劑載體的情況在內,調製此等各催化劑載體時之燒成溫度宜選擇可使最終調製品之比表面積提高的溫度,雖然也依起始原料而異,舉例來說以300℃至1100℃為宜。又,就本發明之固體催化劑載體而言,雖然含有上述元素以外之在催化劑製程等中混入之不可避免的雜質也無妨,但仍以儘可能不混入雜質為宜。 By such a method, a solid catalyst carrier composed of a compound of cerium oxide and zirconium oxide (specifically, such as CeO 2 -ZrO 2 ) can be obtained. Further, in the case of including a catalyst carrier composed of cerium oxide and a catalyst carrier composed of zirconia, the firing temperature at the time of preparing each of the catalyst carriers is preferably selected such that the specific surface area of the final preparation is increased. It also varies depending on the starting materials, and is preferably, for example, 300 ° C to 1100 ° C. Further, the solid catalyst carrier of the present invention may contain unavoidable impurities which are mixed in a catalyst process or the like other than the above-mentioned elements, but it is preferred that impurities are not mixed as much as possible.

於此,本發明之催化劑可為粉體或成型體中之任一形態,為成型體時,可為球狀、丸狀、圓柱狀、環狀、輪狀及顆粒狀等中之任一者。 Here, the catalyst of the present invention may be in any form of a powder or a molded body, and in the case of a molded body, it may be any of a spherical shape, a pellet shape, a cylindrical shape, a ring shape, a wheel shape, and a granular shape. .

(二氧化碳) (carbon dioxide)

此外,本發明所使用之二氧化碳不僅可使用調製作為工業氣體之物,也可使用從源自製造各種製品之工廠或製鐵廠、發電廠等的廢氣予以分離回收之物。 Further, the carbon dioxide used in the present invention can be used not only as an industrial gas but also as a product which is separated and recovered from an exhaust gas from a factory for manufacturing various products, a steel plant, a power plant or the like.

(固液分離) (solid-liquid separation)

在一元醇之轉化率為100%且不生成吡啶甲酸甲酯或胺甲酸甲酯般之副產物的條件下,反應後會變成主產物之碳酸酯、副產物之2-吡啶甲醯胺、未反應之2-氰吡啶及CeO2等之固體催化劑。為了使其等分離,首先,以利用有機溶劑之萃取步驟來萃取液體成分(碳酸酯、2-氰吡啶),即可以固定成分(2-吡啶甲醯胺與固定催化劑)與過濾器來分離。於此,使用之有機溶劑以可溶解碳酸酯之烷烴為宜,己烷、辛烷、壬烷、癸烷及十一烷更佳。 Under the condition that the conversion of the monohydric alcohol is 100% and the by-product such as methyl picolinate or methyl carbamate is not formed, the reaction will become the carbonate of the main product, the 2-pyridine formamide of the by-product, and the A solid catalyst such as 2-cyanopyridine or CeO 2 is reacted. In order to separate the same, first, the liquid component (carbonate, 2-cyanopyridine) is extracted by an extraction step using an organic solvent, that is, the component (2-pyridinecarboxamide and a fixed catalyst) can be separated from the filter. Here, the organic solvent to be used is preferably a carbonate-soluble alkane, and more preferably hexane, octane, decane, decane or undecane.

(液體成分之分離) (separation of liquid components)

接著,雖然所分離出之液體成分包含了碳酸酯、2-氰吡啶及有機溶劑,但各物質之熔點及沸點以碳酸酯而言有4℃及90℃(碳酸二甲酯)、-43℃及128℃(碳酸二乙酯)、-41℃及167℃(碳酸二丙酯)、25℃以下及207℃(碳酸二丁酯)等,此外還有24℃及215℃(2-氰吡啶)、-95℃及69℃(例如己烷),因此,可藉蒸餾來分離碳酸酯,並可以高純度來回收製品之碳酸酯。此外,除了蒸餾之外,也可將階段性冷卻至熔點以下而固化之物以過濾器分離並回收。 Next, although the separated liquid component contains carbonate, 2-cyanopyridine, and an organic solvent, the melting point and boiling point of each substance are 4 ° C and 90 ° C (dimethyl carbonate), -43 ° C in terms of carbonate. And 128 ° C (diethyl carbonate), -41 ° C and 167 ° C (dipropyl carbonate), below 25 ° C and 207 ° C (dibutyl carbonate), in addition to 24 ° C and 215 ° C (2-cyanide ), -95 ° C and 69 ° C (for example, hexane), therefore, the carbonate can be separated by distillation, and the carbonate of the product can be recovered in high purity. Further, in addition to the distillation, the solidified matter may be cooled and cooled to a temperature below the melting point to be separated and recovered by a filter.

(固體成分之分離) (separation of solid components)

再者,作為固體成分而被分離出之2-吡啶甲醯胺與固體催化劑可利用親水性溶劑而僅將2-吡啶甲醯胺萃取出再以固體催化劑與過濾器來分離。於此,考慮到處置之容易度及後續階段之分離,所使用之親水性溶劑宜為丙酮、乙醇、醚類及水。溶於親水性溶劑之2-吡啶甲醯胺可藉蒸餾來分離,且可以高純度地純化副生成之2-吡啶甲醯胺。 Further, the 2-pyridinecarboxamide which is separated as a solid component and the solid catalyst can be extracted only by 2-hydroxyformamide using a hydrophilic solvent, and then separated by a solid catalyst and a filter. Here, in view of ease of handling and separation in subsequent stages, the hydrophilic solvent to be used is preferably acetone, ethanol, ethers and water. The 2-pyridinecarbendamine dissolved in a hydrophilic solvent can be separated by distillation, and the by-produced 2-pyridinecarboxamide can be purified in high purity.

(已分離之固體催化劑之再生處理) (Regeneration treatment of separated solid catalyst)

已分離出之固體催化劑可在再生催化劑之步驟中作再生處理並再次利用於第1反應步驟中。催化劑再生步驟為一施行加熱以將固體催化劑上之雜質等燒除的步驟,其係以400~700℃(宜500~600℃)燒成3小時程度。為了防止急遽昇溫引起固體催化劑之結構破壞,燒成前宜先實施乾燥步驟,且以110℃下使其燒成2小時程度為佳。 The separated solid catalyst can be regenerated in the step of regenerating the catalyst and reused in the first reaction step. The catalyst regeneration step is a step of heating to burn off impurities or the like on the solid catalyst, which is baked at 400 to 700 ° C (preferably 500 to 600 ° C) for 3 hours. In order to prevent structural damage of the solid catalyst caused by rapid temperature rise, it is preferred to carry out the drying step before firing and to heat it at 110 ° C for 2 hours.

(殘留成分) (residual component)

此外,未反應之一元醇殘留時,或者,反應溫度達130 ℃以上之高溫或是反應時間達24小時以上之長時間而生成了吡啶甲酸甲酯或胺甲酸甲酯般之副產物時,熔點及沸點以一元醇而言分別有-97℃及65℃(甲醇)、-114℃及78℃(乙醇)、-126℃及97℃(1-丙醇)、-90℃及117℃(1-丁醇)等,又有103℃及233℃(吡啶甲酸甲酯)、52℃及177℃(胺甲酸甲酯),因此,可在前述蒸餾中階段性地升溫到180℃程度,藉此分離出一元醇、有機溶劑、碳酸酯及胺甲酸甲酯與吡啶甲酸甲酯及2-氰吡啶,之後冷卻到30~100℃,藉此以過濾器過濾已固化之吡啶甲酸甲酯,即可與2-氰吡啶分離。 In addition, when one of the unreacted alcohol remains, or the reaction temperature reaches 130 When the high temperature above °C or the reaction time is longer than 24 hours to produce a by-product such as methyl picolinate or methyl carbamate, the melting point and boiling point are -97 ° C and 65 ° C for monohydric alcohol, respectively. Methanol), -114 ° C and 78 ° C (ethanol), -126 ° C and 97 ° C (1-propanol), -90 ° C and 117 ° C (1-butanol), etc., and 103 ° C and 233 ° C (picolinic acid Methyl ester), 52 ° C and 177 ° C (methyl carbamate), therefore, can be gradually increased to 180 ° C in the above distillation, thereby separating monohydric alcohol, organic solvent, carbonate and methyl carbamate Methyl picolinate and 2-cyanopyridine are then cooled to 30-100 ° C, whereby the solidified methyl picolinate is filtered through a filter to be separated from 2-cyanopyridine.

一元醇及有機溶劑大半都是有機溶劑,因此可藉由有機溶劑下之萃取步驟予以再利用。然而,副產物越少,分離到系統外之後的處理步驟越不耗工夫而較理想。 Most of the monohydric alcohol and the organic solvent are organic solvents, and thus can be reused by an extraction step under an organic solvent. However, the less the by-products, the less the processing steps after separation into the system are less laborious.

(第2反應步驟) (second reaction step)

其次,於本發明之第2反應步驟中,使第1反應步驟所副生成之2-吡啶甲醯胺從碳酸酯生成反應後之系統分離,之後藉由脫水反應來製造2-氰吡啶。第2反應步驟相當於上述2-氰吡啶之製造方法。 Next, in the second reaction step of the present invention, 2-pyridinecarbendamine which is produced by the first reaction step is separated from the system after the carbonate formation reaction, and then 2-cyanopyridine is produced by a dehydration reaction. The second reaction step corresponds to the above-described method for producing 2-cyanopyridine.

該2-氰吡啶之製造過程係在載持有鹼性金屬氧化物之催化劑與有機溶劑存在下,使2-吡啶甲醯胺進行脫水反應來生成2-氰吡啶。 The 2-cyanopyridine is produced by subjecting 2-pyridinecarboxamide to a dehydration reaction in the presence of a catalyst carrying a basic metal oxide and an organic solvent to form 2-cyanopyridine.

於此,本發明所使用之催化劑是使用會成為鹼性之鹼金屬(K、Li、Na、Rb、Cs)的氧化物,載體則可使用一般而言可成為催化劑載體之物質,但經探討各種載體之結果,明確得知在使用下述催化劑時會格外顯示出高性能,即:載持在SiO2、CeO2、ZrO2及其等之2種以上(例如CeO2-ZrO2等)之物。 Here, the catalyst used in the present invention is an oxide which is an alkali metal (K, Li, Na, Rb, Cs) which is basic, and the carrier can be used as a catalyst carrier in general, but it has been discussed. As a result of the various carriers, it is clear that high performance is exhibited when the following catalysts are used, that is, two or more kinds of SiO 2 , CeO 2 , ZrO 2 , and the like (for example, CeO 2 -ZrO 2 , etc.) are supported. Things.

這是由於,因2-吡啶甲醯胺內之吡啶環顯示弱鹼性,一旦使用酸性之催化劑,催化劑之活性點有可能會吸附吡啶而被毒化,進而引起活性降低,因此,以具有鹼性性質之金屬為宜。此外,經本案發明人精心探討之結果,以使用令鹼金屬氧化物高分散地載持於SiO2而成之催化劑尤佳,且鹼金屬氧化物可載持1種或2種以上。 This is because the pyridine ring in the 2-pyridine formamide exhibits a weak basicity. When an acidic catalyst is used, the active site of the catalyst may adsorb pyridine and be poisoned, thereby causing a decrease in activity, and therefore, it is alkaline. The metal of nature is suitable. In addition, as a result of careful study by the inventors of the present invention, it is preferable to use a catalyst in which an alkali metal oxide is highly dispersed and supported on SiO 2 , and the alkali metal oxide may be carried by one type or two or more types.

有關此處所用之載體的製造方法,若於下述舉例言之,以SiO2之一般製造方法而言,可大致分為乾式法與溼式法。乾式法有燃燒法、電弧法等,濕式法則有沉澱法、凝膠法等,無論以任一方法皆可製造出催化劑載體,但若以凝膠法以外之上述方法,則在技術上及經濟上難以成形為球狀,因此,仍以可使二氧化矽熔膠在氣體介質或液體介質中噴霧而容易地成形為球狀之凝膠法為宜。 The method for producing the carrier used herein can be roughly classified into a dry method and a wet method in the general production method of SiO 2 as exemplified below. The dry method includes a combustion method, an arc method, etc., and the wet method includes a precipitation method, a gel method, etc., and the catalyst carrier can be produced by any method. However, if the above method other than the gel method is used, it is technically Since it is economically difficult to form a spherical shape, it is preferable to use a gel method in which the cerium oxide melt can be easily formed into a spherical shape by spraying in a gaseous medium or a liquid medium.

再者,以CeO2之情況而言,可藉由在空氣環境下燒成乙醯丙酮鈰水合物或氫氧化鈰、硫酸鈰、乙酸鈰、硝酸鈰、硝酸鈰銨、碳酸鈰、草酸鈰、過氯酸鈰、磷酸鈰、硬脂酸鈰等各種鈰化合物來調製。此外,使用試劑之氧化鈰時,可直接使用或是在空氣環境下將其乾燥或燒成後作 使用。進一步來說,也可從已溶有鈰之溶液沉澱後,藉由進行過濾、乾燥及燒成後作使用。 Further, in the case of CeO 2 , it can be calcined in an air atmosphere to form acetamidine oxime hydrate or barium hydroxide, barium sulfate, barium acetate, barium nitrate, barium ammonium nitrate, barium carbonate, barium oxalate, It is prepared by various hydrazine compounds such as bismuth perchlorate, strontium phosphate, and strontium stearate. In addition, when the cerium oxide of the reagent is used, it can be used as it is or dried or fired in an air environment. Further, it may be used after being precipitated from the solution in which the cerium has been dissolved, followed by filtration, drying, and baking.

另一方面,以ZrO2之情況而言,可藉由在空氣環境下燒成乙氧基鋯、丁氧基鋯、碳酸鋯、氫氧化鋯、磷酸鋯、乙酸鋯、氯氧化鋯、氧化二硝酸鋯、硫酸鋯等各種鋯化合物來調製。又,使用試劑之氧化鋯時,可直接使用或是於空氣環境下將其乾燥或燒成後作使用。進一步來說,也可從已溶有鋯之溶液沉澱後,藉由進行過濾、乾燥及燒成後作使用。 On the other hand, in the case of ZrO 2 , ethoxy zirconium, zirconium butoxide, zirconium carbonate, zirconium hydroxide, zirconium phosphate, zirconium acetate, zirconium oxychloride, oxidized two can be fired in an air atmosphere. Various zirconium compounds such as zirconium nitrate and zirconium sulfate are prepared. Further, when the zirconia of the reagent is used, it can be used as it is, or dried or fired in an air atmosphere. Further, it may be used after being precipitated from a solution in which zirconium has been dissolved, followed by filtration, drying, and baking.

再者,以CeO2與ZrO2之化合物的情況而言,可在含有鈰與鋯之溶液中添加鹼,藉由共沉澱形成氫氧化物後,將業經過濾及水洗之物置於空氣環境下予以乾燥、燒成以進行調製。又,雖也可藉由將CeO2與ZrO2之粉末互為物理混合並予以燒成來進行調製,但最終調製品之比表面積不會增高,因此仍以容易進行反應之共沉澱法為宜。 Further, in the case of a compound of CeO 2 and ZrO 2 , a base may be added to a solution containing cerium and zirconium, and a hydroxide may be formed by coprecipitation, and then the filtered and washed product is placed in an air atmosphere. Dry and fire to prepare. Further, although the powders of CeO 2 and ZrO 2 can be physically mixed with each other and fired, the specific surface area of the final preparation is not increased, so that the coprecipitation method which is easy to carry out the reaction is suitable. .

藉由此等方法,可獲得由氧化鈰與氧化鋯之化合物(具體來說,諸如CeO2-ZrO2)所構成之固體催化劑載體。另,包含調製氧化鈰所構成之催化劑載體及氧化鋯所構成之催化劑載體的情況在內,調製此等各催化劑載體時之燒成溫度宜選擇可使最終調製品之比表面積提高的溫度,雖然也依起始原料而異,舉例來說以300℃至1100℃為宜。又,就本發明之固體催化劑載體而言,雖然含有上述元素以外在催化劑製程等中混入之不可避免的雜質也無妨,但仍以儘可能不混入雜質為宜。 By such a method, a solid catalyst carrier composed of a compound of cerium oxide and zirconium oxide (specifically, such as CeO 2 -ZrO 2 ) can be obtained. Further, in the case of including a catalyst carrier composed of cerium oxide and a catalyst carrier composed of zirconia, the firing temperature at the time of preparing each of the catalyst carriers is preferably selected such that the specific surface area of the final preparation is increased. It also varies depending on the starting materials, and is preferably, for example, 300 ° C to 1100 ° C. Further, the solid catalyst carrier of the present invention may contain unavoidable impurities which are mixed in a catalyst process or the like other than the above-mentioned elements, but it is preferred that impurities are not mixed as much as possible.

就本發明之催化劑製造法而言,若於下述中舉例,當載體為SiO2時可使用市售之粉末或球狀SiO2,為求可均勻載持活性金屬,需整粒到100mesh(0.15mm)以下,且為去除水分,宜在空氣中以700℃進行1小時之預備燒成。此外,雖然SiO2包含了各種性狀之物,但表面積越大越可使活性金屬高度分散而使2-氰吡啶之生成量提高,因此較為理想。具體來說,以300m2/g以上之表面積為宜。但調製後之催化劑表面積有時會因為SiO2與活性金屬之相互作用等而僅較SiO2之表面積低。此時,宜令製造後之催化劑表面積在150m2/g以上。活性種之金屬氧化物的載持可藉由初溼含浸(Incipient wetness)法或蒸發乾涸法等之含浸法來進行載持。 In terms of catalyst production method of the present invention, if in the following example, when the carrier is SiO 2 usable time of commercially available spherical powder or SiO 2, for the sake of uniformly supported active metal, sieved to 100 mesh required ( 0.15 mm) or less, and in order to remove moisture, it is preferable to perform preliminary baking in air at 700 ° C for 1 hour. Further, although SiO 2 contains various properties, the larger the surface area, the higher the active metal concentration and the higher the amount of 2-cyanopyridine produced. Specifically, a surface area of 300 m 2 /g or more is preferred. However, the surface area of the catalyst after the preparation is sometimes lower than the surface area of SiO 2 due to the interaction of SiO 2 with the active metal or the like. At this time, it is preferred that the surface area of the catalyst after the production be 150 m 2 /g or more. The carrier of the metal oxide of the active species can be carried by an impregnation method such as an incipient wetness method or an evaporation dry method.

前驅物之金屬鹽僅需為水溶性即可,若為鹼金屬,則可使用諸如碳酸鹽、碳酸氫鹽、氯化物鹽、硝酸鹽、矽酸鹽等各種化合物。使鹼性金屬之前驅物水溶液含浸到載體後,藉由將其乾燥、燒成即可用作催化劑,燒成溫度雖也依所用前驅物而異,但以400~600℃為宜。 The metal salt of the precursor may only be water-soluble, and if it is an alkali metal, various compounds such as carbonate, hydrogencarbonate, chloride salt, nitrate, citrate may be used. After the alkaline metal precursor aqueous solution is impregnated into the carrier, it can be used as a catalyst by drying and baking, and the firing temperature varies depending on the precursor to be used, but it is preferably 400 to 600 °C.

又,就本發明之催化劑而言,雖然除了上述元素以外還包含在催化劑製程等中混入之不可避免的雜質也無妨,但仍以儘可能不混入雜質為宜。 Further, the catalyst of the present invention may contain unavoidable impurities mixed in a catalyst process or the like in addition to the above-mentioned elements, but it is preferable to prevent impurities from being mixed as much as possible.

於此,本發明之載持於載體上的催化劑可為粉體或成型體中之任一形態,為成型體時,可為球狀、丸狀、圓柱狀、環狀、輪狀、顆粒狀等之任一者。 Herein, the catalyst supported on the carrier of the present invention may be in any form of a powder or a molded body, and in the case of a molded body, it may be in the form of a sphere, a pellet, a cylinder, a ring, a wheel, or a pellet. Any of them.

(反應形式) (reaction form)

其次,本發明之使用催化劑的2-氰吡啶製造方法就反應形式而言並未特別受限,可使用批式反應器、半批式反應器以及連續槽型反應器或管型反應器等之流通式反應器中之任一者。此外,催化劑可應用固定床及漿態床等中之任一者。 Further, the method for producing 2-cyanopyridine using the catalyst of the present invention is not particularly limited in terms of the reaction form, and a batch reactor, a semi-batch reactor, a continuous tank reactor or a tubular reactor may be used. Any of the flow-through reactors. Further, the catalyst may be applied to any of a fixed bed and a slurry bed.

(脫水) (dehydration)

即使是在從本發明製造方法所副生成之2-吡啶甲醯胺生成(再生)出2-氰吡啶的第2反應步驟,亦與製造碳酸酯之步驟同樣,宜一邊去除脫水反應所生成之副產物之水一邊進行反應,例如,宜在系統內設置回流或蒸餾、沸石等之脫水劑,一邊去除副產物水一邊進行反應。經本案發明人精心研討之結果,可由下述方式提高2-氰吡啶之生成量:使用索氏萃取管及冷卻器,在萃取管內設置沸石(分子篩)或氫化鈣作為脫水劑並於反應管中裝入催化劑、2-吡啶甲醯胺及有機溶劑後,使其回流並在常壓下反應。 Even in the second reaction step of producing (regenerating) 2-cyanopyridine from the 2-pyridinecarbachamide produced by the production method of the present invention, it is preferable to remove the dehydration reaction as in the step of producing the carbonate. The water of the by-product is reacted. For example, it is preferred to provide a dehydrating agent such as reflux or distillation or zeolite in the system, and carry out the reaction while removing by-product water. As a result of careful study by the inventors of the present invention, the amount of 2-cyanopyridine can be increased by using a Soxhlet extraction tube and a cooler, and a zeolite (molecular sieve) or calcium hydride is provided as a dehydrating agent in the extraction tube and in the reaction tube. After charging the catalyst, 2-pyridinecarboxamide and an organic solvent, it is refluxed and reacted under normal pressure.

(有機溶劑) (Organic solvents)

用於脫水反應之有機溶劑以沸點為130℃以上之物質為宜,可舉例如氯苯、(鄰、間、對)二甲苯及對稱三甲苯等,但以對稱三甲苯尤佳。 The organic solvent used for the dehydration reaction is preferably a material having a boiling point of 130 ° C or higher, and examples thereof include chlorobenzene, (o-, m-, p-) xylene, and symmetrical trimethylbenzene, and the like, but it is preferably symmetrical toluene.

(反應條件) (Reaction conditions)

本發明之使用催化劑的2-氰吡啶製造方法中,反應條件宜在脫水反應速度與溶劑沸點、以及反應時所發生之CO2排出量及經濟性等之觀點下作選擇,例如,可使其在反應溫度160~200℃、壓力常壓及反應時間數小時~500小時之程 度的條件下進行,但並不特別受此等條件所侷限。 In the method for producing 2-cyanopyridine using a catalyst according to the present invention, the reaction conditions are preferably selected from the viewpoints of the dehydration reaction rate and the boiling point of the solvent, and the amount of CO 2 emission and economy which are generated during the reaction, and the like. It is carried out under the conditions of a reaction temperature of 160 to 200 ° C, a pressure normal pressure, and a reaction time of several hours to 500 hours, but is not particularly limited by these conditions.

此外,用作脫水劑之分子篩之種類、形狀並未特別受限,但舉例來說,可使用3A、4A、5A等一般吸水性較高且為球狀或丸狀之物。此外,宜在事前預先使其乾燥,且以在300~500℃下乾燥1小時左右為佳。 Further, the type and shape of the molecular sieve used as the dehydrating agent are not particularly limited, but for example, 3A, 4A, 5A or the like which is generally highly water-absorptive and spherical or pellet-shaped can be used. Further, it is preferred to dry it beforehand and preferably to dry at 300 to 500 ° C for about 1 hour.

(反應生成物) (reaction product)

2-吡啶甲醯胺之脫水反應係如上述,雖可想見會因2-吡啶甲醯胺之分解而副生成吡啶甲酸或吡啶,但本發明在使用催化劑之脫水反應後,僅有反應物之微量殘留的2-吡啶甲醯胺、生成物之2-氰吡啶及副產物之水、有機溶劑,而幾乎不會生成如上述般之副產物。 The dehydration reaction of 2-pyridinecarbamamine is as described above, although it is conceivable that pyridylcarboxylic acid or pyridine is formed by decomposition of 2-pyridinecarbamide, but the present invention has only a reactant after dehydration reaction using a catalyst. A small amount of residual 2-pyridylcarbamide, a product of 2-cyanopyridine and a by-product of water, an organic solvent, and almost no by-products as described above.

使用索氏萃取管及冷卻器回流時,將反應管周邊加熱到160~200℃。各物質之熔點為110℃(2-吡啶甲醯胺)、24℃(2-氰吡啶)、-45℃(有機溶劑,例如對稱三甲苯),此外,沸點為143℃(2-吡啶甲醯胺)、212℃(2-氰吡啶)、100℃(水)、165℃(有機溶劑,例如對稱三甲苯),因此,反應相除了催化劑為固體之外全部成為液體,一部分已氣化之2-吡啶甲醯胺、副產物之水、有機溶劑則在冷卻器中冷卻,副產物之水被脫水劑吸附,2-吡啶甲醯胺及有機溶劑回到反應管而再次貢獻反應。 When using a Soxhlet extraction tube and a cooler to reflow, the periphery of the reaction tube is heated to 160 to 200 °C. The melting point of each substance is 110 ° C (2-pyridinecarbendazim), 24 ° C (2-cyanopyridine), -45 ° C (organic solvent, such as symmetrical trimethylbenzene), in addition, the boiling point is 143 ° C (2-pyridine formazan) Amine), 212 ° C (2-cyanopyridine), 100 ° C (water), 165 ° C (organic solvent, such as symmetrical trimethylbenzene), therefore, the reaction phase is all liquid except the catalyst is solid, part of which has been vaporized 2 The pyridine carbenamide, the water of the by-product, and the organic solvent are cooled in a cooler, the water of the by-product is adsorbed by the dehydrating agent, and the 2-pyridine formamide and the organic solvent are returned to the reaction tube to contribute to the reaction again.

(2-氰吡啶之再利用) (reuse of 2-cyanopyridine)

於第2反應步驟再生之2-氰吡啶可再次利用於第1反應步驟中。 The 2-cyanopyridine regenerated in the second reaction step can be reused in the first reaction step.

<5. 碳酸酯之製造裝置> <5. Carbonate production device>

其次,顯示具體例於下以進一步詳細說明本發明之製造裝置。圖1為本發明之合宜設備的一例。又,將圖1中本設備各步驟中之各物質狀態顯示於圖2。本設備可使用在一元醇轉化率100%且不生成吡啶甲酸甲酯或胺甲酸甲酯之副產物的反應條件情況下。 Next, specific examples will be described below to further explain the manufacturing apparatus of the present invention in further detail. Figure 1 is an illustration of a suitable apparatus of the present invention. Further, the state of each substance in each step of the apparatus of Fig. 1 is shown in Fig. 2. The apparatus can be used under the reaction conditions of a monohydric alcohol conversion of 100% and no by-product of methyl picolinate or methyl carbamate.

(第1反應步驟) (first reaction step)

就第1反應步驟而言,其將CeO2及ZrO2中任一方或雙方之固體催化劑(固相)、一元醇12(液相)、2-氰吡啶13(液相)充填至第1反應塔1(第1反應部)中,且經由昇壓鼓風機10(加壓部)而二氧化碳(氣相)充填至第1反應塔1(第1反應部)中。固體催化劑可於反應前使用新充填或是經再生塔6再生之固體催化劑14(固相)。又,2-氰吡啶於反應開始時使用新品,但可再利用業經第1蒸餾塔3純化之未反應2-氰吡啶20(液相)與經第3蒸餾塔9純化且從2-吡啶甲醯胺再生之2-氰吡啶。 In the first reaction step, a solid catalyst (solid phase) of either or both of CeO 2 and ZrO 2 , a monohydric alcohol 12 (liquid phase), and 2-cyanopyridine 13 (liquid phase) are charged to the first reaction. In the column 1 (first reaction unit), carbon dioxide (gas phase) is charged into the first reaction column 1 (first reaction unit) via the booster blower 10 (pressurizing unit). The solid catalyst can be used as a solid catalyst 14 (solid phase) which is newly filled or regenerated by the regeneration column 6 before the reaction. Further, 2-cyanopyridine is used at the beginning of the reaction, but the unreacted 2-cyanopyridine 20 (liquid phase) purified by the first distillation column 3 can be reused and purified by the third distillation column 9 and from 2-pyridine 2-Cyanopyridine regenerated by indoleamine.

其次,本發明中使用CeO2及ZrO2中任一方或雙方之固體催化劑之碳酸酯的直接合成裝置可使用批式反應器、半批式反應器以及連續槽型反應器或管型反應器等之流通式反應器中之任一者。 Next, in the present invention, a direct synthesis apparatus using a carbonate of a solid catalyst of either or both of CeO 2 and ZrO 2 may be used in a batch reactor, a semi-batch reactor, a continuous tank reactor or a tubular reactor. Any of the flow-through reactors.

(反應溫度) (temperature reflex)

宜令第1反應塔1中之反應溫度為50~300℃。反應溫度 小於50℃時反應速度低落,碳酸酯合成反應及2-氰吡啶之水合反應均幾乎不進行,而有碳酸酯之生產性低落之傾向。又,反應溫度超過150℃時,雖然各反應之反應速度提高,但容易發生碳酸酯之分解或改質,2-吡啶甲醯胺容易與一元醇發生反應,因此碳酸酯之產率有降低之傾向。更宜為100~150℃。但可想見的是此一溫度會依固體催化劑之種類及量以及原料(一元醇、2-氰吡啶)之量及比例而異,宜適當地設定最佳條件。由於較佳之反應溫度為100~150℃,宜在第1反應塔之前段以蒸汽將原料(一元醇、2-氰吡啶)預加熱。 The reaction temperature in the first reaction column 1 should be 50 to 300 °C. temperature reflex When the temperature is lower than 50 ° C, the reaction rate is low, and the carbonate synthesis reaction and the hydration reaction of 2-cyanopyridine are hardly carried out, and the productivity of the carbonate tends to be low. Further, when the reaction temperature exceeds 150 ° C, the reaction rate of each reaction is increased, but decomposition or modification of the carbonate is liable to occur, and 2-pyridine formamide is easily reacted with the monohydric alcohol, so that the yield of the carbonate is lowered. tendency. More preferably 100~150 °C. However, it is conceivable that the temperature varies depending on the type and amount of the solid catalyst and the amount and ratio of the raw materials (monohydric alcohol, 2-cyanopyridine), and the optimum conditions should be appropriately set. Since the preferred reaction temperature is from 100 to 150 ° C, it is preferred to preheat the starting material (monohydric alcohol, 2-cyanopyridine) with steam in the first stage of the first reaction column.

(反應壓力) (reaction pressure)

宜令反應壓力為0.1~5MPa(絕對壓力)。反應壓力小於0.1MPa(絕對壓力)時,減壓裝置變得必要,不僅是設備複雜且成本提高,減壓所需之動能也變得必要而使能量效率變差。此外,反應壓力超過5MPa時,2-氰吡啶之水合反應變得不易進行,不僅是碳酸酯之產率惡化,昇壓所必須之動能也變得必要而使能量效率變差。又,從提高碳酸酯產率之觀點來看,反應壓力宜為0.1~4MPa(絕對壓力),更宜為0.2~2MPa(絕對壓力)。 The reaction pressure should be 0.1~5MPa (absolute pressure). When the reaction pressure is less than 0.1 MPa (absolute pressure), the pressure reducing device becomes necessary, and the equipment is complicated and the cost is increased, and the kinetic energy required for the pressure reduction is also required to deteriorate the energy efficiency. Further, when the reaction pressure exceeds 5 MPa, the hydration reaction of 2-cyanopyridine becomes difficult to proceed, and not only the yield of the carbonate is deteriorated, but also the kinetic energy necessary for the pressure increase becomes necessary, and the energy efficiency is deteriorated. Further, from the viewpoint of improving the yield of the carbonate, the reaction pressure is preferably 0.1 to 4 MPa (absolute pressure), more preferably 0.2 to 2 MPa (absolute pressure).

(2-氰吡啶之用量) (the amount of 2-cyanopyridine)

此外,用於水合反應之2-氰吡啶宜為原料之醇類體積的0.1倍以上且1倍以下,且宜在反應前預先導入反應器中。以小於0.1倍導入時,貢獻給水合反應之2-氰吡啶較少而有使碳酸酯產率惡化之虞。另一方面,以超過1倍導入時,由 於反應結束後容易與生成物分離且可再利用,並無特別問題。此外,可以想見的是,相對於固體催化劑之一元醇及2-氰吡啶之量會視固體催化劑之種類及量、以及一元醇之種類及其與2-氰吡啶之比例而異,宜適當地設定最佳條件。 Further, the 2-cyanopyridine used for the hydration reaction is preferably 0.1 times or more and 1 time or less the volume of the alcohol of the raw material, and is preferably introduced into the reactor before the reaction. When it is introduced at less than 0.1 times, the amount of 2-cyanopyridine contributing to the hydration reaction is small and the yield of the carbonate is deteriorated. On the other hand, when importing more than 1 time, After the reaction is completed, it is easily separated from the product and can be reused without any particular problem. Further, it is conceivable that the amount of one of the alcohol and the amount of 2-cyanopyridine relative to the solid catalyst varies depending on the kind and amount of the solid catalyst, the type of the monohydric alcohol, and the ratio of the 2-cyanopyridine. Set the best conditions.

(反應生成物之分離) (separation of reaction product)

於第1反應塔1反應後之反應液15係在第1萃取塔2(第1分離部)分離為液相與固相。含在反應液15中之物質為碳酸酯(液相)、未反應之2-氰吡啶(液相)與2-吡啶甲醯胺(固相)、固體催化劑(固相),利用有機溶劑(液相)萃取之。於此,所使用之有機溶劑以烷烴為合適,且從後段蒸餾之分離容易度來看,以己烷、辛烷、壬烷、癸烷及十一烷為宜。第1萃取塔2之萃取步驟為了抑制能量消費,萃取時之溫度宜在常溫下進行,但若是較有機溶劑之沸點更低之溫度(例如,以己烷之情況而言,因沸點為69℃,加熱到50℃程度),亦可藉由加熱以使萃取時間縮短。 The reaction liquid 15 after the reaction in the first reaction column 1 is separated into a liquid phase and a solid phase in the first extraction column 2 (first separation unit). The substance contained in the reaction liquid 15 is a carbonate (liquid phase), unreacted 2-cyanopyridine (liquid phase), 2-pyridinecarbamide (solid phase), a solid catalyst (solid phase), and an organic solvent ( Liquid phase) extraction. Here, the organic solvent to be used is suitably an alkane, and hexane, octane, decane, decane, and undecane are preferable from the viewpoint of ease of separation in the latter stage distillation. Extraction step of the first extraction column 2 In order to suppress energy consumption, the temperature at the time of extraction is preferably carried out at normal temperature, but if it is lower than the boiling point of the organic solvent (for example, in the case of hexane, the boiling point is 69 ° C) It is heated to a temperature of 50 ° C. It can also be heated to shorten the extraction time.

在第1萃取塔2萃取出之萃取液17包含碳酸酯、未反應之2-氰吡啶及烷烴。於第1蒸餾塔3(第2分離部)中利用各物質之沸點為90℃(例如碳酸二甲酯)、215℃(2-氰吡啶)、69℃(例如己烷)一事進行蒸餾,而分離為製品之碳酸酯19、未反應之2-氰吡啶20及業經用於萃取之烷烴16。 The extract 17 extracted in the first extraction column 2 contains carbonate, unreacted 2-cyanopyridine, and an alkane. Distillation is carried out in the first distillation column 3 (second separation unit) by using the boiling point of each substance at 90 ° C (for example, dimethyl carbonate), 215 ° C (2-cyanopyridine), and 69 ° C (for example, hexane). The product is separated into a carbonate of the product 19, unreacted 2-cyanopyridine 20 and an alkane 16 which is used for extraction.

另一方面,第1萃取塔2分離出之固相18中包含了2-吡啶甲醯胺與固體催化劑,而在第2萃取塔4(第3分離部)被分離。於此,所使用之溶劑以可溶解2-吡啶甲醯胺之親 水性溶劑(液相)為合適,從後段蒸餾之分離容易度來看,以丙酮、乙醇、醚類及水為宜。第2萃取塔4之萃取步驟也為了抑制能量消費,萃取時之溫度以在常溫下進行為宜,但若是較親水性溶劑之沸點更低的溫度(例如,以丙酮的情況而言,因沸點為56.5℃,加熱到40℃程度),則也可藉由加熱而使萃取時間縮短。 On the other hand, the solid phase 18 separated by the first extraction column 2 contains 2-pyridinecarbamide and a solid catalyst, and is separated in the second extraction column 4 (third separation unit). Here, the solvent used is a pro-soluble 2-pyridinecarbamamine pro The aqueous solvent (liquid phase) is suitable, and acetone, ethanol, ethers and water are preferred from the viewpoint of ease of separation in the latter stage distillation. The extraction step of the second extraction column 4 is also for suppressing energy consumption, and the temperature at the time of extraction is preferably carried out at normal temperature, but if it is a temperature lower than the boiling point of the hydrophilic solvent (for example, in the case of acetone, the boiling point is When the temperature is 56.5 ° C and heated to 40 ° C), the extraction time can also be shortened by heating.

含有2-吡啶甲醯胺與親水性溶劑之萃取液21係於第2蒸餾塔5蒸餾,而按各物質之沸點分離為143℃(2-吡啶甲醯胺)與57℃(例如丙酮)。 The extract 21 containing 2-pyridinecarbendamine and a hydrophilic solvent is distilled in the second distillation column 5, and is separated into 143 ° C (2-pyridinecarbamide) and 57 ° C (for example, acetone) at the boiling points of the respective materials.

此外,於第2萃取塔4分離出之固體催化劑22(固相)可於催化劑再生塔6再生處理而回到第1反應塔1。催化劑再生係一加熱來燒除固體催化劑上之雜質等的步驟,其以400~700℃(宜500~600℃)燒成3小時程度。為了防止急遽昇溫造成固體催化劑之結構破壞,燒成前宜先實施乾燥步驟,且以110℃下乾燥2小時程度為佳。 Further, the solid catalyst 22 (solid phase) separated in the second extraction column 4 can be regenerated in the catalyst regeneration column 6 and returned to the first reaction column 1. The catalyst regeneration is a step of heating to burn off impurities or the like on the solid catalyst, and is baked at 400 to 700 ° C (preferably 500 to 600 ° C) for 3 hours. In order to prevent structural damage of the solid catalyst caused by rapid temperature rise, it is preferred to carry out the drying step before firing and to dry at 110 ° C for 2 hours.

已於第2蒸餾塔5純化之2-吡啶甲醯胺23(固相)為了再生為2-氰吡啶而朝第2反應塔7(第2反應部)輸送,但為了避免在配管內栓塞,配管宜以低壓蒸汽等加熱到熔點之103℃以上。 The 2-pyridinecarboxamide 23 (solid phase) purified in the second distillation column 5 is transported to the second reaction column 7 (second reaction unit) for regeneration to 2-cyanopyridine, but in order to avoid embedding in the pipe, The piping should be heated to a temperature of 103 ° C or higher with low pressure steam or the like.

反應後之溶液於催化劑分離裝置8中以過濾器過濾而僅分離出呈固體之催化劑,可視為用畢之催化劑26而予以回收。此時,可藉一般之過濾等的固液分離方法來輕易回收。催化劑分離後,由於存在於系統內之各物質沸點係如上述般各自相異,可藉由在第3蒸餾塔9施行蒸餾而輕 易分離為2-氰吡啶、有機溶劑、2-吡啶甲醯胺及水,有機溶劑27及2-吡啶甲醯胺28可再循環利用於2-吡啶甲醯胺之脫水反應中。又,已純化之2-氰吡啶13則可在進行製造碳酸酯之反應中再次利用。 The solution after the reaction is filtered in a catalyst separation device 8 by a filter to separate only the solid catalyst, which can be regarded as being recovered by using the catalyst 26. At this time, it can be easily recovered by a solid-liquid separation method such as general filtration. After the separation of the catalyst, since the boiling points of the respective substances present in the system are different as described above, it can be lightly distilled by the third distillation column 9 It is easily separated into 2-cyanopyridine, an organic solvent, 2-pyridinecarboxamide and water, and the organic solvent 27 and 2-pyridinecarbamide 28 can be recycled in the dehydration reaction of 2-pyridinecarbamide. Further, the purified 2-cyanopyridine 13 can be reused in the reaction for producing a carbonate.

(第2反應步驟) (second reaction step)

就第2反應步驟而言,其係以第2反應塔7利用2-吡啶甲醯胺之脫水反應來生成2-氰吡啶。本發明之製造裝置係一在載持有鹼性金屬氧化物之催化劑與有機溶劑之存在下使2-吡啶甲醯胺進行脫水反應而生成2-氰吡啶之裝置。就反應形式而言並未特別受限,可使用批式反應器、半批式反應器以及連續槽型反應器或管型反應器等之流通式反應器中之任一者。此外,催化劑可應用固定床及漿態床等中之任一者。第2反應塔7之溫度可依反應形式來變更,但使用索氏萃取管及冷卻器回流時,宜將反應管周邊加熱到160~200℃。本發明之製造裝置宜一邊去除脫水反應所生成之副產物水一邊進行,舉例來說,宜在系統內部設置回流或蒸餾、沸石等之脫水劑而一邊去除副產物之水一邊進行反應。經本案發明人精心研討之結果,可由下述方式提高2-氰吡啶之生成量:使用索氏萃取管及冷卻器,在萃取管內設置沸石(分子篩)或氫化鈣作為脫水劑,於反應管中裝入催化劑、2-吡啶甲醯胺及有機溶劑後,使其回流並在常壓下反應。有機溶劑以沸點為130℃以上之物質為佳,可舉例如氯苯、(鄰、間、對)二甲苯及對稱三甲苯等。 In the second reaction step, the second reaction column 7 is subjected to a dehydration reaction of 2-pyridinecarbamide to form 2-cyanopyridine. The apparatus for producing a present invention is a device for producing 2-cyanopyridine by subjecting 2-pyridinecarboxamide to a dehydration reaction in the presence of a catalyst carrying an alkali metal oxide and an organic solvent. The reaction form is not particularly limited, and any one of a batch reactor, a semi-batch reactor, and a flow reactor such as a continuous tank reactor or a tubular reactor may be used. Further, the catalyst may be applied to any of a fixed bed and a slurry bed. The temperature of the second reaction column 7 can be changed depending on the reaction form, but when the Soxhlet extraction tube and the cooler are used for reflux, the periphery of the reaction tube should be heated to 160 to 200 °C. The production apparatus of the present invention is preferably carried out while removing the by-product water produced by the dehydration reaction. For example, it is preferred to carry out a reaction while refluxing or distilling a dehydrating agent such as zeolite in the system while removing water of by-products. As a result of careful study by the inventors of the present invention, the amount of 2-cyanopyridine can be increased by using a Soxhlet extraction tube and a cooler, and a zeolite (molecular sieve) or calcium hydride is provided as a dehydrating agent in the extraction tube. After charging the catalyst, 2-pyridinecarboxamide and an organic solvent, it is refluxed and reacted under normal pressure. The organic solvent preferably has a boiling point of 130 ° C or higher, and examples thereof include chlorobenzene, (o-, m-, p-) xylene, and symmetrical trimethylbenzene.

使用索氏萃取管及冷卻器回流時,將反應管周邊 加熱到160~200℃。各物質之熔點為110℃(2-吡啶甲醯胺)、24℃(2-氰吡啶)、-45℃(有機溶劑,例如對稱三甲苯),此外,沸點為143℃(2-吡啶甲醯胺)、212℃(2-氰吡啶)、100℃(水)、165℃(有機溶劑,例如對稱三甲苯),因此,反應相除了催化劑為固體之外全部成為液體,一部分已氣化之2-吡啶甲醯胺、副產物之水、有機溶劑則在冷卻器中冷卻,副產物之水被脫水劑吸附,2-吡啶甲醯胺及有機溶劑回到反應管而再次貢獻反應。 When using a Soxhlet extraction tube and a cooler to recirculate, surround the reaction tube Heat to 160~200 °C. The melting point of each substance is 110 ° C (2-pyridinecarbendazim), 24 ° C (2-cyanopyridine), -45 ° C (organic solvent, such as symmetrical trimethylbenzene), in addition, the boiling point is 143 ° C (2-pyridine formazan) Amine), 212 ° C (2-cyanopyridine), 100 ° C (water), 165 ° C (organic solvent, such as symmetrical trimethylbenzene), therefore, the reaction phase is all liquid except the catalyst is solid, part of which has been vaporized 2 The pyridine carbenamide, the water of the by-product, and the organic solvent are cooled in a cooler, the water of the by-product is adsorbed by the dehydrating agent, and the 2-pyridine formamide and the organic solvent are returned to the reaction tube to contribute to the reaction again.

反應後之溶液係以低壓蒸汽等加熱到2-吡啶甲醯胺熔點之103℃以上後,直接以催化劑分離塔8(第4分離部)僅分離出催化劑,而視為用畢之催化劑26予以回收。此時,可藉一般之過濾等的固液分離方法來輕易回收。催化劑分離後,由於存在於系統內之各物質沸點係如上述般各自相異,可藉由在第3蒸餾塔9(第5分離部)施行蒸餾而輕易分離為2-氰吡啶13、有機溶劑27、2-吡啶甲醯胺28及水29,有機溶劑27及2-吡啶甲醯胺28會回到第3反應塔7之前段而可再循環利用。又,已純化之2-氰吡啶13則以輸送部輸送到進行製造碳酸酯之第1反應塔1,於第1反應塔1中再次利用。 After the reaction, the solution is heated to a temperature of 103 ° C or higher at a melting point of 2-pyridinecarboxamide by a low-pressure steam or the like, and the catalyst is separated directly from the catalyst separation column 8 (fourth separation portion), and is regarded as a catalyst 26 to be used. Recycling. At this time, it can be easily recovered by a solid-liquid separation method such as general filtration. After the separation of the catalyst, the boiling points of the respective substances present in the system are different as described above, and can be easily separated into 2-cyanopyridine 13 and an organic solvent by performing distillation in the third distillation column 9 (the fifth separation unit). 27. 2-Pyridylcarbamide 28 and water 29, organic solvent 27 and 2-pyridinecarbamide 28 are returned to the third stage of the third reaction column 7 for recycling. Further, the purified 2-cyanopyridine 13 is transported to the first reaction column 1 for producing a carbonate by a transport unit, and is reused in the first reaction column 1.

(碳酸酯之製造方法及裝置之其他例) (Other examples of the method and apparatus for producing carbonate)

又,圖3為本發明之合宜設備的另一例,圖4為圖3之設備在各步驟中之各物質狀態。本設備在未反應之一元醇殘留且會生成吡啶甲酸甲酯或胺甲酸甲酯之副產物的反應條件下也可使用。基本結構與前述圖1相同,經第1萃取塔2萃 取之萃取液17除了碳酸酯、未反應之2-氰吡啶、烷烴及一元醇之外,還含有胺甲酸甲酯與吡啶甲酸甲酯。利用各物質之沸點為90℃(例如碳酸二甲酯)、215℃(2-氰吡啶)、69℃(例如己烷)、65℃(例如甲醇)、177℃(胺甲酸甲酯)、233℃(吡啶甲酸甲酯)一事,以第1蒸餾塔3階段性地使溫度上昇到180℃程度藉此進行蒸餾,而分離為製品之碳酸酯19、業經用於萃取之烷烴與未反應之一元醇的混合物33、以及胺甲酸甲酯32。此外,蒸餾後冷卻到30~100℃程度,藉此,熔點為103℃之吡啶甲酸甲酯會固化,可以過濾器30等施行固液分離,而可分離為未反應之2-氰吡啶20及吡啶甲酸甲酯31。又,烷烴與一元醇之混合物33大半為烷烴,因此可作為萃取用溶劑而再次利用。 Further, Fig. 3 is another example of a suitable apparatus of the present invention, and Fig. 4 is a view showing the state of each substance in each step of the apparatus of Fig. 3. The apparatus can also be used under the reaction conditions in which one of the unreacted alcohol remains and a by-product of methyl picolinate or methyl carbamate is formed. The basic structure is the same as that of FIG. 1 described above, and is extracted by the first extraction tower 2 The extract 17 is contained in addition to carbonate, unreacted 2-cyanopyridine, an alkane and a monohydric alcohol, and further contains methyl carbamate and methyl picolinate. The boiling point of each substance is 90 ° C (such as dimethyl carbonate), 215 ° C (2-cyanopyridine), 69 ° C (such as hexane), 65 ° C (such as methanol), 177 ° C (methyl carbamate), 233 °C (methyl pyridinecarboxylate), in the first distillation column 3, the temperature is raised to 180 ° C in stages to carry out distillation, and the carbonate is separated into the product, the alkane used for extraction and the unreacted one element Mixture 33 of alcohol and methyl carbamate 32. Further, after distillation, it is cooled to a temperature of 30 to 100 ° C, whereby methyl pyridinecarboxylate having a melting point of 103 ° C is solidified, and solid-liquid separation can be carried out by a filter 30 or the like, and can be separated into unreacted 2-cyanopyridine 20 and Methyl picolinate 31. Further, since most of the mixture 33 of the alkane and the monohydric alcohol is an alkane, it can be reused as a solvent for extraction.

<6. 使用3-氰吡啶、4-氰吡啶之碳酸酯製造方法及製造裝置> <6. Method and apparatus for producing carbonate using 3-cyanopyridine or 4-cyanopyridine>

於上述碳酸酯之製造方法及製造裝置中,可也使用3-氰吡啶或4-氰吡啶來取代2-氰吡啶。 In the above method and apparatus for producing a carbonate, 3-cyanopyridine or 4-cyanopyridine may be used instead of 2-cyanopyridine.

<7. 使用苯甲腈之碳酸酯製造方法> <7. Method for producing carbonate using benzonitrile>

如上所述,本案發明人已成功想出一種由苯甲醯胺進行再生為苯甲腈的方法,其無需使用強烈試劑且可同時一併抑制副產物之發生。而後,本案發明人更藉由將此一知識見解應用在碳酸酯之製造方法上而進一步思及下述說明之碳酸酯製造方法。 As described above, the inventors of the present invention have succeeded in conceiving a method of regenerating benzonitrile from benzamide, which does not require the use of a strong reagent and can simultaneously suppress the occurrence of by-products. Then, the inventors of the present invention further conceived the carbonate production method described below by applying this knowledge knowledge to the method for producing a carbonate.

(第1反應步驟) (first reaction step)

本發明之碳酸酯製造方法中,第1反應步驟是在CeO2 及ZrO2中任一方或雙方之固體催化劑與苯甲腈存在下,使一元醇與二氧化碳直接反應而生成碳酸酯之步驟。 In the method for producing a carbonate according to the present invention, the first reaction step is a step of directly reacting a monohydric alcohol with carbon dioxide in the presence of a solid catalyst of either or both of CeO 2 and ZrO 2 and benzonitrile to form a carbonate.

於本步驟中,一旦使一元醇與二氧化碳反應,除了碳酸酯之外也會生成水,但藉由苯甲腈之存在而利用其與所生成之水之水合反應來生成苯甲醯胺,再從反應系統中去除或減少已生成之水,如此即可促進碳酸酯之生成。 In this step, once the monohydric alcohol is reacted with carbon dioxide, water is formed in addition to the carbonate, but by the presence of benzonitrile, it is reacted with the produced water to form benzamide, and then The water formed is removed or reduced from the reaction system, thus promoting the formation of carbonate.

(一元醇) (monohydric alcohol)

於此,一元醇可使用選自第一級醇、第二級醇及第三級醇中一種或二種以上之任一醇類,但使用甲醇、乙醇、1-丙醇、異丙醇、1-丁醇、1-戊醇、1-已醇、1-庚醇、1-辛醇、1-壬醇、烯丙醇、2-甲基-1-丙醇、環己甲醇、苄基醇時,生成物之產率較高且反應速度也快,較為理想。此時,所生成之碳酸酯分別為碳酸二甲酯、碳酸二乙酯、碳酸二丙酯、碳酸二異丙酯、碳酸二丁酯、碳酸二戊酯、碳酸二己酯、碳酸二庚酯、碳酸二辛酯、碳酸二壬酯、碳酸二烯丙酯、碳酸二2-甲基-丙酯、碳酸二環己甲酯、碳酸二苄酯。 Here, the monohydric alcohol may be one or more selected from the group consisting of a first alcohol, a second alcohol, and a third alcohol, but using methanol, ethanol, 1-propanol, isopropanol, 1-butanol, 1-pentanol, 1-hexanol, 1-heptanol, 1-octanol, 1-nonanol, allyl alcohol, 2-methyl-1-propanol, cyclohexylmethanol, benzyl In the case of an alcohol, the yield of the product is high and the reaction rate is also fast, which is preferable. At this time, the carbonates formed are respectively dimethyl carbonate, diethyl carbonate, dipropyl carbonate, diisopropyl carbonate, dibutyl carbonate, diamyl carbonate, dihexyl carbonate, diheptyl carbonate. , dioctyl carbonate, dinonyl carbonate, diallyl carbonate, di-2-methyl-propyl carbonate, dicyclohexyl carbonate, dibenzyl carbonate.

(碳酸酯製造用催化劑) (catalyst for carbonate production)

此外,CeO2及ZrO2中任一方或雙方之固體催化劑係指僅CeO2、僅ZrO2、CeO2與ZrO2之混合物或者CeO2與ZrO2之固溶體或複合氧化物,尤以僅CeO2為宜。此外,就CeO2 與ZrO2之固溶體或複合氧化物而言,CeO2與ZrO2混合比(莫耳比)並未特別受限,例如可為1:99~99:1,舉例來說也可為50:50。 Further, either one of CeO 2 and ZrO 2 or both of the solid catalyst refers only CeO 2, ZrO 2 only, a mixture of CeO 2 and ZrO 2 or CeO 2 solid solution or a composite oxide of ZrO 2, especially only CeO 2 is preferred. Furthermore, a solid solution or a composite oxide of CeO 2 in terms of ZrO 2, CeO 2 and ZrO 2 mixing ratio (molar ratio) is not particularly limited, for example, it may be 1: 99 to 99: 1, for example to It can also be 50:50.

經本案發明人精心探究之結果,用於直接合成碳酸酯之催化劑必須具有酸鹼複合機能,且以具有酸性度相對較低且鹼性度相對較高之性質為佳。若酸性度過高,與其說是合成碳酸酯,毋寧是變成多量合成醚類,並不理想。就具有適度酸鹼複合機能之催化劑而言,可想見具有如下機制:醇類以R-O-M(M為催化劑)之形式解離吸附於鹼性點上而與CO2之間形成RO-C(=O)-O...M,另一方面,醇類以HO-R...M之形式吸附於酸性點上,而在兩吸附種之間生成RO-C(=O)-OR。 As a result of intensive investigation by the inventors of the present invention, the catalyst for direct synthesis of carbonate must have an acid-base composite function, and it is preferable to have a property of relatively low acidity and relatively high basicity. If the acidity is too high, it is not so much a synthetic carbonate, but it is a lot of synthetic ethers. In the case of a catalyst having a moderate acid-base complex function, it is conceivable to have a mechanism in which the alcohol is dissociated and adsorbed on the basic point in the form of ROM (M is a catalyst) to form RO-C (CO) with CO 2 . )-O...M, on the other hand, the alcohol is adsorbed to the acid sites in the form of HO-R...M, and RO-C(=O)-OR is formed between the two adsorbed species.

此外,該固體催化劑對於合成碳酸酯時所副生成之水與苯甲腈的水合反應也會顯示出催化劑活性。因此,本催化劑表面上雖會成為碳酸酯合成反應與水合反應兩者並進之狀態,但即便在以反應平衡而言不利於碳酸酯合成反應之低壓條件下,苯甲腈之水合反應仍會受到催化劑作用而進行,而使碳酸酯合成反應所副生成之水迅速脫離催化劑表面,進而使碳酸酯合成反應之平衡朝向生成系統偏移,推測碳酸酯合成反應是如此而可在低反應壓力之溫和條件下仍不受平衡制約而獲得碳酸酯之高度反應率。反過來說,可想見的是,在高壓下催化劑表面會吸附多量CO2分子,在合成碳酸酯時難以與生成之水分子接觸,因此,其與苯甲腈之水合反應變得不易進行,僅能在接***衡制 約之狀態下生產碳酸酯,結果則是高壓下生產性不會提高。 Further, the hydration reaction of the solid catalyst with the benzonitrile in the water produced by the synthesis of the carbonate also exhibits catalyst activity. Therefore, although the surface of the catalyst becomes a state in which both the carbonate synthesis reaction and the hydration reaction proceed together, the hydration reaction of benzonitrile is still affected even under a low pressure condition which is disadvantageous to the carbonate synthesis reaction in terms of reaction equilibrium. The catalyst acts to cause the water formed by the carbonate synthesis reaction to rapidly desorb from the catalyst surface, thereby shifting the balance of the carbonate synthesis reaction toward the generation system, and it is presumed that the carbonate synthesis reaction is so low and the reaction pressure is mild. Under the conditions, the high reaction rate of the carbonate is obtained without being restricted by the balance. Conversely, it is conceivable that a large amount of CO 2 molecules are adsorbed on the surface of the catalyst under high pressure, and it is difficult to contact the generated water molecules when synthesizing the carbonate, and therefore, the hydration reaction with benzonitrile becomes difficult to proceed. It is only possible to produce carbonates in a state close to equilibrium, and as a result, productivity is not improved under high pressure.

有關上述推測,若從苯甲腈之反應觀點來說明,則推測如下:苯甲腈在液相下會受到本發明固體催化劑之催化劑作用而使水合反應在其表面受到促進。因此,一旦成為高壓,固體催化劑表面會被CO2所包覆,而成為與主反應所生成之水分子間之水合反應不易受到催化劑作用的狀態,因此水合反應速度降低。另一方面,非專利文獻4、非專利文獻5所記載之縮醛或2,2-二甲氧基丙烷在液相下完全不受催化劑作用,而與主反應生成之水分子引起水合反應。因此,主反應在高壓下會優先進行,故而推測水合反應是在高壓下開始。 The above speculation is explained from the viewpoint of the reaction of benzonitrile, and it is presumed that benzonitrile is subjected to the action of the catalyst of the solid catalyst of the present invention in the liquid phase to promote the hydration reaction on the surface thereof. Therefore, when the pressure is high, the surface of the solid catalyst is coated with CO 2 , and the hydration reaction between the water molecules generated by the main reaction is less likely to be affected by the catalyst, so that the hydration reaction rate is lowered. On the other hand, the acetal or 2,2-dimethoxypropane described in Non-Patent Document 4 and Non-Patent Document 5 is completely free from the action of the catalyst in the liquid phase, and causes hydration reaction with the water molecules formed by the main reaction. Therefore, the main reaction is preferentially carried out under high pressure, so it is presumed that the hydration reaction starts under high pressure.

此外,就本發明之催化劑製造法而言,若於下述中舉例,首先,以氧化鈰(CeO2)之情況而言,可藉由在空氣環境下燒成乙醯丙酮鈰水合物或氫氧化鈰、硫酸鈰、乙酸鈰、硝酸鈰、硝酸鈰銨、碳酸鈰、草酸鈰、過氯酸鈰、磷酸鈰、硬脂酸鈰等各種鈰化合物來調製。此外,使用試劑之氧化鈰時,可直接使用或是在空氣環境下將其乾燥或燒成後作使用。進一步來說,也可從已溶有鈰之溶液沉澱後,藉由進行過濾、乾燥及燒成後作使用。 Further, in the catalyst production method of the present invention, as exemplified below, first, in the case of cerium oxide (CeO 2 ), acetonitrile oxime hydrate or hydrogen can be calcined in an air atmosphere. It is prepared by various cerium compounds such as cerium oxide, cerium sulfate, cerium acetate, cerium nitrate, cerium ammonium nitrate, cerium carbonate, cerium oxalate, cerium perchlorate, cerium phosphate, cerium stearate. In addition, when the cerium oxide of the reagent is used, it can be used as it is or dried or fired in an air environment. Further, it may be used after being precipitated from the solution in which the cerium has been dissolved, followed by filtration, drying, and baking.

另一方面,以ZrO2之情況而言,可藉由在空氣環境下燒成乙氧基鋯、丁氧基鋯、碳酸鋯、氫氧化鋯、磷酸鋯、乙酸鋯、氯氧化鋯、氧化二硝酸鋯、硫酸鋯等各種鋯化合物來調製。又,使用試劑之氧化鋯時,可直接使用或是於 空氣環境下將其乾燥或燒成後作使用。進一步來說,也可從已溶有鋯之溶液沉澱後,藉由進行過濾、乾燥及燒成後作使用。 On the other hand, in the case of ZrO 2 , ethoxy zirconium, zirconium butoxide, zirconium carbonate, zirconium hydroxide, zirconium phosphate, zirconium acetate, zirconium oxychloride, oxidized two can be fired in an air atmosphere. Various zirconium compounds such as zirconium nitrate and zirconium sulfate are prepared. Further, when the zirconia of the reagent is used, it can be used as it is, or dried or fired in an air atmosphere. Further, it may be used after being precipitated from a solution in which zirconium has been dissolved, followed by filtration, drying, and baking.

再者,以CeO2與ZrO2之化合物(諸如固溶體或複合氧化物)的情況而言,可在含有鈰與鋯之溶液中添加鹼,藉由共沉澱形成氫氧化物後,將業經過濾及水洗之物置於空氣環境下予以乾燥、燒成以進行調製。又,雖也可藉由將CeO2與ZrO2之粉末互為物理混合並予以燒成來進行調製,但最終調製品之比表面積不會增高,因此仍以容易進行反應之共沉澱法為宜。 Further, in the case of a compound of CeO 2 and ZrO 2 (such as a solid solution or a composite oxide), a base may be added to a solution containing cerium and zirconium, and a hydroxide may be formed by coprecipitation. The filtered and washed materials are dried and fired in an air atmosphere to prepare. Further, although the powders of CeO 2 and ZrO 2 can be physically mixed with each other and fired, the specific surface area of the final preparation is not increased, so that the coprecipitation method which is easy to carry out the reaction is suitable. .

藉由此等方法,可獲得由氧化鈰與氧化鋯之化合物(具體來說,諸如CeO2-ZrO2)所構成之固體催化劑載體。另,包含調製氧化鈰所構成之催化劑載體及氧化鋯所構成之催化劑載體的情況在內,調製此等各催化劑載體時之燒成溫度宜選擇可使最終調製品之比表面積提高的溫度,雖然也依起始原料而異,舉例來說以300℃至1100℃為宜。又,就本發明之固體催化劑載體而言,雖然除了上述元素以外含有在催化劑製程等中混入之不可避免的雜質也無妨,但仍以儘可能不混入雜質為宜。雜質相對於催化劑宜小於1質量%。 By such a method, a solid catalyst carrier composed of a compound of cerium oxide and zirconium oxide (specifically, such as CeO 2 -ZrO 2 ) can be obtained. Further, in the case of including a catalyst carrier composed of cerium oxide and a catalyst carrier composed of zirconia, the firing temperature at the time of preparing each of the catalyst carriers is preferably selected such that the specific surface area of the final preparation is increased. It also varies depending on the starting materials, and is preferably, for example, 300 ° C to 1100 ° C. Further, the solid catalyst carrier of the present invention may contain unavoidable impurities which are mixed in a catalyst process or the like in addition to the above-mentioned elements, but it is preferred that impurities are not mixed as much as possible. The impurity is preferably less than 1% by mass based on the catalyst.

於此,本發明之催化劑可為粉體或成型體中之任一形態,為成型體時,可為球狀、丸狀、圓柱狀、環狀、輪狀、顆粒狀等之任一者。 Here, the catalyst of the present invention may be in any form of a powder or a molded body, and in the case of a molded body, it may be any of a spherical shape, a pellet shape, a cylindrical shape, a ring shape, a wheel shape, and a pellet shape.

(二氧化碳) (carbon dioxide)

此外,本發明所使用之二氧化碳不僅可使用調製作為工業氣體之物,也可使用從源自製造各種製品之工廠或製鐵廠、發電廠等的廢氣經分離回收之物。 Further, the carbon dioxide used in the present invention can be used not only as an industrial gas but also as a product which is separated and recovered from exhaust gas derived from a factory for manufacturing various products, a steel plant, a power plant or the like.

(固液分離) (solid-liquid separation)

在一元醇之轉化率為100%且不生成吡啶甲酸甲酯或胺甲酸甲酯般之副產物的條件下,反應後會變成:主產物之碳酸酯、副產物之2-吡啶甲醯胺、未反應之苯甲腈及CeO2等之固體催化劑。為了使其等分離,首先,以利用有機溶劑之萃取步驟來萃取液體成分(碳酸酯、苯甲腈),即可以固定成分(苯甲醯胺與固定催化劑)與過濾器來分離。於此,使用之有機溶劑以可溶解碳酸酯之烷烴為宜,己烷、辛烷、壬烷、癸烷及十一烷更佳。 Under the condition that the conversion of monohydric alcohol is 100% and no by-product such as methyl picolinate or methyl carbamate is formed, the reaction becomes: carbonate of the main product, 2-pyridinecarboxamide of by-product, A solid catalyst of unreacted benzonitrile and CeO 2 or the like. In order to separate the particles, first, the liquid component (carbonate, benzonitrile) is extracted by an extraction step using an organic solvent, that is, the component (benzamide and the immobilized catalyst) can be separated from the filter. Here, the organic solvent to be used is preferably a carbonate-soluble alkane, and more preferably hexane, octane, decane, decane or undecane.

(液體成分之分離) (separation of liquid components)

接著,雖然所分離出之液體成分包含了碳酸酯、苯甲腈及有機溶劑,但各物質之熔點及沸點以碳酸酯而言有4℃及90℃(碳酸二甲酯)、-43℃及128℃(碳酸二乙酯)、-41℃及167℃(碳酸二丙酯)、25℃以下及207℃(碳酸二丁酯)等,此外還有-13℃及188℃(苯甲腈)、-95℃及69℃(例如己烷),因此,可藉蒸餾來分離碳酸酯,並可以高純度來回收製品之碳酸酯。此外,除了蒸餾之外,也可將階段性冷卻至熔點以下而固化之物以過濾器分離並回收。 Next, although the separated liquid component contains carbonate, benzonitrile and an organic solvent, the melting point and boiling point of each substance are 4 ° C and 90 ° C (dimethyl carbonate), -43 ° C in terms of carbonate. 128 ° C (diethyl carbonate), -41 ° C and 167 ° C (dipropyl carbonate), below 25 ° C and 207 ° C (dibutyl carbonate), in addition to -13 ° C and 188 ° C (benzonitrile) -95 ° C and 69 ° C (for example, hexane), therefore, the carbonate can be separated by distillation, and the carbonate of the product can be recovered in high purity. Further, in addition to the distillation, the solidified matter may be cooled and cooled to a temperature below the melting point to be separated and recovered by a filter.

(固體成分之分離) (separation of solid components)

再者,作為固體成分而被分離出之苯甲醯胺與固體催化劑可利用親水性溶劑而僅將苯甲醯胺萃取出再以固體催 化劑與過濾器來分離。於此,考慮到處置之容易度及後段之分離,所使用之親水性溶劑宜為丙酮、乙醇、醚類及水。溶於親水性溶劑之苯甲醯胺可藉蒸餾來分離,且可以高純度地純化副生成之苯甲醯胺。 Further, the benzamide and the solid catalyst separated as a solid component can be extracted only with benzidine by a hydrophilic solvent and then with a solid The agent is separated from the filter. Here, in view of easiness of handling and separation of the latter stage, the hydrophilic solvent to be used is preferably acetone, ethanol, ethers and water. The benzamide dissolved in the hydrophilic solvent can be separated by distillation, and the by-produced benzamide can be purified in a high purity.

再者,已溶於親水性溶劑之苯甲醯胺之分離除了蒸餾以外,也可將已冷卻到熔點以下而固化之苯甲醯胺與液體之親水性溶劑以過濾器分離並予以回收。 Further, the separation of benzamide dissolved in a hydrophilic solvent may be carried out by separating the hydrophilic solvent of benzamide which has been cooled to below the melting point and the liquid, and recovering it by a filter, in addition to distillation.

(業已分離之固體催化劑之再生處理) (Recycling of solid catalysts that have been separated)

業已分離之固體催化劑可在使催化劑再生之步驟中作再生處理而於第1反應步驟中再次利用。催化劑再生步驟係一加熱燒除固體催化劑上之雜質等的步驟,宜以400~700℃(更宜500~600℃)燒成3小時程度。為了防止急遽昇溫造成固體催化劑之結構破壞,燒成前宜先實施乾燥步驟,且以110℃下乾燥2小時程度為佳。 The solid catalyst which has been separated can be reused in the first reaction step in the step of regenerating the catalyst. The catalyst regeneration step is a step of heating and burning off impurities on the solid catalyst, and is preferably calcined at 400 to 700 ° C (more preferably 500 to 600 ° C) for 3 hours. In order to prevent structural damage of the solid catalyst caused by rapid temperature rise, it is preferred to carry out the drying step before firing and to dry at 110 ° C for 2 hours.

(殘留成分) (residual component)

此外,未反應之一元醇殘留時,或者,反應溫度達130℃以上之高溫或是反應時間達24小時以上之長時間而生成了苯甲酸甲酯或胺甲酸甲酯般之副產物時,熔點及沸點以一元醇而言分別有-97℃及65℃(甲醇)、-114℃及78℃(乙醇)、-126℃及97℃(1-丙醇)、-90℃及117℃(1-丁醇)等,又有-15℃及198℃(苯甲酸甲酯)、52℃及177℃(胺甲酸甲酯),因此,可在前述蒸餾中階段性地升溫到180℃程度,藉此分離出一元醇、有機溶劑、碳酸酯及胺甲酸甲酯與苯甲腈,之後冷卻並以過濾器過濾已固化之苯甲酸甲酯,即可與苯甲腈分 離。 In addition, when one of the unreacted alcohol remains, or the reaction temperature reaches a high temperature of 130 ° C or higher or the reaction time is longer than 24 hours to form a by-product such as methyl benzoate or methyl carbamate, the melting point And the boiling point of monohydric alcohol is -97 ° C and 65 ° C (methanol), -114 ° C and 78 ° C (ethanol), -126 ° C and 97 ° C (1-propanol), -90 ° C and 117 ° C (1 -butanol), etc., and -15 ° C and 198 ° C (methyl benzoate), 52 ° C and 177 ° C (methyl carbamate), therefore, in the above-mentioned distillation, the temperature is gradually increased to 180 ° C, This separates the monohydric alcohol, the organic solvent, the carbonate and the methyl carbamate and the benzonitrile, and then cools and filters the solidified methyl benzoate with a filter, which can be separated from the benzonitrile. from.

一元醇及有機溶劑大半為有機溶劑,因此可在有機溶劑之萃取步驟中再次利用。但副產物越少,分離到系統外後之處理步驟越不耗事而較理想。 Most of the monohydric alcohol and the organic solvent are organic solvents, and thus can be reused in the extraction step of the organic solvent. However, the fewer the by-products, the less the processing steps after separation into the system are less troublesome.

(第2反應步驟) (second reaction step)

接著,就本發明之第2反應步驟而言,其係使第1反應步驟所副生成之苯甲醯胺從碳酸酯生成反應後之系統分離,之後利用脫水反應來製造苯甲腈。第2反應步驟相當於上述之苯甲腈製造方法。 Next, in the second reaction step of the present invention, benzamide produced in the first reaction step is separated from the system after the carbonate formation reaction, and then the benzonitrile is produced by a dehydration reaction. The second reaction step corresponds to the above-described method for producing benzonitrile.

就該苯甲腈之製造而言,其係在載持有鹼性金屬氧化物之催化劑與有機溶劑存在下,使苯甲醯胺進行脫水反應而生成苯甲腈。 In the production of the benzonitrile, the benzamide is dehydrated to form benzonitrile in the presence of a catalyst carrying a basic metal oxide and an organic solvent.

(苯甲腈製造用催化劑) (catalyst for the production of benzonitrile)

於此,本發明所使用之催化劑可使用下述者:使在金屬與氧之間具有雙鍵之金屬種(鉬、鎢、錸、鈦、鈮)的氧化物(金屬氧化物)載持在一般而言可成為催化劑載體之物質的催化劑;但經探討各種載體之結果,明確得知,使用載持在下述催化劑載體之催化劑時會格外顯示出高性能,即:載持在由SiO2、TiO2、CeO2、ZrO2、Al2O3及C中任1種或2種以上所構成的催化劑載體。 Here, as the catalyst used in the present invention, an oxide (metal oxide) of a metal species (molybdenum, tungsten, rhenium, titanium, ruthenium) having a double bond between a metal and oxygen may be used. In general, it can be used as a catalyst for a catalyst carrier; however, as a result of examining various carriers, it is clear that high performance is exhibited when a catalyst supported on a catalyst carrier described below is used, that is, supported by SiO 2 , A catalyst carrier composed of one or more of TiO 2 , CeO 2 , ZrO 2 , Al 2 O 3 and C.

特別是,若使用SiO2、TiO2、CeO2及ZrO2中之任 1種或2種以上之催化劑載體,會顯示出更高之性能而尤為理想。這是因為,可以想見在與苯甲醯胺之反應中,金屬與氧之間的雙鍵部分有可能會顯示活性,因此以在金屬氧化物之中具有雙鍵之金屬元素為宜。 In particular, it is particularly preferable to use a catalyst carrier of any one or two or more of SiO 2 , TiO 2 , CeO 2 and ZrO 2 to exhibit higher performance. This is because it is conceivable that in the reaction with benzamide, the double bond portion between the metal and oxygen may exhibit activity, and therefore it is preferred to use a metal element having a double bond among the metal oxides.

此外,經本案發明人精心探討之結果,得知使用使鉬高分散地載持於SiO2之催化劑尤佳。至於是否呈現高分散,可藉由電子顯微鏡(SEM、TEM等)之影像等來確認。 Further, as a result of intensive investigation by the inventors of the present invention, it has been found that it is particularly preferable to use a catalyst in which molybdenum is highly dispersed and supported on SiO 2 . Whether or not high dispersion is exhibited can be confirmed by an image of an electron microscope (SEM, TEM, etc.).

有關此處所用之載體的製造方法,若於下述舉例言之,以SiO2之一般製造方法而言,可大致分為乾式法與溼式法。乾式法有燃燒法、電弧法等,濕式法則有沉澱法、凝膠法等,無論以任一方法皆可製造出催化劑載體,但若以凝膠法以外之上述方法,則在技術上及經濟上難以成形為球狀,因此,仍以可使二氧化矽熔膠在氣體介質或液體介質中噴霧而容易地成形為球狀之凝膠法為宜。 The method for producing the carrier used herein can be roughly classified into a dry method and a wet method in the general production method of SiO 2 as exemplified below. The dry method includes a combustion method, an arc method, etc., and the wet method includes a precipitation method, a gel method, etc., and the catalyst carrier can be produced by any method. However, if the above method other than the gel method is used, it is technically Since it is economically difficult to form a spherical shape, it is preferable to use a gel method in which the cerium oxide melt can be easily formed into a spherical shape by spraying in a gaseous medium or a liquid medium.

再者,以CeO2之情況而言,可藉由在空氣環境下燒成乙醯丙酮鈰水合物或氫氧化鈰、硫酸鈰、乙酸鈰、硝酸鈰、硝酸鈰銨、碳酸鈰、草酸鈰、過氯酸鈰、磷酸鈰、硬脂酸鈰等各種鈰化合物來調製。此外,使用試劑之氧化鈰時,可直接使用或是在空氣環境下將其乾燥或燒成後作使用。進一步來說,也可從已溶有鈰之溶液沉澱後,藉由進行過濾、乾燥及燒成後作使用。 Further, in the case of CeO 2 , it can be calcined in an air atmosphere to form acetamidine oxime hydrate or barium hydroxide, barium sulfate, barium acetate, barium nitrate, barium ammonium nitrate, barium carbonate, barium oxalate, It is prepared by various hydrazine compounds such as bismuth perchlorate, strontium phosphate, and strontium stearate. In addition, when the cerium oxide of the reagent is used, it can be used as it is or dried or fired in an air environment. Further, it may be used after being precipitated from the solution in which the cerium has been dissolved, followed by filtration, drying, and baking.

以ZrO2之情況而言,可藉由在空氣環境下燒成乙氧基鋯、丁氧基鋯、碳酸鋯、氫氧化鋯、磷酸鋯、乙酸鋯、氯氧化鋯、氧化二硝酸鋯、硫酸鋯等各種鋯化合物來調製。 又,使用試劑之氧化鋯時,可直接使用或是於空氣環境下將其乾燥或燒成後作使用。進一步來說,也可從已溶有鋯之溶液沉澱後,藉由進行過濾、乾燥及燒成後作使用。 In the case of ZrO 2 , ethoxy zirconium, zirconium zirconate, zirconium carbonate, zirconium hydroxide, zirconium phosphate, zirconium acetate, zirconium oxychloride, zirconium oxynitrate, sulfuric acid can be fired in an air atmosphere. It is prepared by various zirconium compounds such as zirconium. Further, when the zirconia of the reagent is used, it can be used as it is, or dried or fired in an air atmosphere. Further, it may be used after being precipitated from a solution in which zirconium has been dissolved, followed by filtration, drying, and baking.

以TiO2或Al2O3的情況而言,也可使用一般方法予以製造。C是以碳作為主體者,只要在本反應期間中不發生變質,呈任何形態皆可,舉例來說以活性碳等為宜,但並不限於此。 In the case of TiO 2 or Al 2 O 3 , it can also be produced by a general method. C is a carbon-based one, and it may be in any form as long as it does not deteriorate during the reaction period. For example, activated carbon or the like is preferable, but it is not limited thereto.

再者,以含有2種以上金屬種之化合物的情況而言,可在含有2種以上金屬鹽之溶液中添加鹼,藉由共沉澱形成氫氧化物後,使業經過濾及水洗之物於空氣環境下乾燥、燒成來進行調製。此外,雖也可將2種以上之氧化物粉末互為物理混合並燒成來進行調製,但最終調製品之比表面積不會增高,因此仍以易進行反應之共沉澱法為宜。 Further, in the case of a compound containing two or more kinds of metal species, a base may be added to a solution containing two or more kinds of metal salts, and a hydroxide may be formed by coprecipitation, and then the filtered and washed matter is allowed to be air. The environment is dried and fired to prepare. Further, although two or more kinds of oxide powders may be physically mixed and calcined to prepare each other, the specific surface area of the final preparation is not increased, so that a coprecipitation method which is easy to carry out the reaction is preferable.

例如,以CeO2與ZrO2之化合物的情況而言,可在含有鈰與鋯之溶液中添加鹼,藉由共沉澱形成氫氧化物後,將業經過濾及水洗之物置於空氣環境下予以乾燥、燒成以進行調製。 For example, in the case of a compound of CeO 2 and ZrO 2 , a base may be added to a solution containing cerium and zirconium, and after the hydroxide is formed by coprecipitation, the filtered and washed product is dried in an air atmosphere. , firing to make modulation.

藉由此等方法,可獲得由氧化鈰與氧化鋯之化合物(具體來說,諸如CeO2-ZrO2)所構成之固體催化劑載體。另,包含調製氧化鈰所構成之催化劑載體及氧化鋯所構成之催化劑載體的情況在內,調製此等各催化劑載體時之燒成溫度宜選擇可使最終調製品之比表面積提高的溫度,雖然也依起始原料而異,舉例來說以300℃至1100℃為宜。又,就本發明之固體催化劑載體而言,雖然除了上述元素以外 含有在催化劑製程等中混入之不可避免的雜質也無妨,但仍以儘可能不混入雜質為宜。 By such a method, a solid catalyst carrier composed of a compound of cerium oxide and zirconium oxide (specifically, such as CeO 2 -ZrO 2 ) can be obtained. Further, in the case of including a catalyst carrier composed of cerium oxide and a catalyst carrier composed of zirconia, the firing temperature at the time of preparing each of the catalyst carriers is preferably selected such that the specific surface area of the final preparation is increased. It also varies depending on the starting materials, and is preferably, for example, 300 ° C to 1100 ° C. Further, the solid catalyst carrier of the present invention may contain unavoidable impurities which are mixed in a catalyst process or the like in addition to the above-mentioned elements, but it is preferred that impurities are not mixed as much as possible.

選自SiO2、TiO2、CeO2、ZrO2、Al2O3及C中任1種或2種以上之載體的表面積越大,越可高分散地載持活性金屬種而使苯甲腈之生成量提升,因而較為理想。具體來說,雖然表面積也會因載體之種類而異,但表面積以BET法測定宜在10m2/g以上。 The larger the surface area of the carrier selected from one or more of SiO 2 , TiO 2 , CeO 2 , ZrO 2 , Al 2 O 3 and C, the higher the dispersion of the active metal species and the benzonitrile The increase in the amount of production is therefore ideal. Specifically, although the surface area varies depending on the type of the carrier, the surface area is preferably 10 m 2 /g or more as measured by the BET method.

本發明催化劑之製造僅需以習知方法使將成為活性種之金屬氧化物載持於載體上即可。除了一般使用溶液之沉澱載持法之外,例如,可藉由初溼含浸(Incipient wetness)法或蒸發乾涸法等之含浸法來進行載持。 The production of the catalyst of the present invention requires only a metal oxide to be an active species to be supported on a carrier by a conventional method. In addition to the precipitation method generally used for the solution, for example, it may be carried by an impregnation method such as an incipient wetness method or an evaporation dry method.

於下列舉較佳例。當載體為SiO2時可使用市售之粉末或球狀SiO2,為求可均勻載持活性金屬,需整粒到100mesh(0.15mm)以下,且為去除水分,宜在空氣中以700℃進行1小時之預備燒成。此外,雖然SiO2包含了各種性狀之物,但表面積越大越可使活性金屬高度分散而使苯甲腈之生成量提高,因此較為理想。具體來說,以300m2/g以上之表面積為宜。但調製後之催化劑表面積有時會因為SiO2與活性金屬之相互作用等而僅較SiO2之表面積低。此時,宜令製造後之催化劑表面積在150m2/g以上。 The preferred examples are listed below. When the carrier is SiO 2 , a commercially available powder or spherical SiO 2 may be used. In order to uniformly carry the active metal, it is required to be granulated to 100 mesh (0.15 mm) or less, and in order to remove moisture, it is preferably 700 ° C in air. Prepare for 1 hour of baking. Further, although SiO 2 contains various properties, the larger the surface area, the higher the active metal can be dispersed and the amount of benzonitrile formed is increased. Specifically, a surface area of 300 m 2 /g or more is preferred. However, the surface area of the catalyst after the preparation is sometimes lower than the surface area of SiO 2 due to the interaction of SiO 2 with the active metal or the like. At this time, it is preferred that the surface area of the catalyst after the production be 150 m 2 /g or more.

將成為活性種之金屬氧化物之前驅物的金屬鹽僅需對各種溶劑具高溶解度即可,可使用如碳酸鹽、碳酸氫鹽、氯化物鹽、硝酸鹽、硫酸鹽及矽酸鹽等各種化合物。使金屬化合物之前驅物水溶液含浸到載體後,藉由將其乾 燥、燒成即可用作催化劑,燒成溫度雖也依所用前驅物而異,但以400~600℃為宜。 The metal salt of the precursor of the metal oxide to be an active species only needs to have high solubility for various solvents, and various kinds of such as carbonate, hydrogencarbonate, chloride salt, nitrate, sulfate, and citrate can be used. Compound. After impregnating the metal compound precursor aqueous solution with the carrier, by drying it Drying and calcination can be used as a catalyst, and the firing temperature varies depending on the precursor used, but it is preferably 400 to 600 °C.

此外,雖然金屬氧化物之載持量僅需適當設定即可,但舉例來說,以全催化劑重量為基準,宜將金屬氧化物之金屬換算載持量設定在0.1~1.5mmol/g程度,特別是0.1~1mmol/g程度,更宜0.2~0.8mmol/g程度。載持量若多於此量,則有金屬氧化物粗大化致使活性降低之虞。又,就反應時之催化劑使用量而言,也是適當設定即可。 In addition, although the amount of the metal oxide supported is only required to be appropriately set, for example, the metal conversion amount of the metal oxide is preferably set to be 0.1 to 1.5 mmol/g based on the total catalyst weight. In particular, it is about 0.1 to 1 mmol/g, more preferably about 0.2 to 0.8 mmol/g. When the amount of the support is more than this amount, there is a possibility that the metal oxide is coarsened to lower the activity. Further, the amount of the catalyst used in the reaction may be appropriately set.

又,本發明之催化劑除了上述元素以外,包含在催化劑製程等中混入之不可避免的雜質亦無妨。但仍以儘可能不混入雜質為宜。 Further, the catalyst of the present invention may contain, in addition to the above-mentioned elements, impurities which are inevitably mixed in a catalyst process or the like. However, it is advisable to avoid impurities as much as possible.

於此,本發明之已載持於載體上的催化劑可為粉體或成型體中之任一形態,為成型體時,可為球狀、丸狀、圓柱狀、環狀、輪狀、顆粒狀等之任一者。 Herein, the catalyst supported on the carrier of the present invention may be in any form of a powder or a molded body, and in the case of a molded body, it may be a spherical shape, a pellet shape, a cylindrical shape, a ring shape, a wheel shape, or a particle shape. Any of them.

(有機溶劑) (Organic solvents)

用於脫水反應之有機溶劑可適宜地使用沸點為130℃以上之各種物質,但其中以氯苯、(鄰、間、對)二甲苯及對稱三甲苯等更適於使用,且以對稱三甲苯尤佳。 The organic solvent used for the dehydration reaction may suitably use various substances having a boiling point of 130 ° C or higher, but among them, chlorobenzene, (o-, m-, p-) xylene, and symmetrical toluene are more suitable for use, and symmetrical trimethylbenzene Especially good.

(反應條件) (Reaction conditions)

本發明之使用催化劑的苯甲腈製造方法中,反應條件宜在脫水反應速度與溶劑沸點、以及反應時所發生之CO2排出量及經濟性等之觀點下作選擇,例如,可使其在反應溫度160~200℃、壓力常壓及反應時間數小時~24小時之程度的條件下進行,但並不特別受此等條件所侷限。 In the method for producing benzonitrile using a catalyst according to the present invention, the reaction conditions are preferably selected from the viewpoints of the dehydration reaction rate and the boiling point of the solvent, and the amount of CO 2 emission and economy which are generated during the reaction, and the like, for example, The reaction temperature is 160 to 200 ° C, the pressure is normal, and the reaction time is several hours to 24 hours, but is not particularly limited by these conditions.

(反應形式) (reaction form)

其次,本發明之使用催化劑之苯甲腈製造方法就反應形式而言並未特別受限,可使用批式反應器、半批式反應器以及連續槽型反應器或管型反應器等之流通式反應器中之任一者。此外,催化劑可應用固定床及漿態床等中之任一者。 Further, the benzonitrile production method using the catalyst of the present invention is not particularly limited in terms of the reaction form, and a batch reactor, a semi-batch reactor, and a continuous tank reactor or a tubular reactor can be used. Any of the reactors. Further, the catalyst may be applied to any of a fixed bed and a slurry bed.

(脫水) (dehydration)

就本發明之製造方法而言,從副生成之苯甲醯胺生成(再生)苯甲腈之第2反應步驟亦與製造碳酸酯之步驟相同,宜一邊去除脫水反應所生成之副產物水一邊進行反應,舉例來說,宜在系統內部設置沸石等之脫水劑而一邊去除副產物水一邊進行反應。經本案發明人精心研討之結果,可由下述方式提高苯甲腈之生成量:使用索氏萃取管及冷卻器,在萃取管內設置沸石(分子篩)或氫化鈣作為脫水劑,並於反應管中裝入催化劑、苯甲醯胺及有機溶劑後,使其回流並在常壓下反應。 In the production method of the present invention, the second reaction step of producing (regenerating) benzonitrile from the by-produced benzamide is also the same as the step of producing the carbonate, and it is preferable to remove the by-product water formed by the dehydration reaction. To carry out the reaction, for example, it is preferred to provide a dehydrating agent such as zeolite in the system and carry out the reaction while removing by-product water. As a result of careful study by the inventors of the present invention, the amount of benzonitrile can be increased by using a Soxhlet extraction tube and a cooler, and a zeolite (molecular sieve) or calcium hydride is provided as a dehydrating agent in the extraction tube, and in the reaction tube. After charging the catalyst, benzamide and an organic solvent, it is refluxed and reacted under normal pressure.

又,用作脫水劑之分子篩之種類、形狀並未特別受限,但舉例來說,可使用3A、4A、5A等一般吸水性較高且為球狀或丸狀之物。此外,宜在事前預先使其乾燥,且以在300~500℃下乾燥1小時左右為佳。 Further, the type and shape of the molecular sieve used as the dehydrating agent are not particularly limited, and for example, 3A, 4A, 5A or the like which is generally water-absorbent and spherical or pellet-shaped can be used. Further, it is preferred to dry it beforehand and preferably to dry at 300 to 500 ° C for about 1 hour.

(反應生成物) (reaction product)

苯甲醯胺之脫水反應係如上述,雖可想見會因苯甲醯胺之分解而副生成吡啶甲酸或吡啶,但本發明在使用催化劑之脫水反應後,僅會有反應物之微量殘留的苯甲醯胺、生成物之苯甲腈及副產物之水、有機溶劑,而幾乎不會生成如上述般之副產物。 The dehydration reaction of benzamidine is as described above, although it is conceivable that pyridylcarboxylic acid or pyridine is formed by the decomposition of benzamide, but in the present invention, only a small amount of the reactant remains after the dehydration reaction using the catalyst. The benzamide, the benzonitrile of the product, the water of the by-product, and the organic solvent hardly produce by-products as described above.

使用索氏萃取管及冷卻器回流時,反應溫度宜為可使苯甲醯胺之脫水反應在液相下進行之條件。若慮及反應效率,則在液相條件下以更高溫為宜,在常壓下進行反應時,宜將反應管周邊加熱到160~200℃。在典型例之反應系統中,各物質之熔點為127℃(苯甲醯胺)、-13℃(苯甲腈)、-45℃(有機溶劑,例如對稱三甲苯),此外,沸點為288℃(苯甲醯胺)、188℃(苯甲腈)、100℃(水)、165℃(有機溶劑,例如對稱三甲苯),因此,若為上述溫度,反應相除了催化劑為固體之外幾乎全部成為液體,一部分已氣化之苯甲醯胺、副產物水、有機溶劑則在冷卻器中冷卻,副產物之水被脫水劑吸附,苯甲醯胺及有機溶劑回到反應管而再次貢獻反應。 When refluxing using a Soxhlet extraction tube and a cooler, the reaction temperature is preferably a condition in which the dehydration reaction of benzamide is carried out in the liquid phase. When considering the reaction efficiency, it is preferable to use a higher temperature under liquid phase conditions, and when the reaction is carried out under normal pressure, the periphery of the reaction tube should be heated to 160 to 200 °C. In a typical reaction system, the melting point of each substance is 127 ° C (benzamide), -13 ° C (benzonitrile), -45 ° C (organic solvent, such as symmetrical trimethylbenzene), in addition, the boiling point is 288 ° C (benzamide), 188 ° C (benzonitrile), 100 ° C (water), 165 ° C (organic solvent, such as symmetrical trimethylbenzene), therefore, if the temperature is above, the reaction phase is almost all except the catalyst is solid As a liquid, a part of the vaporized benzamide, by-product water, and organic solvent are cooled in a cooler, the by-product water is adsorbed by the dehydrating agent, and the benzamide and the organic solvent are returned to the reaction tube to contribute again. .

(苯甲腈之再利用) (reuse of benzonitrile)

於第2反應步驟再生之苯甲腈可再次利用於第1反應步驟中。 The benzonitrile regenerated in the second reaction step can be reused in the first reaction step.

<8. 碳酸酯之製造裝置> <8. Carbonate manufacturing device>

其次,顯示具體例於下,俾進一步詳細說明本發明所使用之製造裝置及操作條件(反應條件)。於此,使用苯甲腈之碳酸酯製造裝置具有與使用2-氰吡啶之製造裝置實質相 同之構成。概略來說,使用苯甲腈之碳酸酯製造裝置係將圖1等中之2-氰吡啶及2-吡啶甲醯胺取代為苯甲腈及苯甲醯胺而成之物。於此,使用圖1~圖4,將使用苯甲腈之碳酸酯製造裝置說明於下。 Next, specific examples will be described below, and the production apparatus and operating conditions (reaction conditions) used in the present invention will be further described in detail. Here, the carbonate production apparatus using benzonitrile has a substantial phase with a manufacturing apparatus using 2-cyanopyridine The same composition. Briefly, a carbonate production apparatus using benzonitrile is obtained by substituting 2-cyanopyridine and 2-pyridinecarboxamide in Fig. 1 and the like into benzonitrile and benzamide. Here, a carbonate production apparatus using benzonitrile will be described below using FIGS. 1 to 4 .

圖1為本發明之合宜設備的一例。又,將圖1中本設備各步驟中之各物質狀態顯示於圖2。本設備可使用在一元醇轉化率100%且不生成苯甲酸甲酯或胺甲酸甲酯之副產物的反應條件情況下。 Figure 1 is an illustration of a suitable apparatus of the present invention. Further, the state of each substance in each step of the apparatus of Fig. 1 is shown in Fig. 2. The apparatus can be used in the case of a reaction condition in which the monohydric alcohol conversion rate is 100% and no by-product of methyl benzoate or methyl carbamate is formed.

(第1反應步驟) (first reaction step)

就第1反應步驟而言,其將CeO2及ZrO2中任一方或雙方之固體催化劑(固相)、一元醇12(液相)、苯甲腈13(液相)充填至第1反應塔1(第1反應部)中,且經由昇壓鼓風機10(加壓部)而將二氧化碳(氣相)充填至第1反應塔1(第1反應部)中。固體催化劑可於反應前使用新充填或是經再生塔6再生之固體催化劑14(固相)。又,苯甲腈於反應開始時使用新品,但可再利用業經第1蒸餾塔3純化之未反應苯甲腈20(液相)與經第3蒸餾塔9純化且從苯甲醯胺再生之苯甲腈。 In the first reaction step, a solid catalyst (solid phase) of one or both of CeO 2 and ZrO 2 , a monohydric alcohol 12 (liquid phase), and benzonitrile 13 (liquid phase) are charged to the first reaction column. In the first reaction unit (first reaction unit), carbon dioxide (gas phase) is charged into the first reaction column 1 (first reaction unit) via the booster blower 10 (pressurizing unit). The solid catalyst can be used as a solid catalyst 14 (solid phase) which is newly filled or regenerated by the regeneration column 6 before the reaction. Further, benzonitrile is used as a new product at the beginning of the reaction, but the unreacted benzonitrile 20 (liquid phase) purified by the first distillation column 3 can be reused and purified by the third distillation column 9 and regenerated from benzamide. Benzoonitrile.

其次,本發明中使用CeO2及ZrO2中任一方或雙方之固體催化劑之碳酸酯的直接合成裝置可使用批式反應器、半批式反應器及連續槽型反應器、管型反應器般之流通式反應器中之任一者。 Next, in the present invention, a direct synthesis apparatus using a carbonate of a solid catalyst of either or both of CeO 2 and ZrO 2 may be used in a batch reactor, a semi-batch reactor, a continuous tank reactor, or a tubular reactor. Any of the flow-through reactors.

(反應溫度) (temperature reflex)

宜令第1反應塔1中之反應溫度為50~300℃。反應溫度小於50℃時反應速度低落,碳酸酯合成反應及苯甲腈之水 合反應均幾乎不進行,而有碳酸酯之生產性低落之傾向。又,反應溫度超過150℃時,雖然各反應之反應速度提高,但容易發生碳酸酯之分解或改質,苯甲醯胺容易與一元醇發生反應,因此碳酸酯之產率有降低之傾向。更宜為100~150℃。但可想見的是此一溫度會依固體催化劑之種類及量以及原料(一元醇、苯甲腈)之量及比例而異,宜適當地設定最佳條件。由於較佳之反應溫度為100~150℃,宜在第1反應塔之前段以蒸汽將原料(一元醇、苯甲腈)預加熱。 The reaction temperature in the first reaction column 1 should be 50 to 300 °C. When the reaction temperature is less than 50 ° C, the reaction rate is low, the carbonate synthesis reaction and the water of benzonitrile The combined reaction hardly proceeds, and there is a tendency that the productivity of the carbonate is lowered. Further, when the reaction temperature exceeds 150 ° C, the reaction rate of each reaction is increased, but decomposition or modification of the carbonate is liable to occur, and benzamide easily reacts with the monohydric alcohol, so that the yield of the carbonate tends to decrease. More preferably 100~150 °C. However, it is conceivable that the temperature will vary depending on the type and amount of the solid catalyst and the amount and ratio of the raw materials (monohydric alcohol, benzonitrile), and the optimum conditions should be appropriately set. Since the preferred reaction temperature is from 100 to 150 ° C, it is preferred to preheat the starting material (monohydric alcohol, benzonitrile) with steam in the first stage of the first reaction column.

(反應壓力) (reaction pressure)

宜令反應壓力為0.1~5MPa(絕對壓力)。反應壓力小於0.1MPa(絕對壓力)時,減壓裝置變得必要,不僅是設備複雜且成本提高,減壓所需之動能也變得必要而使能量效率變差。此外,反應壓力超過5MPa時,苯甲腈之水合反應變得不易進行,不僅是碳酸酯之產率惡化,昇壓所必須之動能也變得必要而使能量效率變差。又,從提高碳酸酯產率之觀點來看,反應壓力宜為0.1~4MPa(絕對壓力),更宜為0.2~2MPa(絕對壓力)。 The reaction pressure should be 0.1~5MPa (absolute pressure). When the reaction pressure is less than 0.1 MPa (absolute pressure), the pressure reducing device becomes necessary, and the equipment is complicated and the cost is increased, and the kinetic energy required for the pressure reduction is also required to deteriorate the energy efficiency. Further, when the reaction pressure exceeds 5 MPa, the hydration reaction of benzonitrile becomes difficult to proceed, and not only the yield of the carbonate is deteriorated, but also the kinetic energy necessary for the pressure increase becomes necessary, and the energy efficiency is deteriorated. Further, from the viewpoint of improving the yield of the carbonate, the reaction pressure is preferably 0.1 to 4 MPa (absolute pressure), more preferably 0.2 to 2 MPa (absolute pressure).

(苯甲腈之用量) (the amount of benzonitrile)

此外,用於水合反應之苯甲腈宜為原料之醇類體積的0.1倍以上且1倍以下,並且宜在反應前預先導入反應器中。以小於0.1倍導入時,貢獻給水合反應之苯甲腈較少而有使碳酸酯產率惡化之虞。另一方面,以超過1倍導入時,由於反應結束後容易與生成物分離且可再利用,並無特別問題。此外,可以想見的是,相對於固體催化劑之一元醇及苯甲 腈的量會視固體催化劑之種類及量、以及一元醇之種類及其與2-氰吡啶之比例而異,因此宜適當地設定最佳條件。 Further, the benzonitrile used for the hydration reaction is preferably 0.1 times or more and 1 time or less the volume of the alcohol of the raw material, and is preferably introduced into the reactor before the reaction. When introduced at less than 0.1 times, the amount of benzonitrile contributed to the hydration reaction is small, and the yield of the carbonate is deteriorated. On the other hand, when it introduces more than one time, since it is easy to isolate|separate from a product after the completion of a reaction, it can re In addition, it is conceivable that one of the solid catalysts and the benzene The amount of the nitrile varies depending on the kind and amount of the solid catalyst, the type of the monohydric alcohol, and the ratio of the monocyanohydrin to the 2-cyanopyridine. Therefore, it is preferred to appropriately set the optimum conditions.

(反應生成物之分離) (separation of reaction product)

於第1反應塔1反應後之反應液15係在第1萃取塔2(第1分離部)分離為液相與固相。含在反應液15中之物質為碳酸酯(液相)、未反應之苯甲腈(液相)與苯甲醯胺(固相)、固體催化劑(固相),而利用有機溶劑(液相)萃取之。於此,所使用之有機溶劑以烷烴為合適,且從後段蒸餾之分離容易度來看,以己烷、辛烷、壬烷、癸烷及十一烷為宜。第1萃取塔2之萃取步驟為了抑制能量消費,萃取時之溫度宜在常溫下進行,但若是較有機溶劑之沸點更低之溫度(例如,以己烷之情況而言,因沸點為69℃,加熱到50℃程度),亦可藉由加熱以使萃取時間縮短。 The reaction liquid 15 after the reaction in the first reaction column 1 is separated into a liquid phase and a solid phase in the first extraction column 2 (first separation unit). The substance contained in the reaction liquid 15 is a carbonate (liquid phase), unreacted benzonitrile (liquid phase) and benzamide (solid phase), a solid catalyst (solid phase), and an organic solvent (liquid phase) ) Extracted. Here, the organic solvent to be used is suitably an alkane, and hexane, octane, decane, decane, and undecane are preferable from the viewpoint of ease of separation in the latter stage distillation. Extraction step of the first extraction column 2 In order to suppress energy consumption, the temperature at the time of extraction is preferably carried out at normal temperature, but if it is lower than the boiling point of the organic solvent (for example, in the case of hexane, the boiling point is 69 ° C) It is heated to a temperature of 50 ° C. It can also be heated to shorten the extraction time.

在第1萃取塔2萃取出之萃取液17包含碳酸酯、未反應之苯甲腈及烷烴。於第1蒸餾塔3(第2分離部)中利用各物質之沸點為90℃(例如碳酸二甲酯)、188℃(苯甲腈)、69℃(例如己烷)一事進行蒸餾,而分離為製品之碳酸酯19、未反應之苯甲腈20及業經用於萃取之烷烴16。 The extract 17 extracted in the first extraction column 2 contains carbonate, unreacted benzonitrile, and an alkane. Distillation is carried out in the first distillation column 3 (second separation unit) by using a boiling point of 90 ° C (for example, dimethyl carbonate), 188 ° C (benzonitrile), and 69 ° C (for example, hexane). It is a carbonate of the product 19, unreacted benzonitrile 20 and an alkane 16 which is used for extraction.

另一方面,第1萃取塔2分離出之固相18中包含了苯甲醯胺與固體催化劑,而以第2萃取塔4(第3分離部)分離。於此,所使用之溶劑以可溶解苯甲醯胺之親水性溶劑(液相)為合適,且從後段蒸餾之分離容易度來看,以丙酮、乙醇、醚類及水為宜。第2萃取塔4之萃取步驟也為了抑制能量消費,萃取時之溫度以在常溫下進行為宜,但若是較親水性 溶劑之沸點更低的溫度(例如,以丙酮的情況而言,因沸點為56.5℃,加熱到40℃程度),則也可藉由加熱而使萃取時間縮短。 On the other hand, the solid phase 18 separated by the first extraction column 2 contains benzamide and a solid catalyst, and is separated by the second extraction column 4 (third separation unit). Here, the solvent to be used is suitably a hydrophilic solvent (liquid phase) in which benzylamine can be dissolved, and acetone, ethanol, ethers and water are preferred from the viewpoint of easiness of separation in the latter stage distillation. The extraction step of the second extraction column 4 is also for suppressing energy consumption, and the temperature at the time of extraction is preferably carried out at normal temperature, but if it is relatively hydrophilic When the boiling point of the solvent is lower (for example, in the case of acetone, since the boiling point is 56.5 ° C and heated to 40 ° C), the extraction time can be shortened by heating.

含有苯甲醯胺與親水性溶劑之萃取液21係於第2蒸餾塔5蒸餾,而按各物質之沸點分離為127℃(苯甲醯胺)與57℃(例如丙酮)。 The extract 21 containing benzamidine and a hydrophilic solvent is distilled in the second distillation column 5, and is separated into 127 ° C (benzamide) and 57 ° C (for example, acetone) at the boiling point of each substance.

此外,於第2萃取塔4分離出之固體催化劑22(固相)可於催化劑再生塔6再生處理而回到第1反應塔1。催化劑再生係一進行加熱來燒除固體催化劑上之雜質等的步驟,其以400~700℃(宜500~600℃)燒成3小時程度。為了防止急遽昇溫造成固體催化劑之結構破壞,燒成前宜先實施乾燥步驟,且以110℃下乾燥2小時程度為佳。 Further, the solid catalyst 22 (solid phase) separated in the second extraction column 4 can be regenerated in the catalyst regeneration column 6 and returned to the first reaction column 1. The catalyst regeneration is a step of heating to burn off impurities or the like on the solid catalyst, and is baked at 400 to 700 ° C (preferably 500 to 600 ° C) for 3 hours. In order to prevent structural damage of the solid catalyst caused by rapid temperature rise, it is preferred to carry out the drying step before firing and to dry at 110 ° C for 2 hours.

已於第2蒸餾塔5純化之苯甲醯胺23(固相)為了再生為苯甲腈而朝第2反應塔7(第2反應部)輸送,但為了避免在配管內栓塞,配管宜以低壓蒸汽等加熱到熔點之127℃以上。 The benzamide 23 (solid phase) purified in the second distillation column 5 is transported to the second reaction column 7 (second reaction unit) for regeneration to benzonitrile, but in order to avoid embedding in the pipe, the pipe is preferably The low pressure steam or the like is heated to a temperature above 127 ° C.

反應後之溶液於催化劑分離裝置8中以過濾器過濾而僅分離出呈固體之催化劑,可視為用畢之催化劑26而予以回收。此時,可藉一般之過濾等的固液分離方法來輕易回收。催化劑分離後,由於存在於系統內之各物質沸點係如上述般各自相異,可藉由在第3蒸餾塔9施行蒸餾而輕易分離為苯甲腈、有機溶劑、苯甲醯胺及水,有機溶劑27及苯甲醯胺28可再循環利用於苯甲醯胺之脫水反應中。又,已純化之苯甲腈13則可在進行製造碳酸酯之反應中再次利 用。 The solution after the reaction is filtered in a catalyst separation device 8 by a filter to separate only the solid catalyst, which can be regarded as being recovered by using the catalyst 26. At this time, it can be easily recovered by a solid-liquid separation method such as general filtration. After the separation of the catalyst, since the boiling points of the respective substances present in the system are different as described above, it can be easily separated into benzonitrile, an organic solvent, benzamide, and water by performing distillation in the third distillation column 9. The organic solvent 27 and benzamide 28 can be recycled to the dehydration reaction of benzamide. In addition, the purified benzonitrile 13 can be used again in the reaction for producing carbonates. use.

(第2反應步驟) (second reaction step)

就第2反應步驟而言,其係以第2反應塔7利用苯甲醯胺之脫水反應來生成苯甲腈。本發明之製造裝置係一在載持有具雙鍵之金屬氧化物的催化劑與有機溶劑之存在下使苯甲醯胺進行脫水反應而生成苯甲腈之裝置。就反應形式而言並未特別受限,可使用批式反應器、半批式反應器以及連續槽型反應器及管型反應器般之流通式反應器中之任一者。此外,催化劑可應用固定床及漿態床等中之任一者。第2反應塔之溫度可依反應形式來變更,但使用索氏萃取管及冷卻器回流時,宜將反應管周邊加熱到160~200℃。本發明之製造裝置宜一邊去除脫水反應所生成之副產物水一邊進行,舉例來說,宜在系統內部設置回流或蒸餾、沸石等之脫水劑而一邊去除副產物之水一邊進行反應。經本案發明人精心研討之結果,可由下述方式提高苯甲腈之生成量:使用索氏萃取管及冷卻器,在萃取管內設置沸石(分子篩)或氫化鈣作為脫水劑,於反應管中裝入催化劑、苯甲醯胺及有機溶劑後,使其回流並在常壓下反應。有機溶劑以沸點為130℃以上之物質為佳,可舉例如氯苯、(鄰、間、對)二甲苯及對稱三甲苯等。 In the second reaction step, benzonitrile is produced by the dehydration reaction of benzamide in the second reaction column 7. The production apparatus of the present invention is a device for producing benzonitrile by dehydrating a benzamide in the presence of a catalyst carrying a metal oxide having a double bond and an organic solvent. The reaction form is not particularly limited, and any one of a batch reactor, a semi-batch reactor, and a continuous tank type reactor and a tubular reactor-like flow reactor can be used. Further, the catalyst may be applied to any of a fixed bed and a slurry bed. The temperature of the second reaction column may be changed depending on the reaction form, but when the Soxhlet extraction tube and the cooler are used for reflux, the periphery of the reaction tube should be heated to 160 to 200 °C. The production apparatus of the present invention is preferably carried out while removing the by-product water produced by the dehydration reaction. For example, it is preferred to carry out a reaction while refluxing or distilling a dehydrating agent such as zeolite in the system while removing water of by-products. As a result of careful study by the inventors of the present invention, the amount of benzonitrile can be increased by using a Soxhlet extraction tube and a cooler, and a zeolite (molecular sieve) or calcium hydride is provided as a dehydrating agent in the reaction tube in the reaction tube. After charging the catalyst, benzamide and an organic solvent, it is refluxed and reacted under normal pressure. The organic solvent preferably has a boiling point of 130 ° C or higher, and examples thereof include chlorobenzene, (o-, m-, p-) xylene, and symmetrical trimethylbenzene.

使用索氏萃取管及冷卻器回流時,將反應管周邊加熱到160~200℃。各物質之熔點為127℃(苯甲醯胺)、-13℃(苯甲腈)、-45℃(有機溶劑,例如對稱三甲苯),此外,沸點為288℃(苯甲醯胺)、188℃(苯甲腈)、100℃(水)、165℃(有 機溶劑,例如對稱三甲苯),因此,反應相除了催化劑為固體之外全部成為液體,一部分已氣化之苯甲醯胺、副產物之水、有機溶劑則在冷卻器中冷卻,副產物之水被脫水劑吸附,苯甲醯胺及有機溶劑回到反應管而再次貢獻反應。 When using a Soxhlet extraction tube and a cooler to reflow, the periphery of the reaction tube is heated to 160 to 200 °C. The melting point of each substance is 127 ° C (benzamide), -13 ° C (benzonitrile), -45 ° C (organic solvent, such as symmetrical trimethylbenzene), in addition, the boiling point of 288 ° C (benzamide), 188 °C (benzonitrile), 100 ° C (water), 165 ° C (with An organic solvent, such as symmetrical trimethylbenzene). Therefore, the reaction phase is completely liquid except that the catalyst is a solid, and a part of the vaporized benzamide, a by-product water, and an organic solvent are cooled in a cooler, and by-products are The water is adsorbed by the dehydrating agent, and the benzamide and the organic solvent are returned to the reaction tube to contribute to the reaction again.

反應後之溶液係以低壓蒸汽等加熱到苯甲醯胺熔點之288℃以上,之後直接以催化劑分離塔8(第4分離部)僅分離出催化劑,而視為用畢之催化劑26予以回收。此時,可藉一般之過濾等的固液分離方法來輕易回收。催化劑分離後,由於存在於系統內之各物質沸點係如上述般各自相異,可藉由在第3蒸餾塔9(第5分離部)施行蒸餾而輕易分離為苯甲腈13、有機溶劑27、苯甲醯胺28及水29,有機溶劑27及苯甲醯胺28會回到第3反應塔7之前段而可再循環利用。又,已純化之苯甲腈13則以輸送部輸送到進行製造碳酸酯之第1反應塔1,於第1反應塔1中再次利用。 The solution after the reaction is heated to a temperature of 288 ° C or more of the melting point of benzamide by low-pressure steam or the like, and then the catalyst is separated only by the catalyst separation column 8 (fourth separation portion), and is recovered as the catalyst 26 . At this time, it can be easily recovered by a solid-liquid separation method such as general filtration. After the separation of the catalyst, the boiling points of the respective substances present in the system are different as described above, and can be easily separated into benzonitrile 13 and organic solvent by performing distillation in the third distillation column 9 (the fifth separation unit). Benzomethane 28 and water 29, organic solvent 27 and benzamide 28 are returned to the third stage of the third reaction column 7 for recycling. Further, the purified benzonitrile 13 is transported to the first reaction column 1 where the carbonate is produced by the transport unit, and is reused in the first reaction column 1.

(碳酸酯之製造方法及裝置之其他例) (Other examples of the method and apparatus for producing carbonate)

又,圖3為本發明之合宜設備的另一例,圖4為圖3之設備在各步驟中之各物質狀態。本設備在未反應之一元醇殘留且會生成苯甲酸甲酯或胺甲酸甲酯之副產物的反應條件下也可使用。基本結構與前述圖1相同,但經第1萃取塔2萃取之萃取液17除了碳酸酯、未反應之苯甲腈、烷烴之外,還含有胺甲酸甲酯與苯甲酸甲酯。於第1萃取塔3,利用各物質之沸點為90℃(例如碳酸二甲酯)、215℃(2-氰吡啶)、69℃(例如己烷)、65℃(例如甲醇)、177℃(胺甲酸甲酯)、233℃(苯甲酸甲酯)一事,階段性地使溫度上昇到180℃程度藉 此進行蒸餾,而分離為製品之碳酸酯19、業經用於萃取之烷烴與未反應之一元醇的混合物33、以及胺甲酸甲酯32。此外,蒸餾後冷卻到30~100℃程度,藉此,熔點為103℃之苯甲酸甲酯會固化,可以過濾器30等施行固液分離,而可分離為未反應之苯甲腈20及苯甲酸甲酯31。又,烷烴與一元醇之混合物33大半為烷烴,因此可作為萃取用溶劑而再次利用。 Further, Fig. 3 is another example of a suitable apparatus of the present invention, and Fig. 4 is a view showing the state of each substance in each step of the apparatus of Fig. 3. The apparatus can also be used under the reaction conditions in which one of the unreacted alcohol remains and a by-product of methyl benzoate or methyl carbamate is formed. The basic structure is the same as that of Fig. 1 described above, but the extract 17 extracted by the first extraction column 2 contains methyl carbamate and methyl benzoate in addition to carbonate, unreacted benzonitrile or alkane. In the first extraction column 3, the boiling point of each substance is 90 ° C (for example, dimethyl carbonate), 215 ° C (2-cyanopyridine), 69 ° C (for example, hexane), 65 ° C (for example, methanol), 177 ° C ( Methyl urethane), 233 ° C (methyl benzoate), staged the temperature to 180 ° C This is carried out by distillation, which is separated into a carbonate 19 of the product, a mixture 33 of an alkane for extraction and an unreacted monohydric alcohol, and a methyl carbamate 32. Further, after distillation, it is cooled to a temperature of 30 to 100 ° C, whereby methyl benzoate having a melting point of 103 ° C is solidified, and solid-liquid separation can be carried out by a filter 30 or the like, and can be separated into unreacted benzonitrile 20 and benzene. Methyl formate 31. Further, since most of the mixture 33 of the alkane and the monohydric alcohol is an alkane, it can be reused as a solvent for extraction.

實施例 Example

以下,利用實施例更詳盡地說明本發明,但本發明不受此等實施例所侷限。首先,就氰吡啶之製造方法的實施例及比較例予以說明。 Hereinafter, the present invention will be described in more detail by way of examples, but the invention is not limited by the examples. First, examples and comparative examples of the method for producing cyanopyridine will be described.

(實施例1) (Example 1)

將成為載體之SiO2(FUJI SILYSIA CHEMICAL LTD.製,CARiACT,G-6,表面積:535m2/g)整粒到100mesh以下,以700℃預燒成約1小時。之後,為了載持鹼金屬之Na,使用Na2CO3(關東化學製,特級)調整水溶液使Na金屬載持量最終成為0.5mmol/g,再浸漬到SiO2中。之後,於110℃下乾燥約6小時,再以500℃燒成約3小時而獲得Na2O/SiO2催化劑。 SiO 2 (CARJI, G-6, surface area: 535 m 2 /g, manufactured by FUJI SILYSIA CHEMICAL LTD.) was granulated to 100 mesh or less, and pre-fired at 700 ° C for about 1 hour. Then, in order to carry Na of an alkali metal, Na 2 CO 3 (manufactured by Kanto Chemical Co., Ltd., special grade) was used to adjust the aqueous solution so that the Na metal loading amount was finally 0.5 mmol/g, and then immersed in SiO 2 . Thereafter, it was dried at 110 ° C for about 6 hours, and further calcined at 500 ° C for about 3 hours to obtain a Na 2 O/SiO 2 catalyst.

於此,於試管中導入磁攪拌器、上述催化劑(0.1g)、2-吡啶甲醯胺(2-PA,1mmol)及對稱三甲苯(20ml),連接已充填有分子篩4A(已於300℃下事前乾燥1小時)之索氏萃取器、李必氏冷卻器(Liebig condenser),將冷卻器溫度設定為10℃,磁攪拌裝置設定為約200℃、600rpm。以Ar氣沖洗冷 卻器、索氏萃取管及試管內部後,以溶液開始蒸發之時間作為反應開始時間,使其反應24小時。 Here, a magnetic stirrer, the above catalyst (0.1 g), 2-pyridinecarboxamide (2-PA, 1 mmol) and symmetrical trimethylbenzene (20 ml) were introduced into a test tube, and the mixture was filled with molecular sieve 4A (already at 300 ° C). A Soxhlet extractor and a Liebig condenser which were dried for 1 hour beforehand, the cooler temperature was set to 10 ° C, and the magnetic stirring device was set to about 200 ° C and 600 rpm. Rinse with Ar gas After the apparatus, the Soxhlet extraction tube and the inside of the test tube, the reaction was started for 24 hours with the time when the solution started to evaporate.

反應後,將試管(溶液)冷卻至室溫,於反應溶液中加入乙醇20ml及內部標準物質之蒽(0.1g)後,採取樣本並以GC-MS(氣體層析-質量分析計)定性分析,以FID-GC定量分析。結果如表1所示,2-氰吡啶(2-CP)產生了0.42mmol。副產物僅有水,產率為42%,選擇率為100%。 After the reaction, the test tube (solution) was cooled to room temperature, and 20 ml of ethanol and hydrazine (0.1 g) of the internal standard substance were added to the reaction solution, and then the sample was taken and qualitatively analyzed by GC-MS (gas chromatography-mass spectrometry). , quantitative analysis by FID-GC. The results are shown in Table 1. 2-Cyanopyridine (2-CP) produced 0.42 mmol. The by-product was only water, the yield was 42%, and the selectivity was 100%.

(實施例2) (Example 2)

雖與實施例1相同,但在調製催化劑時,使用Li2CO3(關東化學製,特級)調整水溶液使Li金屬載持量最終成為0.5mmol/g,再浸漬到SiO2中。之後,於110℃下乾燥約6小時,再於500℃下燒成約3小時,獲得Li2O/SiO2催化劑。除了使用Li2O/SiO2催化劑之外,利用與實施例1相同方式從2-PA製出2-CP。其結果如表1所示,2-CP生成了0.43mmol。副產物僅有水,產率為43%,選擇率為100%。 In the same manner as in the first embodiment, when the catalyst was prepared, the aqueous solution was adjusted using Li 2 CO 3 (manufactured by Kanto Chemical Co., Ltd.) to finally bring the Li metal supporting amount to 0.5 mmol/g, and then immersed in SiO 2 . Thereafter, it was dried at 110 ° C for about 6 hours, and further baked at 500 ° C for about 3 hours to obtain a Li 2 O/SiO 2 catalyst. 2-CP was produced from 2-PA in the same manner as in Example 1 except that the Li 2 O/SiO 2 catalyst was used. The results are shown in Table 1, and 2-CP produced 0.43 mmol. The by-product was only water, the yield was 43%, and the selectivity was 100%.

(實施例3) (Example 3)

雖與實施例1相同,但在調製催化劑時,使用K2CO3(關東化學製,特級)調整水溶液使K金屬載持量最終成為0.5mmol/g,再浸漬到SiO2中。之後,於110℃下乾燥約6小時,再於500℃下燒成約3小時,獲得K2O/SiO2催化劑。除了使用K2O/SiO2催化劑之外,利用與實施例1相同方式從2-PA製出2-CP。其結果如表1所示,2-CP生成了0.42mmol。副產物僅有水,產率為42%,選擇率為100%。 In the same manner as in the first embodiment, in the preparation of the catalyst, K 2 CO 3 (manufactured by Kanto Chemical Co., Ltd., special grade) was used to adjust the aqueous solution so that the K metal loading amount was finally 0.5 mmol/g, and was further immersed in SiO 2 . Thereafter, it was dried at 110 ° C for about 6 hours, and further baked at 500 ° C for about 3 hours to obtain a K 2 O/SiO 2 catalyst. 2-CP was produced from 2-PA in the same manner as in Example 1 except that the K 2 O/SiO 2 catalyst was used. The results are shown in Table 1, and 2-CP produced 0.42 mmol. The by-product was only water, the yield was 42%, and the selectivity was 100%.

(實施例4) (Example 4)

雖與實施例1相同,但在調製催化劑時,使用Rb2CO3(關東化學製,特級)調整水溶液使Rb金屬載持量最終成為0.5mmol/g,再浸漬到SiO2中。之後,於110℃下乾燥約6小時,再於500℃下燒成約3小時,獲得Rb2O/SiO2催化劑。除了使用Rb2O/SiO2催化劑之外,利用與實施例1相同方式從2-PA製出2-CP。其結果如表1所示,2-CP生成了0.43mmol。副產物僅有水,產率為43%,選擇率為100%。 In the same manner as in the first embodiment, when the catalyst was prepared, the aqueous solution was adjusted using Rb 2 CO 3 (manufactured by Kanto Chemical Co., Ltd.) to finally bring the Rb metal supporting amount to 0.5 mmol/g, and then immersed in SiO 2 . Thereafter, it was dried at 110 ° C for about 6 hours, and further baked at 500 ° C for about 3 hours to obtain an Rb 2 O/SiO 2 catalyst. 2-CP was produced from 2-PA in the same manner as in Example 1 except that the Rb 2 O/SiO 2 catalyst was used. The results are shown in Table 1, and 2-CP produced 0.43 mmol. The by-product was only water, the yield was 43%, and the selectivity was 100%.

(實施例5) (Example 5)

雖與實施例1相同,但在調製催化劑時,使用Cs2CO3(關東化學製,4N)調整水溶液使Cs金屬載持量最終成為0.5mmol/g,再浸漬到SiO2中。之後,於110℃下乾燥約6小時,再於500℃下燒成約3小時,獲得Cs2O/SiO2催化劑。除了使用Cs2O/SiO2催化劑之外,利用與實施例1相同方式從2-PA製出2-CP。其結果如表1所示,2-CP生成了0.45mmol。副產物僅有水,產率為45%,選擇率為100%。 In the same manner as in the first embodiment, when the catalyst was prepared, the aqueous solution was adjusted with Cs 2 CO 3 (manufactured by Kanto Chemical Co., Ltd., 4N) to finally carry the Cs metal supporting amount to 0.5 mmol/g, and then immersed in SiO 2 . Thereafter, it was dried at 110 ° C for about 6 hours, and further baked at 500 ° C for about 3 hours to obtain a Cs 2 O/SiO 2 catalyst. 2-CP was produced from 2-PA in the same manner as in Example 1 except that the Cs 2 O/SiO 2 catalyst was used. The results are shown in Table 1, and 2-CP produced 0.45 mmol. The by-product was only water, the yield was 45%, and the selectivity was 100%.

(實施例6) (Example 6)

雖與實施例1相同,但在調製催化劑時,使用Na2CO3(關東化學製,特級)、K2CO3(關東化學製,特級)並使莫耳比變更以調整水溶液,使Na金屬載持量與K金屬載持量之總量最終成為0.5mmol/g,再浸漬到SiO2中。之後,於110℃下 乾燥約6小時,再於500℃下燒成約3小時,獲得Na2O-K2O/SiO2催化劑。除了使用Na2O-K2O/SiO2催化劑之外,利用與實施例1相同方式從2-PA製出2-CP。其結果如表2所示,任一莫耳比均生成了2-CP,副產物僅有水,產率為41~43%,選擇率為100%。從上述結果得知,可因應市場價格來變更鹼金屬使用量。 In the same manner as in the first embodiment, in the preparation of the catalyst, Na 2 CO 3 (manufactured by Kanto Chemical Co., Ltd., special grade), K 2 CO 3 (manufactured by Kanto Chemical Co., Ltd., special grade) was used, and the molar ratio was changed to adjust the aqueous solution to make the Na metal. The total amount of the supported amount and the K metal supporting amount finally became 0.5 mmol/g, and was further immersed in SiO 2 . Thereafter, it was dried at 110 ° C for about 6 hours and then calcined at 500 ° C for about 3 hours to obtain a Na 2 OK 2 O/SiO 2 catalyst. 2-CP was produced from 2-PA in the same manner as in Example 1 except that the Na 2 OK 2 O/SiO 2 catalyst was used. The results are shown in Table 2. All of the molar ratios produced 2-CP, the by-product only water, the yield was 41 to 43%, and the selectivity was 100%. From the above results, it is known that the amount of alkali metal used can be changed in response to market prices.

(比較例1) (Comparative Example 1)

除了催化劑僅使用已整粒到100mesh以下且經700℃預燒成約1小時之SiO2(FUJI SILYSIA CHEMICAL LTD.製,CARiACT,G-6,表面積:535m2/g)之外均與實施例1相同。其結果如表3所示,2-CP僅生成0.03mmol,活性非常低。 Except for the catalyst, only SiO 2 (manufactured by FUJI SILYSIA CHEMICAL LTD., CARiACT, G-6, surface area: 535 m 2 /g) which had been sized to 100 mesh or less and pre-fired at 700 ° C for about 1 hour was used. 1 is the same. The results are shown in Table 3. 2-CP produced only 0.03 mmol, and the activity was very low.

(比較例2) (Comparative Example 2)

除了催化劑僅使用1mmol之Na2CO3(關東化學製,特級)之外均與實施例1相同。其結果如表3所示,完全未生成2-CP。 The same procedure as in Example 1 was carried out except that only 1 mmol of Na 2 CO 3 (manufactured by Kanto Chemical Co., Ltd.) was used. As a result, as shown in Table 3, 2-CP was not generated at all.

(比較例3) (Comparative Example 3)

除了催化劑僅使用1mmol之Li2CO3(關東化學製,特級)之外均與實施例1相同。其結果如表3所示,2-CP僅生成了0.01mmol。 The same procedure as in Example 1 was carried out except that only 1 mmol of Li 2 CO 3 (manufactured by Kanto Chemical Co., Ltd.) was used. The results are shown in Table 3, and 2-CP produced only 0.01 mmol.

(比較例4) (Comparative Example 4)

除了催化劑僅使用1mmol之K2CO3(關東化學製,特級)之外均與實施例1相同。其結果如表3所示,完全未生成2-CP。 The same procedure as in Example 1 was carried out except that only 1 mmol of K 2 CO 3 (manufactured by Kanto Chemical Co., Ltd.) was used as the catalyst. As a result, as shown in Table 3, 2-CP was not generated at all.

(比較例5) (Comparative Example 5)

除了催化劑僅使用1mmol之Rb2CO3(關東化學製,特級)之外均與實施例1相同。其結果如表3所示,幾乎未生成2-CP。 The same procedure as in Example 1 was carried out except that only 1 mmol of Rb 2 CO 3 (manufactured by Kanto Chemical Co., Ltd.) was used as the catalyst. As a result, as shown in Table 3, almost no 2-CP was produced.

(比較例6) (Comparative Example 6)

除了催化劑僅使用1mmol之Cs2CO3(關東化學製,4N)之外均與實施例1相同。其結果如表3所示,2-CP僅生成0.01mmol,活性非常低。 The same procedure as in Example 1 was carried out except that only 1 mmol of Cs 2 CO 3 (manufactured by Kanto Chemical Co., Ltd., 4N) was used. The results are shown in Table 3. The 2-CP produced only 0.01 mmol, and the activity was very low.

從以上結果可知,於SiO2載體上載持有鹼金屬氧化物之催化劑甚有效果。 From the above results, it is understood that the catalyst in which the alkali metal oxide is supported on the SiO 2 carrier is effective.

(實施例7) (Example 7)

於調製催化劑時,除了使最終之Na金屬載持量如表4所示並導入5mmol之2-吡啶甲醯胺(PA)及令反應時間為4小時之外,均與實施例1相同。將其結果顯示於表4中。 In the preparation of the catalyst, the same procedure as in Example 1 was carried out except that the final Na metal loading amount was as shown in Table 4, and 5 mmol of 2-pyridinecarboxamide (PA) was introduced and the reaction time was 4 hours. The results are shown in Table 4.

由上述結果可知,Na載持量為0.1~1mmol/g時顯示出高活性,尤以0.5mmol/g程度為合宜之載持量。 From the above results, it was found that when the Na loading amount is 0.1 to 1 mmol/g, high activity is exhibited, and particularly preferably 0.5 mmol/g is a suitable carrying amount.

(實施例8) (Example 8)

於調製催化劑時,除了載體使用已整粒到100mesh以下且經500℃預燒成約3小時之CeO2(第一稀元素製,HS,表面積:74m2/g)之外均與實施例5相同。其結果如表5所示,2-CP生成了0.11mmol。副產物僅有水,產率為11%,選擇率為100%。 In the preparation of the catalyst, except that the carrier was granulated to 100 mesh or less and calcined at 500 ° C for about 3 hours of CeO 2 (manufactured by the first rare element, HS, surface area: 74 m 2 /g), and Example 5 the same. The results are shown in Table 5, and 2-CP produced 0.11 mmol. The by-product was only water, the yield was 11%, and the selectivity was 100%.

(實施例9) (Example 9)

於調製催化劑時,除了載體使用已整粒到100mesh以下且未經預燒成之ZrO2(第一稀元素製,表面積:88m2/g)之外均與實施例5相同。其結果如表5所示,2-CP生成了0.10mmol。副產物僅有水,產率為10%,選擇率為100%。 When the catalyst was prepared, the same procedure as in Example 5 was carried out except that ZrO 2 (manufactured by the first rare element, surface area: 88 m 2 /g) which had been sized to less than 100 mesh and not pre-fired was used. The results are shown in Table 5, and 2-CP produced 0.10 mmol. The by-product was only water, the yield was 10%, and the selectivity was 100%.

(實施例10) (Embodiment 10)

於調製催化劑時,由於載體使用CeO2-ZrO2固溶體之故,於已溶有Ce(NO3)3(關東化學製)與Zr(NO3)4(關東化學製)且Ce為20原子量%之溶液中導入NaOH水溶液使其生成沉澱物,之後將沉澱物過濾、水洗,並於1000℃且空氣環境下燒成3小時後,獲得粉末狀之固溶體(表面積:65m2/g)。將本固溶體整粒到100mesh以下,以500℃預燒成約3小時,除 此以外與實施例5相同。結果如表5所示,2-CP生成了0.11mmol。副產物僅有水,產率為11%,選擇率為100%。 In the preparation of the catalyst, since the carrier is a CeO 2 -ZrO 2 solid solution, Ce(NO 3 ) 3 (manufactured by Kanto Chemical Co., Ltd.) and Zr(NO 3 ) 4 (manufactured by Kanto Chemical Co., Ltd.) are dissolved and Ce is 20 An aqueous solution of NaOH was introduced into a solution of an atomic weight to form a precipitate, and then the precipitate was filtered, washed with water, and calcined at 1000 ° C for 3 hours in an air atmosphere to obtain a powdery solid solution (surface area: 65 m 2 /g). ). The solid solution was granulated to 100 m or less and calcined at 500 ° C for about 3 hours, except that it was the same as in Example 5. The results are shown in Table 5, and 2-CP produced 0.11 mmol. The by-product was only water, the yield was 11%, and the selectivity was 100%.

(比較例7) (Comparative Example 7)

於調製催化劑時,除了載體使用已整粒到100mesh以下且經1150℃預燒成約3小時之α-Al2O3(住友化學製,KHO-24,表面積:10m2/g)之外均與實施例5相同。其結果如表5所示,2-CP僅生成了0.03mmol,活性非常低。 In the preparation of the catalyst, the α-Al 2 O 3 (KHO-24, surface area: 10 m 2 /g, manufactured by Sumitomo Chemical Co., Ltd.) which has been sized to less than 100 mesh and calcined at 1150 ° C for about 3 hours is used. The same as in the fifth embodiment. As a result, as shown in Table 5, 2-CP produced only 0.03 mmol, and the activity was extremely low.

(比較例8) (Comparative Example 8)

於調製催化劑時,除了載體使用已整粒到100mesh以下且未經預燒成之MgO(宇部興產製,500A,表面積:30m2/g)之外均與實施例5相同。其結果如表5所示,2-CP僅生成了0.004mmol,幾乎不反應。 When the catalyst was prepared, the same procedure as in Example 5 was carried out except that MgO (manufactured by Ube Industries, Ltd., 500 A, surface area: 30 m 2 /g) which had been sized to 100 mesh or less and not pre-fired was used. As a result, as shown in Table 5, 2-CP produced only 0.004 mmol, and almost did not react.

(實施例11) (Example 11)

除了導入5mmol之反應物2-吡啶甲醯胺(2-PA)並令反應時間如表6所示以外,均與實施例1相同。結果顯示於表6。 The same procedure as in Example 1 was carried out except that 5 mmol of the reactant 2-pyridinecarboxamide (2-PA) was introduced and the reaction time was as shown in Table 6. The results are shown in Table 6.

經由以上結果,得以確認反應時間越長2-氰吡啶之生成量越是増加,且在反應500小時的情況下,產率為90%,選擇率為99%。 From the above results, it was confirmed that the longer the reaction time, the more the amount of 2-cyanopyridine produced was increased, and in the case of the reaction for 500 hours, the yield was 90%, and the selectivity was 99%.

(實施例12) (Embodiment 12)

除了溶劑使用鄰二甲苯、間二甲苯、對二甲苯之外,均在與實施例1相同之條件下進行反應而從2-PA製出2-CP。其結果如表4所示,無論以任一載體,均生成了一定量之2-CP。 Except that o-xylene, m-xylene, and p-xylene were used as the solvent, the reaction was carried out under the same conditions as in Example 1 to prepare 2-CP from 2-PA. The results are shown in Table 4, and a certain amount of 2-CP was produced regardless of the carrier.

(實施例13) (Example 13)

除了以菸鹼醯胺、異鹼醯胺取代2-PA作為反應物之外,於與實施例1相同之條件下進行反應,製出3-氰吡啶(3-CP)及4-氰吡啶(4-CP)。其結果如表8所示,無論是以菸鹼醯胺及異菸鹼醯胺中之任一者為反應物皆均生成了CP,得知本發明之在SiO2等上載持有鹼金屬氧化物的催化劑在利用醯胺脫水反應製造氰吡啶上甚是有效。 The reaction was carried out under the same conditions as in Example 1 except that nicotinamide or iso-indolylamine was used in place of 2-PA as a reactant to prepare 3-cyanopyridine (3-CP) and 4-cyanopyridine ( 4-CP). As a result, as shown in Table 8, whether CP was formed as a reactant in any of nicotine amide and isonicotinium amide, it was found that the present invention adsorbed alkali metal oxide on SiO 2 or the like. The catalyst of the catalyst is effective in the production of cyanopyridine by the dehydration reaction of guanamine.

(比較例9) (Comparative Example 9)

在調製催化劑時,使用CaCO3(關東化學製,特級)調整 水溶液使Ca金屬載持量最終成為0.5mmol/g,再浸漬到SiO2中。之後,於110℃下乾燥約6小時,再於500℃下燒成約3小時,獲得CaO/SiO2催化劑。除了使用CaO/SiO2催化劑以外均與實施例1相同。其結果如表8所示,2-CP僅生成了0.06mmol,活性非常低。 In the preparation of the catalyst, the aqueous solution was adjusted using CaCO 3 (manufactured by Kanto Chemical Co., Ltd.) to finally bring the amount of Ca metal supported to 0.5 mmol/g, and then immersed in SiO 2 . Thereafter, it was dried at 110 ° C for about 6 hours and then calcined at 500 ° C for about 3 hours to obtain a CaO/SiO 2 catalyst. The same as Example 1 except that the CaO/SiO 2 catalyst was used. The results are shown in Table 8. The 2-CP produced only 0.06 mmol, and the activity was very low.

(比較例10) (Comparative Example 10)

在調製催化劑時,使用BaCO3(關東化學製,特級)調整水溶液使Ba金屬載持量最終成為0.5mmol/g,再浸漬到SiO2中。之後,於110℃下乾燥約6小時,再於500℃下燒成約3小時,獲得BaO/SiO2催化劑。除了使用BaO/SiO2催化劑以外均與實施例1相同。其結果如表8所示,2-CP僅生成了0.07mmol,活性非常低。 In the preparation of the catalyst, BaCO 3 (manufactured by Kanto Chemical Co., Ltd., special grade) was used to adjust the aqueous solution so that the Ba metal loading amount was finally 0.5 mmol/g, and it was further immersed in SiO 2 . Thereafter, it was dried at 110 ° C for about 6 hours, and further baked at 500 ° C for about 3 hours to obtain a BaO/SiO 2 catalyst. The same as Example 1 except that the BaO/SiO 2 catalyst was used. As a result, as shown in Table 8, 2-CP produced only 0.07 mmol, and the activity was extremely low.

經由以上結果得以確認,載持與鹼金屬氧化物同樣會呈鹼性之鹼土族金屬氧化物的催化劑活性甚低,而得知在SiO2上載持有鹼金屬氧化物之催化劑甚是有效。 From the above results, it was confirmed that the catalyst activity of the alkaline earth metal oxide which is alkaline as well as the alkali metal oxide is very low, and it is found that the catalyst which holds the alkali metal oxide on SiO 2 is effective.

(比較例11) (Comparative Example 11)

在調製催化劑時,使用NH4VO3(Sigma-Aldrich製)調整水溶液使V金屬載持量最終成為0.5mmol/g,再浸漬到SiO2中。之後,於110℃下乾燥約6小時,再於500℃下燒成約3小時,獲得V2O5/SiO2催化劑。除了使用V2O5/SiO2催化劑以外均與實施例1相同。其結果如表7所示,2-CP僅生成了0.06mmol,與比較例1僅使用SiO2之情況相同位準,活性非常低。 In the preparation of the catalyst, the aqueous solution was adjusted with NH 4 VO 3 (manufactured by Sigma-Aldrich) to finally bring the V metal loading amount to 0.5 mmol/g, and then immersed in SiO 2 . Thereafter, it was dried at 110 ° C for about 6 hours, and further baked at 500 ° C for about 3 hours to obtain a V 2 O 5 /SiO 2 catalyst. The same as Example 1 except that the V 2 O 5 /SiO 2 catalyst was used. As a result, as shown in Table 7, 2-CP produced only 0.06 mmol, which was the same level as in the case of using only SiO 2 in Comparative Example 1, and the activity was extremely low.

由以上結果得知,即使將在苯甲醯胺之脫水反應中具有高活性之V系催化劑使用於2-吡啶甲醯胺之脫水反應,仍是幾乎不會進行反應。 From the above results, it has been found that even if a V-based catalyst having high activity in the dehydration reaction of benzamidine is used in the dehydration reaction of 2-pyridinecarbamide, the reaction is hardly carried out.

由於上述實施例僅副生成了2-氰吡啶與水而未生成其他之副產物,因此可藉由蒸餾來單獨回收目的生成物之2-氰吡啶、副產物之水以及未反應之2-吡啶甲醯胺,並將未反應之2-吡啶甲醯胺再次用作反應物。 Since the above examples only produce 2-cyanopyridine and water without generating other by-products, the 2-cyanopyridine of the desired product, the water of the by-product, and the unreacted 2-pyridine can be separately recovered by distillation. Formamidine and unreacted 2-pyridinecarbamamine was reused as the reactant.

(實施例14) (Example 14)

接著,就苯甲腈之實施例及比較例進行說明。將成為載體之SiO2(FUJI SILYSIA CHEMICAL LTD.製,CARiACT,G-6,表面積:535m2/g)整粒到100mesh以下,以700℃預燒成約1小時。之後,為了載持金屬Mo,使用(NH4)6Mo7O24(關東化學製、特級)調整水溶液使Mo金屬載持量最終成為0.5mmol/g,再浸漬到SiO2中。之後,於110℃下乾燥約6小時,再以500℃燒成約3小時而獲得MoO3/SiO2催化劑。 Next, examples and comparative examples of benzonitrile will be described. SiO 2 (CARJI, G-6, surface area: 535 m 2 /g, manufactured by FUJI SILYSIA CHEMICAL LTD.) was granulated to 100 mesh or less, and pre-fired at 700 ° C for about 1 hour. Then, in order to carry the metal Mo, the aqueous solution was adjusted with (NH 4 ) 6 Mo 7 O 24 (manufactured by Kanto Chemical Co., Ltd.) to finally bring the Mo metal loading amount to 0.5 mmol/g, and then immersed in SiO 2 . Thereafter, it was dried at 110 ° C for about 6 hours, and further baked at 500 ° C for about 3 hours to obtain a MoO 3 /SiO 2 catalyst.

於此,於試管中導入磁攪拌器、上述催化劑(0.1g)、苯甲醯胺(以下記為BA,20mmol)及對稱三甲苯(20ml),連接已充填有分子篩4A(已於300℃下事前乾燥1小時)之索氏萃取器、李必氏冷卻器,將冷卻器溫度設定為10℃,磁攪拌裝置設定為約200℃、600rpm。以Ar氣沖洗冷卻器、索氏萃取管及試管內部後,以溶液開始蒸發之時間作為反應開 始時間,使其反應24小時。 Here, a magnetic stirrer, the above catalyst (0.1 g), benzamide (hereinafter referred to as BA, 20 mmol) and symmetrical trimethylbenzene (20 ml) were introduced into a test tube, and the connection was filled with molecular sieve 4A (at 300 ° C). The Soxhlet extractor and the Leipzig cooler were dried for 1 hour beforehand, the cooler temperature was set to 10 ° C, and the magnetic stirring device was set to about 200 ° C and 600 rpm. After flushing the cooler, the Soxhlet extraction tube and the inside of the test tube with Ar gas, the time at which the solution starts to evaporate is used as a reaction. At the beginning, it was allowed to react for 24 hours.

反應後,將試管(溶液)冷卻至室溫,於反應溶液中加入乙醇20ml及內部標準物質之蒽(0.1g)後,採取樣本並以GC-MS(氣體層析-質量分析計)定性分析,以FID-GC定量分析。結果如表9所示,苯甲腈(以下記為BN)產生了5mmol。副產物僅有水,產率為25%,選擇率為100%。 After the reaction, the test tube (solution) was cooled to room temperature, and 20 ml of ethanol and hydrazine (0.1 g) of the internal standard substance were added to the reaction solution, and then the sample was taken and qualitatively analyzed by GC-MS (gas chromatography-mass spectrometry). , quantitative analysis by FID-GC. As a result, as shown in Table 9, benzonitrile (hereinafter referred to as BN) produced 5 mmol. The by-product was only water, the yield was 25%, and the selectivity was 100%.

(實施例15) (Example 15)

雖與實施例14相同,但在調製催化劑時,使用(NH4)6W12O41(關東化學製,鹿一級)調整水溶液使W金屬載持量最終成為0.5mmol/g,再浸漬到SiO2中。之後,於110℃下乾燥約6小時,再於500℃下燒成約3小時,獲得WO3/SiO2催化劑。除了使用WO3/SiO2催化劑之外,利用與實施例14相同方式從BA製出BN。其結果如表9所示,BN生成了3mmol。副產物僅有水,產率為15%,選擇率為100%。 In the same manner as in Example 14, when the catalyst was prepared, the aqueous solution was adjusted using (NH 4 ) 6 W 12 O 41 (manufactured by Kanto Chemical Co., Ltd., deer grade) to finally carry the W metal support amount to 0.5 mmol/g, and then immersed in SiO. 2 in. Thereafter, it was dried at 110 ° C for about 6 hours and then calcined at 500 ° C for about 3 hours to obtain a WO 3 /SiO 2 catalyst. BN was produced from BA in the same manner as in Example 14 except that the WO 3 /SiO 2 catalyst was used. The results are shown in Table 9, and BN produced 3 mmol. The by-product was only water, the yield was 15%, and the selectivity was 100%.

(實施例16) (Embodiment 16)

雖與實施例14相同,但在調製催化劑時,使用NH4ReO4(三津和化學藥品製)調整水溶液使Re載持量最終成為0.5mmol/g,再浸漬到SiO2中。之後,於110℃下乾燥約6小時,再於500℃下燒成約3小時,獲得Re2O7/SiO2催化劑。除了使用Re2O7/SiO2催化劑之外,利用與實施例14相同方式從苯甲醯胺(BA)製出苯甲腈(BN)。其結果如表9所示,BN生成了1mmol。副產物僅有水,產率為5%,選擇率為100%。 In the same manner as in Example 14, in the preparation of the catalyst, the aqueous solution was adjusted using NH 4 ReO 4 (manufactured by Sanjin and Chemical Co., Ltd.) so that the amount of Re supported was finally 0.5 mmol/g, and further immersed in SiO 2 . Thereafter, it was dried at 110 ° C for about 6 hours, and further baked at 500 ° C for about 3 hours to obtain a Re 2 O 7 /SiO 2 catalyst. Benzoonitrile (BN) was prepared from benzamide (BA) in the same manner as in Example 14 except that the Re 2 O 7 /SiO 2 catalyst was used. The results are shown in Table 9, and BN produced 1 mmol. The by-product was only water, the yield was 5%, and the selectivity was 100%.

(實施例17) (Example 17)

雖與實施例14相同,但在調製催化劑時,使用TiCl3(關 東化學製,鹿一級)調整水溶液使Ti載持量最終成為0.5mmol/g,再浸漬到SiO2中。之後,於110℃下乾燥約6小時,再於500℃下燒成約3小時,獲得TiO2/SiO2催化劑。除了使用TiO2/SiO2催化劑之外,利用與實施例14相同方式從BA製出BN。其結果如表9所示,BN生成了1mmol。副產物僅有水,產率為5%,選擇率為100%。 Although the same as in Example 14, when the catalyst was prepared, TiCl 3 (manufactured by Kanto Chemical Co., Ltd., deer grade) was used. The aqueous solution was adjusted so that the Ti loading amount eventually became 0.5 mmol/g, and was further immersed in SiO 2 . Thereafter, it was dried at 110 ° C for about 6 hours and then calcined at 500 ° C for about 3 hours to obtain a TiO 2 /SiO 2 catalyst. BN was produced from BA in the same manner as in Example 14 except that the TiO 2 /SiO 2 catalyst was used. The results are shown in Table 9, and BN produced 1 mmol. The by-product was only water, the yield was 5%, and the selectivity was 100%.

(實施例18) (Embodiment 18)

雖與實施例14相同,但在調製催化劑時,使用(NH4)3(NbO(C2O4)3)(Sigma-Aldrich製,4N)調整水溶液使Nb載持量最終成為0.5mmol/g,再浸漬到SiO2中。之後,於110℃下乾燥約6小時,再於500℃下燒成約3小時,獲得Nb2O5/SiO2催化劑。除了使用Nb2O5/SiO2催化劑之外,利用與實施例14相同方式從BA製出BN。其結果如表9所示,BN生成了1mmol。副產物僅有水,產率為5%,選擇率為100%。 Although the same as in Example 14, when the catalyst was prepared, (NH 4 ) 3 (NbO(C 2 O 4 ) 3 ) (manufactured by Sigma-Aldrich, 4N) was used. The aqueous solution was adjusted so that the Nb loading amount eventually became 0.5 mmol/g, and was further immersed in SiO 2 . Thereafter, it was dried at 110 ° C for about 6 hours, and further baked at 500 ° C for about 3 hours to obtain a Nb 2 O 5 /SiO 2 catalyst. BN was produced from BA in the same manner as in Example 14 except that the Nb 2 O 5 /SiO 2 catalyst was used. The results are shown in Table 9, and BN produced 1 mmol. The by-product was only water, the yield was 5%, and the selectivity was 100%.

(實施例19) (Embodiment 19)

將成為載體之SiO2(FUJI SILYSIA CHEMICAL LTD.製,CARiACT,G-3,表面積:700m2/g)整粒到100mesh以下,以700℃預燒成約1小時。之後,在調製催化劑之過程中, 使用(NH4)6Mo7O24(關東化學製,特級)調整水溶液使Mo載持量最終如表10所示,再浸漬到SiO2中。之後,於110℃下乾燥約6小時,再以500℃燒成約3小時而獲得MoO3/SiO2催化劑。除了使用MoO3/SiO2催化劑之外,利用與實施例14相同方式從BA製出BN。其結果如表10所示,任一莫耳比均生成了BN,副產物僅有水,生成量雖會隨著Mo載持量增加而增多,但到一定程度以上即可見有飽和之傾向。 SiO 2 (CARiACT, G-3, surface area: 700 m 2 /g, manufactured by FUJI SILYSIA CHEMICAL LTD.) was granulated to 100 mesh or less, and calcined at 700 ° C for about 1 hour. Thereafter, during the preparation of the catalyst, (NH 4 ) 6 Mo 7 O 24 (manufactured by Kanto Chemical Co., Ltd., special grade) was used to adjust the aqueous solution so that the Mo loading amount was finally immersed in SiO 2 as shown in Table 10. Thereafter, it was dried at 110 ° C for about 6 hours, and further baked at 500 ° C for about 3 hours to obtain a MoO 3 /SiO 2 catalyst. BN was produced from BA in the same manner as in Example 14 except that the MoO 3 /SiO 2 catalyst was used. As a result, as shown in Table 10, BN was formed in any of the molar ratios, and water was produced as a by-product, and the amount of production increased with the increase in the amount of Mo carried. However, the degree of saturation was observed to a certain extent or more.

(實施例20) (Embodiment 20)

載體使用TiO2(NIPPON AEROSIL CO.,LTD.製,P25,表面積:50m2/g)、ZrO2(第一稀元素製,表面積:88m2/g)、CeO2(第一稀元素製,表面積:74m2/g)、Al2O3(住友化學製,KHO,表面積:10m2/g)、碳黑(Cabot Corporation製,Vulcan,XC-72,表面積:254m2/g),並使用(NH4)6Mo7O24(關東化學製,特級)使Mo載持量為0.19mmol/g,浸漬到各載體中。使用如此調製之催化劑,利用與實施例14相同方式從BA製出BN。其結果如表11所示,無論以任一載體,均生成了一定量之BN。 As the carrier, TiO 2 (manufactured by NIPPON AEROSIL CO., LTD., P25, surface area: 50 m 2 /g), ZrO 2 (manufactured by the first rare element, surface area: 88 m 2 /g), and CeO 2 (manufactured by the first rare element, Surface area: 74 m 2 /g), Al 2 O 3 (manufactured by Sumitomo Chemical Co., Ltd., KHO, surface area: 10 m 2 /g), carbon black (manufactured by Cabot Corporation, Vulcan, XC-72, surface area: 254 m 2 /g), and used (NH 4 ) 6 Mo 7 O 24 (manufactured by Kanto Chemical Co., Ltd.) The Mo loading amount was 0.19 mmol/g, and it was immersed in each carrier. Using the catalyst thus prepared, BN was produced from BA in the same manner as in Example 14. The results are shown in Table 11, and a certain amount of BN was produced regardless of any of the carriers.

(實施例21) (Example 21)

除了溶劑使用鄰二甲苯、間二甲苯、對二甲苯、氯苯以外,均在與實施例14相同之條件下進行反應,從BA製出BN。其結果如表12所示,無論是以任一載體,皆生成了一定量之BN。 The reaction was carried out under the same conditions as in Example 14 except that o-xylene, m-xylene, p-xylene or chlorobenzene were used as the solvent, and BN was obtained from BA. The results are shown in Table 12, and a certain amount of BN was produced regardless of the carrier.

(實施例22) (Example 22)

除了不使用脫水劑之外,利用與實施例14完全相同之方式進行評估。結果,反應24小時後產率為10%,選擇率幾乎達到100%。 Evaluation was carried out in exactly the same manner as in Example 14 except that the dehydrating agent was not used. As a result, the yield was 10% after 24 hours of reaction, and the selectivity was almost 100%.

(比較例12) (Comparative Example 12)

除了使用Mn(NO3)2、Ce(NH4)2(NO3)6及ZrO(NO3)2之各水溶液來載持0.5mmol之Mn、Ce、Zr以作為催化劑之外,均與實施例14相同。其結果則是,無論任一情況皆未檢測出BN而未顯示出活性。 Except that each of Mn(NO 3 ) 2 , Ce(NH 4 ) 2 (NO 3 ) 6 and ZrO(NO 3 ) 2 aqueous solutions was used to carry 0.5 mmol of Mn, Ce, and Zr as catalysts, Example 14 is the same. As a result, no BN was detected in either case and no activity was exhibited.

(比較例13) (Comparative Example 13)

作為催化劑,使用NH4VO3(Sigma-Aldrich製)調整水溶 液,浸漬到SiO2中。之後,於110℃下乾燥約6小時,再於500℃下燒成約3小時,獲得V2O5/SiO2催化劑。除了使用V2O5/SiO2催化劑以外均與實施例14相同。結果,BN僅生成了0.01mmol,活性非常低。由本結果得知,即使是如同已有載述於非專利文獻5之V系催化劑,在如同本反應條件之溫和條件下,苯甲醯胺之脫水反應仍是幾乎不會進行。 As a catalyst, an aqueous solution was adjusted using NH 4 VO 3 (manufactured by Sigma-Aldrich), and immersed in SiO 2 . Thereafter, it was dried at 110 ° C for about 6 hours, and further baked at 500 ° C for about 3 hours to obtain a V 2 O 5 /SiO 2 catalyst. The same as Example 14 except that the V 2 O 5 /SiO 2 catalyst was used. As a result, BN produced only 0.01 mmol, and the activity was very low. From the results, it is understood that even in the case of the V-based catalyst which has been described in Non-Patent Document 5, the dehydration reaction of benzamide is hardly carried out under mild conditions like the reaction conditions.

(比較例14) (Comparative Example 14)

除了催化劑僅使用已整粒到100mesh以下且經700℃下預燒成約1小時之MgO(宇部興產製,500A,表面積:28m2/g)以外,均與實施例14相同。結果,完全未生成BN。 The same procedure as in Example 14 was carried out except that MgO (manufactured by Ube Industries, Ltd., 500 A, surface area: 28 m 2 /g) which had been granulated to 100 mesh or less and calcined at 700 ° C for about 1 hour was used. As a result, BN was not generated at all.

由於上述實施例僅副生成了苯甲腈與水而未生成其他之副產物,因此可藉由蒸餾來單獨回收目的生成物之苯甲腈、副產物之水以及未反應之苯甲醯胺,並將未反應之苯甲醯胺再次用作反應物。 Since the above examples only produce benzonitrile and water without generating other by-products, the benzonitrile of the desired product, the water of the by-product, and the unreacted benzamide can be separately recovered by distillation. Unreacted benzamide was again used as a reactant.

(實施例23) (Example 23)

接著,就使用氰吡啶之碳酸酯之製造方法的實施例予以說明。使用顯示於圖1之製造裝置進行碳酸酯之製造。將CeO2(第一稀元素製,雜質濃度0.02%以下)於873K且空氣環境下燒成3小時,獲得粉末狀之固體催化劑。於此,在190ml之加熱釜(反應器)中導入磁攪拌器、上述固體催化劑(1mmol)、甲醇(100mmol)及2-氰吡啶(2-CP,50mmol),再以約5g之CO2沖洗加熱釜內之空氣3次後,導入預定量之CO2並昇壓。利用電熱圈(band heater)、加熱攪拌器(hot stirrer)將該加熱釜一邊攪拌一邊昇溫到120℃,並以到達目 的溫度之時間作為反應開始時間。於120℃下反應12小時後,將加熱釜水冷,冷卻到室溫後減壓並添加內部標準物質之1-已醇0.2mL,採取生成物並以GC(氣體層析法)分析。如此變更CO2之導入量及反應壓力,進行表13所示之試驗No.37~40。 Next, an example of a method for producing a carbonate of cyanopyridine will be described. The manufacture of the carbonate was carried out using the manufacturing apparatus shown in Fig. 1. CeO 2 (manufactured by the first rare element, impurity concentration 0.02% or less) was baked at 873 K in an air atmosphere for 3 hours to obtain a powdery solid catalyst. Here, a magnetic stirrer, the above solid catalyst (1 mmol), methanol (100 mmol), and 2-cyanopyridine (2-CP, 50 mmol) were introduced into a 190 ml heating kettle (reactor), and then rinsed with about 5 g of CO 2 . After heating the air in the kettle three times, a predetermined amount of CO 2 was introduced and boosted. The heating kettle was heated to 120 ° C while stirring with a band heater and a hot stirrer, and the time until the target temperature was reached was taken as the reaction start time. After reacting at 120 ° C for 12 hours, the autoclave was cooled to water, cooled to room temperature, and then reduced to dryness, and 0.2 mL of 1-hexanol as an internal standard substance was added, and the product was taken and analyzed by GC (gas chromatography). The amount of introduction of CO 2 and the reaction pressure were changed in this manner, and Test Nos. 37 to 40 shown in Table 13 were carried out.

其結果則是得以確認,即使在常壓以下之0.08MPa仍有碳酸二甲酯(DMC)生成,且甲醇基底(methanol base)下之DMC產率在0.08MPa時可得34.8%,在0.2MPa時可得44.4%,1MPa時可得58%,5MPa時則可得86%。又,副產物之2-吡啶甲醯胺(2-PA)之生成量與DMC大致同量,完全未檢測到除此之外的副產物。 As a result, it was confirmed that dimethyl carbonate (DMC) was formed even at 0.08 MPa below atmospheric pressure, and 34.8% of the DMC yield under the methanol base was 0.08 MPa at 0.2 MPa. It can be obtained at 44.4%, 58% at 1 MPa, and 86% at 5 MPa. Further, the amount of 2-pyridinecarboxamide (2-PA) produced as a by-product was approximately the same as that of DMC, and no by-products were detected at all.

於此,由於甲醇(醇類)基底之產率以化學量論比計係醇類:碳酸酯=2:1,而按下式算出。 Here, since the yield of the methanol (alcohol) substrate is calculated by a stoichiometric amount of alcohol: carbonate = 2:1, it is calculated by the following formula.

接著,於各試驗後之固液共存物質中加入己烷200ml並攪拌,以溶劑萃取後以過濾器過濾而分離為液體與固體。液體包含DMC、2-CP、甲醇、己烷,固體則包含2-PA 與CeO2。經己烷溶劑萃取後之液體成分藉由使溫度階段性地升溫到120℃程度之蒸餾方式而分離為DMC、2-CP、己烷及甲醇,成功回收了純度96%以上之DMC。此外,固體成分中之2-PA與CeO2在溶解於丙酮200ml後以過濾器過濾,藉此分離為CeO2與2-PA及丙酮,2-PA與丙酮進一步藉由蒸餾而各自分離,成功回收了純度97%以上之2-PA。 Next, 200 ml of hexane was added to the solid-liquid coexisting material after each test, and the mixture was stirred, extracted with a solvent, and filtered through a filter to separate into a liquid and a solid. The liquid contains DMC, 2-CP, methanol, hexane, and the solid contains 2-PA and CeO 2 . The liquid component extracted by the solvent of hexane was separated into DMC, 2-CP, hexane, and methanol by a distillation method in which the temperature was gradually raised to 120 ° C, and DMC having a purity of 96% or more was successfully recovered. Further, 2-PA and CeO 2 in the solid component were filtered in a filter after dissolving in 200 ml of acetone, thereby separating into CeO 2 and 2-PA and acetone, and 2-PA and acetone were further separated by distillation, respectively. 2-PA having a purity of 97% or more was recovered.

接著,就從所回收之2-PA再生為2-CP一事記載於下。將成為載體之SiO2(FUJI SILYSIA CHEMICAL LTD.製,CARiACT,G-6,表面積:535m2/g)整粒到100mesh以下,以700℃預燒成約1小時。之後,為了載持鹼金屬之Na,使用Na2CO3(關東化學製,特級)調整水溶液使Na金屬載持量最終成為0.5mmol/g,再浸漬到SiO2中。之後,於110℃下乾燥約6小時,再以500℃燒成約3小時而獲得Na2O/SiO2催化劑。於此,於試管中導入磁攪拌器、上述催化劑(0.1g)、生成DMC時副生成之2-PA及對稱三甲苯(20ml),連接已充填有分子篩4A(已於300℃下事前乾燥1小時)之索氏萃取器、李必氏冷卻器,將冷卻器溫度設定為10℃,磁攪拌裝置設定為約200℃、600rpm。以Ar氣沖洗冷卻器、索氏萃取管及試管內部後,以溶液開始蒸發之時間作為反應開始時間,使其反應500小時。反應後,將試管(溶液)冷卻至室溫,於反應溶液中加入乙醇20ml及內部標準物質之蒽(0.1g)後,採取樣本並以GC-MS(氣體層析-質量分析計)定性分析,以FID-GC定量分析。以此種方式,如表13所示般進行試驗No.37~40,結果2-CP分別生成了16.1、20.7、26.6、37.8mmol。 任一實驗之副產物皆僅有水,產率為90%,選擇率為100%。 Next, the reproduction from the recovered 2-PA to 2-CP is described below. SiO 2 (CARJI, G-6, surface area: 535 m 2 /g, manufactured by FUJI SILYSIA CHEMICAL LTD.) was granulated to 100 mesh or less, and pre-fired at 700 ° C for about 1 hour. Then, in order to carry Na of an alkali metal, Na 2 CO 3 (manufactured by Kanto Chemical Co., Ltd., special grade) was used to adjust the aqueous solution so that the Na metal loading amount was finally 0.5 mmol/g, and then immersed in SiO 2 . Thereafter, it was dried at 110 ° C for about 6 hours, and further calcined at 500 ° C for about 3 hours to obtain a Na 2 O/SiO 2 catalyst. Here, a magnetic stirrer, the above catalyst (0.1 g), a 2-PA formed by DMC and a symmetric trimethylbenzene (20 ml) were formed in a test tube, and the molecular sieve 4A was filled in the test tube (it was dried beforehand at 300 ° C) Hours) Soxhlet extractor, Leipzig cooler, the cooler temperature was set to 10 ° C, and the magnetic stirring device was set to about 200 ° C, 600 rpm. After rinsing the cooler, the Soxhlet extraction tube, and the inside of the test tube with Ar gas, the reaction was started for 500 hours as the reaction start time was started. After the reaction, the test tube (solution) was cooled to room temperature, and 20 ml of ethanol and hydrazine (0.1 g) of the internal standard substance were added to the reaction solution, and then the sample was taken and qualitatively analyzed by GC-MS (gas chromatography-mass spectrometry). , quantitative analysis by FID-GC. In this manner, Test Nos. 37 to 40 were carried out as shown in Table 13, and as a result, 2-CP produced 16.1, 20.7, 26.6, and 37.8 mmol, respectively. The by-product of either experiment was only water, the yield was 90%, and the selectivity was 100%.

將上述試驗後之固液共存物質於120℃加熱下以過濾器過濾,分離為液體與固體(催化劑)。液體包含2-CP、水、未反應之2-PA及對稱三甲苯。使該液體成分藉由使溫度階段性上升到180℃程度之蒸餾而分離為2-CP、水、未反應之2-PA及對稱三甲苯,成功回收了純度98%以上之2-CP。而後,所分離出之未反應之2-PA與對稱三甲苯可再次循環利用在2-PA之脫水反應中。 The solid-liquid coexisting substance after the above test was filtered with a filter under heating at 120 ° C to separate into a liquid and a solid (catalyst). The liquid contains 2-CP, water, unreacted 2-PA, and symmetrical trimethylbenzene. The liquid component was separated into 2-CP, water, unreacted 2-PA, and symmetrical trimethylbenzene by distillation in which the temperature was gradually increased to 180 ° C, and 2-CP having a purity of 98% or more was successfully recovered. Then, the separated unreacted 2-PA and symmetrical trimethylbenzene can be recycled again in the dehydration reaction of 2-PA.

使用如此再生之2-CP進行第2次之DMC生成反應。反應條件相同,且為了使2-CP之量成為50mmol,而於第1次反應中未反應之2-CP與再生所得2-CP中追加少量之新品2-CP。其結果則是,確認可與第1次相同地以高產率獲得DMC,且副產物之2-PA生成量也與DMC大致同量,完全未檢測到除此之外的副產物。 The second DMC generation reaction was carried out using the thus-regenerated 2-CP. The reaction conditions were the same, and in order to make the amount of 2-CP into 50 mmol, a small amount of the new 2-CP was added to the 2-CP which was not reacted in the first reaction and the 2-CP obtained by the regeneration. As a result, it was confirmed that DMC was obtained in a high yield in the same manner as in the first time, and the amount of 2-PA produced as a by-product was also approximately the same as that of DMC, and no by-products were detected at all.

由上述結果可知,雖然反應開始時需要50mmol之新品2-CP,但藉由再次利用所分離出之未反應2-CP與從副生成之2-PA再生而得之2-CP,而可削減習知生成DMC所必需之2-CP的絕大部分。此外,2-PA雖也有供用作醫農藥之中間產物的利用方法,但使用量並非如此之多而大量耗費處分費用,此種情況可減少9成以上。再者,從2-PA再生、蒸餾成2-CP之際,由於使溫度上升到180℃程度,於再次利用到製造DMC之際,藉由通過已保溫之配管來供給,將可利用此一熱能。 From the above results, it was found that 50 mmol of the new 2-CP was required at the start of the reaction, but it was possible to reduce the 2-CP obtained by reusing the separated unreacted 2-CP and the secondary-generated 2-PA. It is customary to generate most of the 2-CP necessary for DMC. In addition, although 2-PA has a utilization method for use as an intermediate product of medical pesticides, the amount of use is not so much, and a large amount of cost is disbursed, and this situation can be reduced by more than 90%. In addition, when it is regenerated from 2-PA and distilled into 2-CP, the temperature is raised to 180 °C, and when it is reused in the production of DMC, it can be used by supplying it through the insulated pipe. Thermal energy.

(實施例24) (Example 24)

除了一元醇使用乙醇(100mmol)之外,均與實施例23相同。 The same procedure as in Example 23 was carried out except that ethanol (100 mmol) was used for the monohydric alcohol.

經由表14之結果而可確認,碳酸二乙酯(DEC)的情況雖不若DMC,但乙醇基底下之DEC產率在0.08MPa時可得32.8%,0.2MPa時可得41.8%,1MPa時可得50%,5MPa時可得81%。此外,副產物之2-PA生成量與DEC大致同量,且完全未檢測到除此之外的副產物。 As a result of Table 14, it was confirmed that the case of diethyl carbonate (DEC) is not DMC, but the DEC yield under the ethanol substrate is 32.8% at 0.08 MPa, and 41.8% at 0.2 MPa, at 1 MPa. 50% can be obtained, and 81% can be obtained at 5 MPa. Further, the amount of 2-PA produced by-products was approximately the same as that of DEC, and no by-products were detected at all.

接著,與實施例23同樣地於各試驗後之固液共存物質中加入己烷200ml並攪拌,經溶劑萃取後以過濾器過濾而分離為液體與固體。液體包含DEC、2-CP、乙醇、己烷,固體則包含2-PA與CeO2。經己烷溶劑萃取後之液體成分藉由使溫度階段性地升溫到130℃程度之蒸餾方式而分離為DEC、2-CP、己烷及乙醇,成功回收了純度96%以上之DEC。此外,固體成分中之2-PA與CeO2在溶解於丙酮200ml後以過濾器過濾,藉此分離為CeO2與2-PA及丙酮,2-PA與丙酮進一步藉由蒸餾而各自分離,成功回收了純度97%以上之2-PA。 Then, 200 ml of hexane was added to the solid-liquid coexisting material after each test in the same manner as in Example 23, followed by stirring, solvent extraction, filtration through a filter, and separation into a liquid and a solid. The liquid contains DEC, 2-CP, ethanol, hexane, and the solid contains 2-PA and CeO 2 . The liquid component extracted by the hexane solvent was separated into DEC, 2-CP, hexane, and ethanol by a distillation method in which the temperature was gradually raised to 130 ° C, and DEC having a purity of 96% or more was successfully recovered. Further, 2-PA and CeO 2 in the solid component were filtered in a filter after dissolving in 200 ml of acetone, thereby separating into CeO 2 and 2-PA and acetone, and 2-PA and acetone were further separated by distillation, respectively. 2-PA having a purity of 97% or more was recovered.

接著,就從所回收之2-PA再生為2-CP的部分,也與實施例23同樣地進行。結果,如表14所示般進行試驗 No.41~44,2-CP分別生成了15.5、19.9、21.8、39.1mmol。任一實驗之副產物皆僅有水,產率為90%以上,選擇率為100%。 Next, the portion which was regenerated from the recovered 2-PA to 2-CP was also carried out in the same manner as in Example 23. As a result, the test was carried out as shown in Table 14. No. 41 to 44, 2-CP produced 15.5, 19.9, 21.8, and 39.1 mmol, respectively. The by-product of either experiment was only water, the yield was above 90%, and the selectivity was 100%.

針對上述試驗後之固液共存物質,也與實施例1同樣地分離各液體及固體,成功回收了純度98%以上之2-CP。 The liquid and the solid were separated in the same manner as in Example 1 with respect to the solid-liquid coexisting material after the above test, and 2-CP having a purity of 98% or more was successfully recovered.

使用如此再生之2-CP進行第2次之DEC生成反應。反應條件相同,且為了使2-CP之量成為50mmol,而於第1次反應中未反應之2-CP與再生所得2-CP中追加少量之新品2-CP。其結果則是,確認可與第1次相同地以高產率獲得DEC,且副產物之2-PA生成量也與DEC大致同量,完全未檢測到除此之外的副產物。 The second DEC generation reaction was carried out using the thus-regenerated 2-CP. The reaction conditions were the same, and in order to make the amount of 2-CP into 50 mmol, a small amount of the new 2-CP was added to the 2-CP which was not reacted in the first reaction and the 2-CP obtained by the regeneration. As a result, it was confirmed that DEC was obtained in a high yield in the same manner as in the first time, and the amount of 2-PA produced by-product was also approximately the same as that of DEC, and no by-products were detected at all.

一元醇為乙醇且生成物為DEC的情況下,仍可削減習知生成DEC所必需之2-CP的絕大部分,而可將原本作廢棄處分之2-PA減少9成以上。再者,從2-PA再生、蒸餾成2-CP之際,由於使溫度上升到180℃程度,於再次供用於製造DEC之際,可通過已保溫之配管作供給,藉以利用該熱能。 When the monohydric alcohol is ethanol and the product is DEC, most of the 2-CP necessary for the formation of DEC can be reduced, and the 2-PA which was originally discarded can be reduced by 90% or more. In addition, when the 2-PA is regenerated and distilled into 2-CP, the temperature is raised to 180 ° C, and when it is used again for the production of DEC, it can be supplied by the insulated pipe to utilize the heat energy.

(實施例25) (Embodiment 25)

除了一元醇使用1-丙醇(100mmol)且反應24小時之外,均與實施例23相同。 The same procedure as in Example 23 was carried out except that 1-propanol (100 mmol) was used for the reaction of the monohydric alcohol for 24 hours.

經由表15之結果可確認,碳酸二丙酯(DPrC)的情況雖不若DMC,但1-丙醇基底下之DPrC產率在0.08MPa時可得18.2%,0.2MPa時可得23.2%,1MPa時可得30.8%,5MPa時可得45%。此外,副產物之2-PA生成量與DPrC大致同量,且完全未檢測到除此之外的副產物。 From the results of Table 15, it was confirmed that the case of dipropyl carbonate (DPrC) is not DMC, but the DPrC yield under the 1-propanol substrate is 18.2% at 0.08 MPa, and 23.2% at 0.2 MPa. 30.8% can be obtained at 1 MPa and 45% at 5 MPa. Further, the amount of 2-PA produced by-products was approximately the same as that of DPrC, and no by-products were detected at all.

接著,與實施例23同樣地於各試驗後之固液共存物質中加入己烷200ml並攪拌,經溶劑萃取後以過濾器過濾而分離為液體與固體。液體包含DPrC、2-CP、1-丙醇、己烷,固體則包含2-PA與CeO2。經己烷溶劑萃取後之液體成分藉由使溫度階段性地升溫到170℃程度之蒸餾方式而分離為DPrC、2-CP、己烷及1-丙醇,成功回收了純度96%以上之DPrC。此外,固體成分中之2-PA與CeO2在溶解於丙酮200ml後以過濾器過濾,藉此分離為CeO2與2-PA及丙酮,2-PA與丙酮進一步藉由蒸餾而各自分離,成功回收了純度97%以上之2-PA。 Then, 200 ml of hexane was added to the solid-liquid coexisting material after each test in the same manner as in Example 23, followed by stirring, solvent extraction, filtration through a filter, and separation into a liquid and a solid. The liquid contains DPrC, 2-CP, 1-propanol, hexane, and the solid contains 2-PA and CeO 2 . The liquid component extracted by the hexane solvent was separated into DPrC, 2-CP, hexane and 1-propanol by a distillation method in which the temperature was gradually raised to 170 ° C, and the DPrC having a purity of 96% or more was successfully recovered. . Further, 2-PA and CeO 2 in the solid component were filtered in a filter after dissolving in 200 ml of acetone, thereby separating into CeO 2 and 2-PA and acetone, and 2-PA and acetone were further separated by distillation, respectively. 2-PA having a purity of 97% or more was recovered.

接著,就從所回收之2-PA再生為2-CP的部分,也與實施例1同樣地進行。結果,如表15所示般進行試驗No.45~48,2-CP分別生成了9.5、12.2、15.4、21.4mmol。任一實驗之副產物皆僅有水,產率為90%以上,選擇率為100%。 Next, the portion which was regenerated from the recovered 2-PA to 2-CP was also carried out in the same manner as in Example 1. As a result, as shown in Table 15, Test Nos. 45 to 48 were carried out, and 2-CP was produced in 9.5, 12.2, 15.4, and 21.4 mmol, respectively. The by-product of either experiment was only water, the yield was above 90%, and the selectivity was 100%.

針對上述試驗後之固液共存物質,也與實施例1同樣地分離各液體及固體,成功回收了純度98%以上之2-CP。 The liquid and the solid were separated in the same manner as in Example 1 with respect to the solid-liquid coexisting material after the above test, and 2-CP having a purity of 98% or more was successfully recovered.

使用如此再生之2-CP進行第2次之DPrC生成反應。反應條件相同,且為了使2-CP之量成為50mmol,而於第1次反應中未反應之2-CP與再生所得2-CP中追加少量之新品2-CP。其結果則是,確認可與第1次相同地以高產率獲得DPrC,且副產物之2-PA生成量也與DPrC大致同量,完全未檢測到除此之外的副產物。 The second DPrC generation reaction was carried out using the thus-regenerated 2-CP. The reaction conditions were the same, and in order to make the amount of 2-CP into 50 mmol, a small amount of the new 2-CP was added to the 2-CP which was not reacted in the first reaction and the 2-CP obtained by the regeneration. As a result, it was confirmed that DPrC was obtained in a high yield in the same manner as in the first time, and the amount of 2-PA produced as a by-product was also approximately the same as that of DPrC, and no by-products were detected at all.

一元醇為1-丙醇且生成物為DPrC的情況下,仍可削減習知生成DPrC所必需之2-CP的絕大部分,而可將原本作廢棄處分之2-PA減少9成以上。再者,從2-PA再生、蒸餾成2-CP之際,由於使溫度上升到180℃程度,於再次供用於製造DPrC之際,可通過已保溫之配管作供給,藉以利用該熱能。 When the monohydric alcohol is 1-propanol and the product is DPrC, the majority of the 2-CP necessary for the formation of DPrC can be reduced, and the 2-PA which was originally discarded can be reduced by 90% or more. In addition, when the 2-PA is regenerated and distilled into 2-CP, the temperature is raised to 180 ° C, and when it is used again for the production of DPrC, it can be supplied by the insulated pipe to utilize the heat energy.

(實施例26) (Example 26)

除了一元醇使用2-丙醇(100mmol)且反應24小時以外,均與實施例23相同。 The same procedure as in Example 23 was carried out except that 2-propanol (100 mmol) was used for the reaction of the monohydric alcohol for 24 hours.

經由表16之結果而可確認,碳酸二異丙酯(DiPrC) 的情況雖不若其他碳酸酯,但2-丙醇基底下之DPrC產率在0.08MPa時可得4.4%,0.2MPa時可得5.6%,1MPa時可得7.2%,5MPa時可得10.8%。此外,副產物之2-PA生成量與DiPrC大致同量,且完全未檢測到除此之外的副產物。 It can be confirmed from the results of Table 16 that diisopropyl carbonate (DiPrC) The case is not as good as other carbonates, but the DPrC yield under the 2-propanol substrate is 4.4% at 0.08 MPa, 5.6% at 0.2 MPa, 7.2% at 1 MPa, and 10.8% at 5 MPa. . Further, the amount of 2-PA produced by-products was approximately the same as that of DiPrC, and no by-products were detected at all.

接著,與實施例23同樣地於各試驗後之固液共存物質中加入己烷200ml並攪拌,經溶劑萃取後以過濾器過濾而分離為液體與固體。液體包含DiPrC、2-CP、2-丙醇、己烷,固體則包含2-PA與CeO2。經己烷溶劑萃取後之液體成分藉由使溫度階段性地升溫到170℃程度之蒸餾方式而分離為DiPrC、2-CP、己烷及2-丙醇,成功回收了純度96%以上之DiPrC。此外,固體成分中之2-PA與CeO2在溶解於丙酮200ml後以過濾器過濾,藉此分離為CeO2與2-PA及丙酮,2-PA與丙酮進一步藉由蒸餾而各自分離,成功回收了純度97%以上之2-PA。 Then, 200 ml of hexane was added to the solid-liquid coexisting material after each test in the same manner as in Example 23, followed by stirring, solvent extraction, filtration through a filter, and separation into a liquid and a solid. The liquid contains DiPrC, 2-CP, 2-propanol, hexane, and the solid contains 2-PA and CeO 2 . The liquid component extracted by the solvent of hexane was separated into DiPrC, 2-CP, hexane and 2-propanol by a distillation method in which the temperature was gradually raised to 170 ° C, and DiPrC having a purity of 96% or more was successfully recovered. . Further, 2-PA and CeO 2 in the solid component were filtered in a filter after dissolving in 200 ml of acetone, thereby separating into CeO 2 and 2-PA and acetone, and 2-PA and acetone were further separated by distillation, respectively. 2-PA having a purity of 97% or more was recovered.

接著,就從所回收之2-PA再生為2-CP的部分,也與實施例23同樣地進行。結果,如表16所示般進行試驗No.49~52,2-CP分別生成了2.1、2.7、3.4、4.7mmol。任一實驗之副產物皆僅有水,產率為90%以上,選擇率為100%。 Next, the portion which was regenerated from the recovered 2-PA to 2-CP was also carried out in the same manner as in Example 23. As a result, as shown in Table 16, Test Nos. 49 to 52 were carried out, and 2-CP was produced in 2.1, 2.7, 3.4, and 4.7 mmol, respectively. The by-product of either experiment was only water, the yield was above 90%, and the selectivity was 100%.

針對上述試驗後之固液共存物質,也與實施例23同樣地分離各液體及固體,成功回收了純度98%以上之2-CP。 In the same manner as in Example 23, the liquid and the solid were separated in the same manner as in Example 23, and the 2-CP having a purity of 98% or more was successfully recovered.

使用如此再生之2-CP進行第2次之DiPrC生成反應。與實施例23同樣,反應條件相同,且為了使2-CP之量成為50mmol,而於未反應之2-CP與再生所得2-CP中追加少 量之新品2-CP。其結果則是,確認可與第1次相同地以高產率獲得DiPrC,且副產物之2-PA生成量也與DiPrC大致同量,完全未檢測到除此之外的副產物。 The second DiPrC generation reaction was carried out using the thus-regenerated 2-CP. In the same manner as in Example 23, the reaction conditions were the same, and in order to make the amount of 2-CP 50 mmol, the unreacted 2-CP and the 2-CP obtained by regeneration were added less. The new product 2-CP. As a result, it was confirmed that DiPrC was obtained in a high yield in the same manner as in the first time, and the amount of 2-PA produced as a by-product was also approximately the same as that of DiPrC, and no by-products were detected at all.

一元醇為2-丙醇且生成物為DiPrC的情況下,仍可削減習知生成DiPrC所必需之2-CP的絕大部分,而可將原本作廢棄處分之2-PA減少9成以上。再者,從2-PA再生、蒸餾成2-CP之際,由於使溫度上升到180℃程度,於再次供用於製造DiPrC之際,可通過已保溫之配管作供給,藉以利用該熱能。 When the monohydric alcohol is 2-propanol and the product is DiPrC, most of the 2-CP necessary for the formation of DiPrC can be reduced, and the 2-PA which was originally discarded can be reduced by 90% or more. In addition, when the 2-PA is regenerated and distilled into 2-CP, the temperature is raised to 180 ° C, and when it is used again for the production of DiPrC, it can be supplied by the insulated pipe to utilize the heat energy.

(實施例27) (Example 27)

除了一元醇使用1-丁醇(100mmol)並反應24小時之外,均與實施例23相同。 The same procedure as in Example 23 was carried out except that 1-butanol (100 mmol) was used for the reaction of the monohydric alcohol for 24 hours.

經由表17之結果可確認,碳酸二丁酯(DBtC)的情況雖不若DMC,但1-丁醇基底下之DBtC產率在0.08MPa時可得16.4%,0.2MPa時可得21.0%,1MPa時可得29.0%,5MPa時可得40.6%。此外,副產物之2-PA生成量與DBtC大致同量,完全未檢測到除此之外的副產物。 From the results of Table 17, it was confirmed that although the case of dibutyl carbonate (DBtC) is not DMC, the DBtC yield under the 1-butanol substrate is 16.4% at 0.08 MPa, and 21.0% at 0.2 MPa. 29.0% can be obtained at 1 MPa and 40.6% at 5 MPa. Further, the amount of 2-PA produced by-products was approximately the same as that of DBtC, and no by-products were detected at all.

接著,與實施例23同樣地於各試驗後之固液共存物質中加入己烷200ml並攪拌,經溶劑萃取後以過濾器過濾 而分離為液體與固體。液體包含DBtC、2-CP、1-丁醇、己烷,固體則包含2-PA與CeO2。經己烷溶劑萃取後之液體成分藉由使溫度階段性地升溫到120℃程度之蒸餾方式而分離出己烷、1-丁醇,之後冷卻至約0℃以使2-CP析出,成功回收了純度96%以上之DBC。此外,固體成分中之2-PA與CeO2在溶解於丙酮200ml後以過濾器過濾,藉此分離為CeO2與2-PA及丙酮,2-PA與丙酮進一步藉由蒸餾而各自分離,成功回收了純度97%以上之2-PA。 Then, 200 ml of hexane was added to the solid-liquid coexisting material after each test in the same manner as in Example 23, followed by stirring, solvent extraction, filtration through a filter, and separation into a liquid and a solid. The liquid contains DBtC, 2-CP, 1-butanol, hexane, and the solid contains 2-PA and CeO 2 . The liquid component extracted by the solvent of hexane is separated into hexane and 1-butanol by a distillation method in which the temperature is gradually raised to 120 ° C, and then cooled to about 0 ° C to precipitate 2-CP, and the recovery is successful. DBC with a purity of 96% or more. Further, 2-PA and CeO 2 in the solid component were filtered in a filter after dissolving in 200 ml of acetone, thereby separating into CeO 2 and 2-PA and acetone, and 2-PA and acetone were further separated by distillation, respectively. 2-PA having a purity of 97% or more was recovered.

接著,就從所回收之2-PA再生為2-CP的部分,也與實施例23同樣地進行。結果,如表17所示般進行試驗No.53~56,2-CP分別生成了8.8、11.3、14.1、20.3mmol。任一實驗之副產物皆僅有水,產率為90%以上,選擇率為100%。 Next, the portion which was regenerated from the recovered 2-PA to 2-CP was also carried out in the same manner as in Example 23. As a result, as shown in Table 17, Test Nos. 53 to 56 were carried out, and 2-CP produced 8.8, 11.3, and 14.1, respectively. The by-product of either experiment was only water, the yield was above 90%, and the selectivity was 100%.

針對上述試驗後之固液共存物質,也與實施例23同樣地分離各液體及固體,成功回收了純度98%以上之2-CP。 In the same manner as in Example 23, the liquid and the solid were separated in the same manner as in Example 23, and the 2-CP having a purity of 98% or more was successfully recovered.

使用如此再生之2-CP進行第2次之DBtC生成反應。與實施例23同樣地,反應條件相同,且為了使2-CP之量成為50mmol,而於未反應之2-CP與再生所得2-CP中追加少量之新品2-CP。其結果則是,確認可與第1次相同地以高產率獲得DBtC,且副產物之2-PA生成量也與DBtC大致同量,完全未檢測到除此之外的副產物。 The second DBtC generation reaction was carried out using the thus-regenerated 2-CP. In the same manner as in Example 23, the reaction conditions were the same, and in order to make the amount of 2-CP 50 mmol, a small amount of new 2-CP was added to the unreacted 2-CP and the 2-CP obtained by regeneration. As a result, it was confirmed that DBtC was obtained in a high yield in the same manner as in the first time, and the amount of 2-PA produced by-product was also approximately the same as that of DBtC, and no by-products were detected at all.

一元醇為1-丁醇且生成物為DBtC的情況下,仍可削減習知生成DBtC所必需之2-CP的絕大部分,而可將原本 作廢棄處分之2-PA減少9成以上。再者,從2-PA再生、蒸餾成2-CP之際,由於使溫度上升到180℃程度,於再次供用於製造DBtC之際,可通過已保溫之配管作供給,藉以利用該熱能。 When the monohydric alcohol is 1-butanol and the product is DBtC, the majority of the 2-CP necessary for the formation of DBtC can be reduced, but the original The 2-PA for discarding is reduced by more than 90%. In addition, when it is regenerated from 2-PA and distilled into 2-CP, the temperature is raised to 180 ° C, and when it is used again for the production of DBtC, it can be supplied by the insulated pipe to utilize the heat energy.

(實施例28) (Embodiment 28)

除了一元醇使用烯丙醇(100mmol)且反應24小時以外,均與實施例23相同。 The same procedure as in Example 23 was carried out except that allyl alcohol (100 mmol) was used and the reaction was carried out for 24 hours.

經由表18之結果可確認,碳酸二烯丙酯(DAC)的情況雖不若DMC,但烯丙醇基底下之DAC產率在0.08MPa時可得8.8%,0.2MPa時可得11.2%,1MPa時可得14.6%,5MPa時可得21.6%。此外,副產物之2-PA生成量與DAC大致同量,完全未檢測到除此之外的副產物。 From the results of Table 18, it was confirmed that the case of propylene carbonate (DAC) was not DMC, but the DAC yield under the allyl alcohol substrate was 8.8% at 0.08 MPa, and 11.2% at 0.2 MPa. 14.6% can be obtained at 1 MPa and 21.6% at 5 MPa. Further, the amount of 2-PA produced by-products was approximately the same as that of the DAC, and no by-products were detected at all.

接著,與實施例23同樣地於各試驗後之固液共存物質中加入己烷200ml並攪拌,經溶劑萃取後以過濾器過濾而分離為液體與固體。液體包含DAC、2-CP、烯丙醇、己烷,固體則包含2-PA與CeO2。經己烷溶劑萃取後之液體成分先藉由使溫度階段性地升溫到120℃程度之蒸餾方式而分離出己烷及烯丙醇,之後冷卻到約0℃使2-CP析出,成功回收了純度96%以上之DAC。此外,固體成分中之2-PA與 CeO2在溶解於丙酮200ml後以過濾器過濾,藉此分離為CeO2與2-PA及丙酮,2-PA與丙酮進一步藉由蒸餾而各自分離,成功回收了純度97%以上之2-PA。 Then, 200 ml of hexane was added to the solid-liquid coexisting material after each test in the same manner as in Example 23, followed by stirring, solvent extraction, filtration through a filter, and separation into a liquid and a solid. The liquid contains DAC, 2-CP, allyl alcohol, hexane, and the solid contains 2-PA and CeO 2 . The liquid component extracted by the solvent of hexane was first separated into hexane and allyl alcohol by a distillation method in which the temperature was gradually raised to 120 ° C, and then cooled to about 0 ° C to precipitate 2-CP, and the recovered was successfully recovered. A DAC with a purity of 96% or more. Further, 2-PA and CeO 2 in the solid component were filtered in a filter after dissolving in 200 ml of acetone, thereby separating into CeO 2 and 2-PA and acetone, and 2-PA and acetone were further separated by distillation, respectively. 2-PA having a purity of 97% or more was recovered.

接著,就從所回收之2-PA再生為2-CP的部分,也與實施例23同樣地進行。結果,如表18所示般進行試驗No.57~60,2-CP分別生成了4.1、5.3、6.8、9.5mmol。任一實驗之副產物皆僅有水,產率為90%以上,選擇率為100%。 Next, the portion which was regenerated from the recovered 2-PA to 2-CP was also carried out in the same manner as in Example 23. As a result, as shown in Table 18, Test Nos. 57 to 60 were carried out, and 2-CP produced 4.1, 5.3, 6.8, and 9.5 mmol, respectively. The by-product of either experiment was only water, the yield was above 90%, and the selectivity was 100%.

針對上述試驗後之固液共存物質,也與實施例23同樣地分離各液體及固體,成功回收了純度98%以上之2-CP。 In the same manner as in Example 23, the liquid and the solid were separated in the same manner as in Example 23, and the 2-CP having a purity of 98% or more was successfully recovered.

使用如此再生之2-CP進行第2次之DAC生成反應。反應條件與實施例23相同,且為了使2-CP之量成為50mmol,而於未反應之2-CP與再生所得2-CP中追加少量之新品2-CP。其結果則是,確認可與第1次相同地以高產率獲得DAC,且副產物之2-PA生成量也與DAC大致同量,完全未檢測到除此之外的副產物。 The second DAC generation reaction was carried out using the thus-regenerated 2-CP. The reaction conditions were the same as in Example 23, and in order to make the amount of 2-CP 50 mmol, a small amount of new 2-CP was added to the unreacted 2-CP and the 2-CP obtained by regeneration. As a result, it was confirmed that the DAC was obtained in a high yield in the same manner as the first time, and the amount of 2-PA produced by-product was also approximately the same as that of the DAC, and no by-products were detected at all.

一元醇為烯丙醇且生成物為DAC的情況下,仍可削減習知生成DAC所必需之2-CP的絕大部分,而可將原本作廢棄處分之2-PA減少9成以上。再者,從2-PA再生、蒸餾成2-CP之際,由於使溫度上升到180℃程度,於再次供用於製造DAC之際,可通過已保溫之配管作供給,藉以利用該熱能。 When the monohydric alcohol is allyl alcohol and the product is a DAC, the majority of the 2-CP necessary for the conventional generation of the DAC can be reduced, and the 2-PA which was originally discarded can be reduced by 90% or more. In addition, when the 2-PA is regenerated and distilled into 2-CP, the temperature is raised to 180 ° C, and when it is used again for the manufacture of the DAC, it can be supplied by the insulated pipe to utilize the heat energy.

(實施例29) (Example 29)

除了一元醇使用苄基醇(100mmol)且反應24小時以外, 均與實施例23相同。 Except that the monohydric alcohol was benzyl alcohol (100 mmol) and reacted for 24 hours, Both were the same as in Example 23.

經由表19之結果而可確認,碳酸二苄酯(DBnC)的情況雖不若DMC,但苄基醇基底下之DBnC產率在0.08MPa時可得13.0%,0.2MPa時可得16.6%,1MPa時可得21.8%,5MPa時可得32.2%。此外,副產物之2-PA生成量與DBnC大致同量,完全未檢測到除此之外的副產物。 From the results of Table 19, it was confirmed that the case of dibenzyl carbonate (DBnC) is not DMC, but the DBnC yield under the benzyl alcohol substrate is 13.0% at 0.08 MPa, and 16.6% at 0.2 MPa. 21.8% can be obtained at 1 MPa and 32.2% at 5 MPa. Further, the amount of 2-PA produced by-products was approximately the same as that of DBnC, and no by-products were detected at all.

接著,與實施例23同樣地於各試驗後之固液共存物質中加入己烷200ml並攪拌,經溶劑萃取後以過濾器過濾而分離為液體與固體。液體包含DBnC、2-CP、苄基醇、己烷,固體則包含2-PA與CeO2。經己烷溶劑萃取後之液體成分先藉由使溫度階段性地升溫到120℃程度之蒸餾方式而分離出己烷及苄基醇,之後冷卻至約0℃以使2-CP析出,成功回收了純度96%以上之DBnC。此外,固體成分中之2-PA與CeO2在溶解於丙酮200ml後以過濾器過濾,藉此分離為CeO2與2-PA及丙酮,2-PA與丙酮進一步藉由蒸餾而各自分離,成功回收了純度97%以上之2-PA。 Then, 200 ml of hexane was added to the solid-liquid coexisting material after each test in the same manner as in Example 23, followed by stirring, solvent extraction, filtration through a filter, and separation into a liquid and a solid. The liquid contains DBnC, 2-CP, benzyl alcohol, hexane, and the solid contains 2-PA and CeO 2 . The liquid component extracted by the hexane solvent is first separated into hexane and benzyl alcohol by a temperature-wise distillation method to a temperature of about 120 ° C, and then cooled to about 0 ° C to precipitate 2-CP, and the recovery is successful. DBnC with a purity of 96% or more. Further, 2-PA and CeO 2 in the solid component were filtered in a filter after dissolving in 200 ml of acetone, thereby separating into CeO 2 and 2-PA and acetone, and 2-PA and acetone were further separated by distillation, respectively. 2-PA having a purity of 97% or more was recovered.

接著,就從所回收之2-PA再生為2-CP的部分,也與實施例23同樣地進行。結果,如表19所示般進行試驗No.61~64,2-CP分別生成了6.2、7.9、10.2、14.2mmol。任 一實驗之副產物皆僅有水,產率為90%以上,選擇率為100%。 Next, the portion which was regenerated from the recovered 2-PA to 2-CP was also carried out in the same manner as in Example 23. As a result, as shown in Table 19, Test Nos. 61 to 64 were carried out, and 2-CP produced 6.2, 7.9, 10.2, and 14.2 mmol, respectively. Ren The by-products of one experiment were all water, the yield was over 90%, and the selectivity was 100%.

針對上述試驗後之固液共存物質,也與實施例23同樣地分離各液體及固體,成功回收了純度98%以上之2-CP。 In the same manner as in Example 23, the liquid and the solid were separated in the same manner as in Example 23, and the 2-CP having a purity of 98% or more was successfully recovered.

使用如此再生之2-CP進行第2次之DBnC生成反應。與實施例23同樣地,反應條件相同,且為了使2-CP之量成為50mmol,而於未反應之2-CP與再生所得2-CP中追加少量之新品2-CP。其結果則是,確認可與第1次相同地以高產率獲得DBnC,且副產物之2-PA生成量也與DBnC大致同量,完全未檢測到除此之外的副產物。 The second DBnC generation reaction was carried out using the thus-regenerated 2-CP. In the same manner as in Example 23, the reaction conditions were the same, and in order to make the amount of 2-CP 50 mmol, a small amount of new 2-CP was added to the unreacted 2-CP and the 2-CP obtained by regeneration. As a result, it was confirmed that DBnC was obtained in a high yield in the same manner as the first time, and the amount of 2-PA produced as a by-product was also approximately the same as that of DBnC, and no by-products were detected at all.

一元醇為苄基醇且生成物為DBnC的情況下,仍可削減習知生成DBnC所必需之2-CP的絕大部分,而可將原本作廢棄處分之2-PA減少9成以上。再者,從2-PA再生、蒸餾成2-CP之際,由於使溫度上升到180℃程度,於再次供用於製造DAC之際,可通過已保溫之配管作供給,藉以利用該熱能。 When the monohydric alcohol is benzyl alcohol and the product is DBnC, most of the 2-CP which is necessary for the formation of DBnC can be reduced, and the 2-PA which was originally discarded can be reduced by 90% or more. In addition, when the 2-PA is regenerated and distilled into 2-CP, the temperature is raised to 180 ° C, and when it is used again for the manufacture of the DAC, it can be supplied by the insulated pipe to utilize the heat energy.

(實施例30) (Embodiment 30)

從所回收之2-PA再生為2-CP之調製催化劑的過程中,除了令催化劑為Li2O/SiO2、K2O/SiO2、Rb2O/SiO2、Cs2O/SiO2之外,進行與實施例23相同之試驗NO.65~72。此外,催化劑載體使用上述之物,對催化劑載體之載持催化劑的部分則仿照上述方法進行。 In the process of regenerating the recovered 2-PA into a 2-CP catalyst, the catalyst is Li 2 O/SiO 2 , K 2 O/SiO 2 , Rb 2 O/SiO 2 , Cs 2 O/SiO 2 . The same test Nos. 65 to 72 as in Example 23 were carried out. Further, the catalyst carrier is used as described above, and the portion of the catalyst carrier carrying the catalyst is carried out in the same manner as described above.

從表20之結果得知,即使在令鹼金屬為Li、K、Rb、Cs的狀況下,產率仍為90%左右且選擇率為100%。 From the results of Table 20, even in the case where the alkali metal was Li, K, Rb, and Cs, the yield was about 90% and the selectivity was 100%.

(實施例31) (Example 31)

從所回收之2-PA再生為2-CP的調製催化劑過程中,使用Na2CO3(關東化學製,特級)與K2CO3(關東化學製,特級)並變更莫耳比來調整水溶液,以使Na金屬載持量與K金屬載持量之總量最終成為0.5mmol/g,浸漬到SiO2中。之後,於110℃下乾燥約6小時,於500℃下燒成約3小時,製得Na2O-K2O/SiO2催化劑。除了使用Na2O-K2O/SiO2催化劑之外,與實施例23相同地進行試驗NO.73~80。其結果如表21所示,無論是任一莫耳比皆生成了2-CP,副產物僅有水,產率為90%左右,選擇率為100%。從以上結果得知,可因應市場價格來變更鹼金屬之使用量。 In the process of preparing a 2-CP-regenerated catalyst from the recovered 2-PA, Na 2 CO 3 (manufactured by Kanto Chemical Co., Ltd.) and K 2 CO 3 (manufactured by Kanto Chemical Co., Ltd., special grade) were used to adjust the aqueous solution. The total amount of the Na metal supporting amount and the K metal supporting amount was finally 0.5 mmol/g, and was immersed in SiO 2 . Thereafter, it was dried at 110 ° C for about 6 hours and calcined at 500 ° C for about 3 hours to obtain a Na 2 OK 2 O/SiO 2 catalyst. Tests Nos. 73 to 80 were carried out in the same manner as in Example 23 except that the Na 2 OK 2 O/SiO 2 catalyst was used. The results are shown in Table 21, and any of the molar ratios were 2-CP, the by-product was only water, the yield was about 90%, and the selectivity was 100%. From the above results, it is known that the amount of alkali metal used can be changed in response to market prices.

(實施例32) (Example 32)

從所回收之2-PA再生為2-CP的調製催化劑過程中,除了使最終Na金屬載持量如表22所示並令反應壓力僅有1MPa以外,與實施例23同樣地進行試驗NO.81~88。其結果如表22所示,Na載持量為0.1~1mmol時顯示出高活性,而得知0.5mmol程度為合宜之載持量。另一方面,已確認載持量一旦過多活性將會降低,推測這是因為,SiO2載體之結構會因載持多量Na氧化物而發生變化,表面積大幅降低,Na氧化物也變成了大凝集物。 The test was carried out in the same manner as in Example 23 except that the final Na metal loading amount was as shown in Table 22 and the reaction pressure was only 1 MPa from the recovery of the recovered 2-PA to 2-CP. 81~88. As a result, as shown in Table 22, when the Na loading amount was 0.1 to 1 mmol, high activity was exhibited, and it was found that 0.5 mmol was a suitable carrying amount. On the other hand, it has been confirmed that the excessive activity of the carrier will decrease, which is presumably because the structure of the SiO 2 carrier changes due to the holding of a large amount of Na oxide, the surface area is greatly reduced, and the Na oxide also becomes a large agglomeration. Things.

此外,於上述實施例23~29中,雖然從2-PA再生為2-CP之再生反應中使用了Na2O/SiO2催化劑,但即便使用下述催化劑仍可獲得同樣效果:調整水溶液,使Li、Na、K、Rb及Cs中之任1種或任2種鹼金屬最終成為0.5mmol/g,之後浸漬到SiO2中,於110℃下乾燥約6小時,再於500℃下燒成約3小時所獲得的催化劑。此外,載體除了SiO2以外,使用CeO2、ZrO2、CeO2-ZrO2也可獲得同樣效果。 Further, in the above Examples 23 to 29, although the Na 2 O/SiO 2 catalyst was used for the regeneration reaction from 2-PA to 2-CP, the same effect can be obtained even if the following catalyst is used: the aqueous solution is adjusted. Any one or two of the alkali metals of Li, Na, K, Rb, and Cs are finally made to be 0.5 mmol/g, and then immersed in SiO 2 , dried at 110 ° C for about 6 hours, and then fired at 500 ° C. The catalyst obtained in about 3 hours. Further, the same effect can be obtained by using CeO 2 , ZrO 2 or CeO 2 -ZrO 2 in addition to SiO 2 .

(比較例15) (Comparative Example 15)

於DMC製造反應中導入乙腈(AN,300mmol)作為水合劑,於150℃下使其反應24小時,除此之外與實施例23相同。 In the DMC production reaction, acetonitrile (AN, 300 mmol) was introduced as a hydrating agent, and the mixture was reacted at 150 ° C for 24 hours, except that it was the same as in Example 23.

從表23之結果可以看出,一旦使用AN,與2-CP的情況相較,DMC生成量降低到約1/10,由於甲醇基底下之DMC產率在0.5MPa時最高為8.2%,得知本發明較具有高效率。此外,副產物之乙醯胺(AA)生成量與DMC大致同量,完全未檢測出除此之外之副產物。 From the results of Table 23, it can be seen that once AN is used, the amount of DMC produced is reduced to about 1/10 compared with the case of 2-CP, and the highest DMC yield under the methanol substrate is 8.2% at 0.5 MPa. It is known that the present invention is more efficient. Further, the amount of by-product ethyleneamine (AA) produced was approximately the same as that of DMC, and no by-products were detected at all.

接著,與實施例23同樣地於各試驗後之固液共存物質中加入己烷200ml並攪拌,經溶劑萃取後以過濾器過濾而分離為液體與固體。液體包含DMC、未反應之AN、甲醇及己烷,固體則包含AA與CeO2。由於AN之熔點與沸點分別為-45℃與82℃,經己烷溶劑萃取後之液體成分無法利用蒸餾來分離DMC與AN,可藉由暫時冷卻到-30~0℃使析出之DMC分離。之後,使溫度上升到70℃程度進行蒸餾之際,可分離出甲醇與己烷之混合物及未反應之AN,雖然未反應之AN可再次利用於DMC生成反應,但甲醇與己烷之混合物中所含甲醇濃度較高,難以作為萃取用溶劑來再次利用,必須予以廢棄處理。此外,固體成分中之AA與CeO2在溶解於丙酮100ml後以過濾器過濾,藉此分離為CeO2與AA及丙酮,AA與丙酮進一步藉由加熱到70℃程度之蒸餾而各自分離,成功回收了純度95%以上之AA。 Then, 200 ml of hexane was added to the solid-liquid coexisting material after each test in the same manner as in Example 23, followed by stirring, solvent extraction, filtration through a filter, and separation into a liquid and a solid. The liquid contains DMC, unreacted AN, methanol and hexane, and the solid contains AA and CeO 2 . Since the melting point and boiling point of AN are -45 ° C and 82 ° C, respectively, the liquid component extracted by hexane solvent cannot be separated by distillation to separate DMC and AN, and the precipitated DMC can be separated by temporarily cooling to -30 to 0 ° C. Thereafter, when the temperature is raised to about 70 ° C for distillation, a mixture of methanol and hexane and an unreacted AN can be separated, although the unreacted AN can be reused in the DMC formation reaction, but in a mixture of methanol and hexane. The concentration of methanol contained is high and it is difficult to reuse it as a solvent for extraction, and must be disposed of. Further, AA and CeO 2 in the solid component were filtered through a filter after dissolving in 100 ml of acetone, thereby separating CeO 2 from AA and acetone, and AA and acetone were further separated by distillation to about 70 ° C. AA having a purity of 95% or more was recovered.

接著,就從所回收之AA再生為AN的部分,也與實施例23同樣地進行。結果,如表23所示般進行試驗No.89~91,幾乎未發生反應。可想見的是,相對於固體催化劑呈鹼性,AA呈酸性,AA毒化了固體催化劑上之活性點而致使反應不進行。 Next, the portion which was regenerated from the recovered AA to AN was also carried out in the same manner as in Example 23. As a result, Test Nos. 89 to 91 were carried out as shown in Table 23, and almost no reaction occurred. It is conceivable that AA is acidic relative to the solid catalyst, and AA poisons the active sites on the solid catalyst and causes the reaction to proceed.

因此,無法將副生成之AA脫水來再生AN,故而第2次之DMC生成反應係在未反應之AN中追加新品之AN使AN量為300mmol並於150℃下使其反應24小時,除此之外使其與實施例23同樣反應。結果與第1次相同,相較於2-CP的情況,DMC生成量降低至約1/10,甲醇基底下之DMC產率在0.5MPa時最高為8.0%。 Therefore, the A-formed AA cannot be dehydrated to regenerate the AN. Therefore, the second DMC generation reaction system adds a new AN to the unreacted AN to make the AN amount 300 mmol and react at 150 ° C for 24 hours. The reaction was carried out in the same manner as in Example 23 except for the above. The results were the same as in the first time, and the amount of DMC produced was reduced to about 1/10 compared to the case of 2-CP, and the highest DMC yield under the methanol substrate was 8.0% at 0.5 MPa.

(比較例16) (Comparative Example 16)

除了不進行從2-PA再生為2-CP之步驟以及再生步驟後之分離步驟之外,在與實施例23同樣條件下進行試驗NO.92、93。其結果則是,雖然成功回收了純度96%以上之DMC與純度97%以上之2-PA,但2-PA幾乎不具利用用途,而視為產業廢棄物予以處理。又,第2次之DMC生成反應中,至少需新加入29.2或42.0mmol之2-CP,也導致了原料成本之增加。 Tests Nos. 92 and 93 were carried out under the same conditions as in Example 23, except that the step of regeneration from 2-PA to 2-CP and the separation step after the regeneration step were not carried out. As a result, although DMC having a purity of 96% or more and 2-PA having a purity of 97% or more were successfully recovered, 2-PA was hardly used and was treated as industrial waste. Further, in the second DMC formation reaction, at least 29.2 or 42.0 mmol of 2-CP was newly added, which also resulted in an increase in raw material cost.

(比較例17) (Comparative Example 17)

從所回收之2-PA再生為2-CP之反應過程中,催化劑僅使用已整粒到100mesh以下且經700℃預燒成約1小時之SiO2(FUJI SILYSIA CHEMICAL LTD.製,CARiACT,G-6,表面積:535m2/g)並令反應壓力僅有1MPa,除此之外與實施例23相同。結果如表25(NO.94)所示,2-CP僅生成 0.05mmol,活性非常低。 In the reaction from the recovery of the recovered 2-PA to 2-CP, the catalyst was only SiO 2 (FUJI SILYSIA CHEMICAL LTD., CARiACT, G) which had been sized to less than 100 mesh and pre-fired at 700 ° C for about 1 hour. -6, surface area: 535 m 2 /g) and the reaction pressure was only 1 MPa, except that it was the same as in Example 23. As a result, as shown in Table 25 (NO.94), 2-CP produced only 0.05 mmol, and the activity was very low.

(比較例18) (Comparative Example 18)

從所回收之2-PA再生為2-CP之反應過程中,除了催化劑僅使用1mmol之Na2CO3(關東化學製,特級)且令反應壓力僅為1MPa之外均與實施例23相同。其結果如表25(NO.95)所示,完全未生成2-CP。 In the reaction from the recovery of the recovered 2-PA to 2-CP, the same procedure as in Example 23 was carried out except that only 1 mmol of Na 2 CO 3 (manufactured by Kanto Chemical Co., Ltd., special grade) was used and the reaction pressure was only 1 MPa. As a result, as shown in Table 25 (NO. 95), 2-CP was not produced at all.

(比較例19) (Comparative Example 19)

從所回收之2-PA再生為2-CP之反應過程中,除了催化劑僅使用1mmol之K2CO3(關東化學製,特級)且令反應壓力僅為1MPa之外均與實施例23相同。其結果如表25(NO.96)所示,完全未生成2-CP。 In the reaction from the recovery of the recovered 2-PA to 2-CP, the same procedure as in Example 23 was carried out except that only 1 mmol of K 2 CO 3 (manufactured by Kanto Chemical Co., Ltd.) was used and the reaction pressure was only 1 MPa. As a result, as shown in Table 25 (NO.96), 2-CP was not produced at all.

(比較例20) (Comparative Example 20)

從所回收之2-PA再生為2-CP之反應過程中,除了催化劑僅使用1mmol之Rb2CO3(關東化學製,特級)且令反應壓力僅為1MPa之外之外均與實施例23相同。其結果如表3(NO.97)所示,幾乎未生成2-CP。 From the recovery of the recovered 2-PA to 2-CP, except that only 1 mmol of Rb 2 CO 3 (manufactured by Kanto Chemical Co., Ltd., special grade) was used and the reaction pressure was only 1 MPa, and Example 23 was used. the same. As a result, as shown in Table 3 (NO.97), almost no 2-CP was produced.

(比較例21) (Comparative Example 21)

從所回收之2-PA再生為2-CP之反應過程中,除了催化劑僅使用1mmol之Cs2CO3(關東化學製,4N)且令反應壓力僅為1MPa之外均與實施例23相同。其結果如表25(NO.98)所示,2-CP僅生成0.01mmol,活性非常低。 In the reaction from the recovery of the recovered 2-PA to 2-CP, the same procedure as in Example 23 was carried out except that only 1 mmol of Cs 2 CO 3 (manufactured by Kanto Chemical Co., Ltd., 4N) was used and the reaction pressure was only 1 MPa. The results are shown in Table 25 (NO. 98), and 2-CP produced only 0.01 mmol, and the activity was extremely low.

從以上結果可知,於SiO2載體上載持有鹼金屬氧化物之催化劑對於從2-PA再生為2-CP甚有效果。 From the above results, it is understood that the catalyst in which the alkali metal oxide is supported on the SiO 2 carrier is effective in regenerating from 2-PA to 2-CP.

(比較例22) (Comparative Example 22)

從所回收之2-PA再生為2-CP之反應過程中,在調製催化劑時,使用CaCO3(關東化學製,特級)調整水溶液使Ca金屬載持量最終成為0.5mmol/g,再浸漬到SiO2中。之後,於110℃下乾燥約6小時,再於500℃下燒成約3小時,獲得CaO/SiO2催化劑。除了使用CaO/SiO2催化劑且令反應壓力僅為1MPa以外均與實施例23相同。其結果如表26(NO.99)所示,2-CP僅生成了0.11mmol,活性非常低。 In the reaction process from the recovery of the recovered 2-PA to 2-CP, the CaCO 3 (manufactured by Kanto Chemical Co., Ltd.) was used to adjust the aqueous solution to adjust the Ca metal loading amount to 0.5 mmol/g, and then immersed in the reaction. In SiO 2 . Thereafter, it was dried at 110 ° C for about 6 hours and then calcined at 500 ° C for about 3 hours to obtain a CaO/SiO 2 catalyst. The same as Example 23 except that the CaO/SiO 2 catalyst was used and the reaction pressure was only 1 MPa. As a result, as shown in Table 26 (NO. 99), 2-CP produced only 0.11 mmol, and the activity was extremely low.

(比較例23) (Comparative Example 23)

從所回收之2-PA再生為2-CP之反應過程中,在調製催化劑時,使用BaCO3(關東化學製,特級)調整水溶液使Ba金屬載持量最終成為0.5mmol/g,再浸漬到SiO2中。之後,於110℃下乾燥約6小時,再於500℃下燒成約3小時,獲得BaO/SiO2催化劑。除了使用BaO/SiO2催化劑且令反應壓力僅為1MPa以外均與實施例23相同。其結果如表26(NO.100)所示,2-CP僅生成了0.13mmol,活性非常低。 In the process of regenerating the recovered 2-PA to 2-CP, BaCO 3 (manufactured by Kanto Chemical Co., Ltd.) was used to adjust the aqueous solution to adjust the aqueous solution to a final concentration of 0.5 mmol/g, and then immersed in the reaction. In SiO 2 . Thereafter, it was dried at 110 ° C for about 6 hours, and further baked at 500 ° C for about 3 hours to obtain a BaO/SiO 2 catalyst. The same as in Example 23 except that the BaO/SiO 2 catalyst was used and the reaction pressure was only 1 MPa. As a result, as shown in Table 26 (NO. 100), 2-CP produced only 0.13 mmol, and the activity was extremely low.

經由以上結果得以確認,載持與鹼金屬氧化物同樣會呈鹼性之鹼土族金屬氧化物的催化劑活性甚低,而得知在SiO2上載持有鹼金屬氧化物之催化劑甚是有效。 From the above results, it was confirmed that the catalyst activity of the alkaline earth metal oxide which is alkaline as well as the alkali metal oxide is very low, and it is found that the catalyst which holds the alkali metal oxide on SiO 2 is effective.

(比較例24) (Comparative Example 24)

從所回收之2-PA再生為2-CP之反應過程中,在調製催化劑時,使用NH4VO3(Sigma-Aldrich製)調整水溶液使V金屬載持量最終成為0.5mmol/g,再浸漬到SiO2中。之後,於110℃下乾燥約6小時,再於500℃下燒成約3小時,獲得V2O5/SiO2催化劑。除了使用V2O5/SiO2催化劑且令反應壓力僅為1MPa以外均與實施例23相同。其結果如表26(NO.101)所示,2-CP僅生成了0.11mmol,與比較例17僅使用SiO2之情況相同位準,活性非常低。 In the reaction from the recovery of the recovered 2-PA to 2-CP, the NH 4 VO 3 (manufactured by Sigma-Aldrich) was used to adjust the aqueous solution to adjust the V metal loading amount to 0.5 mmol/g, and then impregnated. Into SiO 2 . Thereafter, it was dried at 110 ° C for about 6 hours, and further baked at 500 ° C for about 3 hours to obtain a V 2 O 5 /SiO 2 catalyst. The same as Example 23 except that the V 2 O 5 /SiO 2 catalyst was used and the reaction pressure was only 1 MPa. As a result, as shown in Table 26 (NO. 101), 2-CP produced only 0.11 mmol, which was the same level as in Comparative Example 17 except that SiO 2 was used, and the activity was extremely low.

由以上結果得知,即使將在苯甲醯胺之脫水反應中具有高活性之V系催化劑使用於2-吡啶甲醯胺之脫水反應,仍是幾乎不會進行反應。 From the above results, it has been found that even if a V-based catalyst having high activity in the dehydration reaction of benzamidine is used in the dehydration reaction of 2-pyridinecarbamide, the reaction is hardly carried out.

(實施例33) (Example 33)

從所回收之2-PA再生為2-CP之過程中,在調製催化劑時,除了載體使用將CeO2(第一稀元素製,HS,表面積:74m2/g)整粒到100mesh以下且經500℃預燒成約3小時之物以外,均與實施例30(NO.71)相同。其結果如表27(NO.102)所示,2-CP生成了3.3mmol。副產物僅有水,產率為11.2%,選擇率為100%。 In the process of regenerating the recovered 2-PA to 2-CP, in the preparation of the catalyst, CeO 2 (manufactured by the first rare element, HS, surface area: 74 m 2 /g) is granulated to less than 100 mesh in addition to the carrier. The same as Example 30 (NO. 71) except that it was calcined at 500 ° C for about 3 hours. The results are shown in Table 27 (NO. 102), and 2-CP produced 3.3 mmol. The by-product was only water, the yield was 11.2%, and the selectivity was 100%.

(實施例34) (Example 34)

從所回收之2-PA再生為2-CP之過程中,在調製催化劑時,除了載體使用將ZrO2(第一稀元素製,HS,表面積:88m2/g)整粒到100mesh以下且經500℃預燒成約3小時之物以外,均與實施例30(NO.71)相同。其結果如表27(NO.103)所示,2-CP生成了3.0mmol。副產物僅有水,產率為10.2%,選擇率為100%。 In the process of regenerating the recovered 2-PA to 2-CP, in the preparation of the catalyst, ZrO 2 (manufactured by the first rare element, HS, surface area: 88 m 2 /g) is granulated to below 100 mesh in addition to the carrier. The same as Example 30 (NO. 71) except that it was calcined at 500 ° C for about 3 hours. The results are shown in Table 27 (NO. 103), and 2-CP produced 3.0 mmol. The by-product was only water, the yield was 10.2%, and the selectivity was 100%.

(實施例35) (Example 35)

從所回收之2-PA再生為2-CP之過程中,在調製催化劑時,由於載體使用CeO2-ZrO2固溶體之故,而於已溶有Ce(NO3)3(關東化學製)與Zr(NO3)4(關東化學製)且Ce為20原子量%之溶液中導入NaOH水溶液使其生成沉澱物,之後將沉澱物過濾、水洗,並於1000℃且空氣環境下燒成3小時後,獲得粉末狀之固溶體(表面積:65m2/g)。使用將本固溶體整粒到100mesh以下並於500℃下預燒成約3小時之物,除此以外與實施例30(NO.71)相同。結果如表27(NO.104)所示,2-CP生成了3.2mmol。副產物僅有水,產率為10.8%,選擇率為100%。 In the process of regenerating the recovered 2-PA to 2-CP, when the catalyst is prepared, the carrier is made of CeO 2 -ZrO 2 solid solution, and Ce(NO 3 ) 3 is dissolved (manufactured by Kanto Chemical Co., Ltd. A solution of Zr(NO 3 ) 4 (manufactured by Kanto Chemical Co., Ltd.) and Ce of 20 atomic % was introduced into a precipitate to form a precipitate, and then the precipitate was filtered, washed with water, and fired at 1000 ° C in an air atmosphere. After the lapse, a powdery solid solution (surface area: 65 m 2 /g) was obtained. The same procedure as in Example 30 (NO. 71) was carried out except that the solid solution was sized to 100 mesh or less and calcined at 500 ° C for about 3 hours. The results are shown in Table 27 (NO. 104), and 2-CP produced 3.2 mmol. The by-product was only water, the yield was 10.8%, and the selectivity was 100%.

由以上結果得知,從2-PA再生為2-CP之過程中, 即使催化劑使用CeO2、ZrO2、CeO2-ZrO2為載體,仍是有效。 From the above results, it was found that the catalyst was regenerated from 2-PA to 2-CP, and it was effective even if the catalyst used CeO 2 , ZrO 2 or CeO 2 -ZrO 2 as a carrier.

(實施例36) (Example 36)

從所回收之2-PA再生為2-CP之步驟中,除了有機溶劑使用鄰二甲苯(20ml)取代對稱三甲苯並令反應壓力僅為1MPa以外,均與實施例1相同。結果如表28(NO.105)所示,2-CP生成了9.5mmol。副產物僅有水,產率為32.2%,選擇率為100%。 In the step of regenerating 2-CP from the recovered 2-PA, the same procedure as in Example 1 was carried out except that o-xylene (20 ml) was used instead of the symmetrical trimethylbenzene as the organic solvent and the reaction pressure was only 1 MPa. The results are shown in Table 28 (NO. 105), and 2-CP produced 9.5 mmol. The by-product was only water, the yield was 32.2%, and the selectivity was 100%.

由以上結果得知,即使有機溶劑使用鄰二甲苯,相較於比較例17~24所示之僅有SiO2載體、僅有鹼金屬(碳酸鹽)、載持鹼土族金屬之SiO2催化劑以及V系催化劑,仍是以高產率進行反應。另,間二甲苯、對二甲苯亦可得同樣效果。 From the above results, it was found that even if o-xylene was used as the organic solvent, the SiO 2 catalyst having only the SiO 2 support, the alkali metal (carbonate), and the alkaline earth metal-supported catalyst as shown in Comparative Examples 17 to 24, The V-based catalyst is still reacted in a high yield. In addition, the same effect can be obtained for m-xylene and p-xylene.

(實施例37) (Example 37)

接著,說明使用苯甲腈之碳酸酯製造方法之實施例及比較例。使用如圖1所示之製造裝置進行碳酸酯之製造。使CeO2(第一稀元素製,雜質濃度0.02%以下)於873K且空氣環境下燒成3小時,獲得粉末狀之固體催化劑。於此,在190ml之加熱釜(反應器)中導入磁攪拌器、上述固體催化劑(1mmol)、甲醇(100mmol)及苯甲腈(BN,50mmol),再以約5g之CO2沖洗加熱釜內之空氣3次後,導入預定量之CO2並 昇壓。利用電熱圈、加熱攪拌器將該加熱釜一邊攪拌一邊昇溫到150℃,並以到達目的溫度之時間作為反應開始時間。於150℃下反應12小時後,將加熱釜水冷,冷卻到室溫後減壓並添加內部標準物質之2-丙醇,採取生成物並以GC(氣體層析法)分析。如此變更CO2之導入量及反應壓力,進行表1所示之試驗No.106~112。 Next, examples and comparative examples of a method for producing a carbonate using benzonitrile will be described. The manufacture of the carbonate was carried out using a manufacturing apparatus as shown in FIG. CeO 2 (manufactured by the first rare element, impurity concentration 0.02% or less) was fired at 873 K in an air atmosphere for 3 hours to obtain a powdery solid catalyst. Here, a magnetic stirrer, the above solid catalyst (1 mmol), methanol (100 mmol), and benzonitrile (BN, 50 mmol) were introduced into a 190 ml heating kettle (reactor), and the inside of the heating kettle was rinsed with about 5 g of CO 2 . After three times of air, a predetermined amount of CO 2 is introduced and boosted. The heating kettle was heated to 150 ° C while stirring with a heating coil and a heating stirrer, and the time until the target temperature was reached was taken as the reaction start time. After reacting at 150 ° C for 12 hours, the autoclave was cooled with water, cooled to room temperature, and then depressurized, and the internal standard substance 2-propanol was added thereto, and the product was taken and analyzed by GC (gas chromatography). The amount of introduction of CO 2 and the reaction pressure were changed in this manner, and Test Nos. 106 to 112 shown in Table 1 were carried out.

其結果則是得以確認,即使在相對低壓之0.08、0.1MPa下仍有碳酸二甲酯(DMC)生成,且甲醇基底下之DMC產率在0.1MPa時可得6%,在5MPa時可得8%。又,副產物之苯甲醯胺(BA)之生成量與DMC大致同量,完全未檢測到除此之外的副產物。 As a result, it was confirmed that even at a relatively low pressure of 0.08 and 0.1 MPa, dimethyl carbonate (DMC) was formed, and the DMC yield under a methanol substrate was 6% at 0.1 MPa, which was obtained at 5 MPa. 8%. Further, the amount of benzamide (BA) produced as a by-product was approximately the same as that of DMC, and no by-products were detected at all.

於此,由於甲醇(醇類)基底之產率以化學量論比計係醇類:碳酸酯=2:1,而按下式算出。 Here, since the yield of the methanol (alcohol) substrate is calculated by a stoichiometric amount of alcohol: carbonate = 2:1, it is calculated by the following formula.

接著,於各試驗後之固液共存物質中加入己烷200ml並攪拌,以溶劑萃取後以過濾器過濾而分離為液體與固體。液體包含DMC、BN、甲醇、己烷,固體則包含BA與CeO2。經己烷溶劑萃取後之液體成分藉由使溫度階段性地升溫到120℃程度之蒸餾方式而分離為DMC、BN、己烷及甲醇,成功回收了純度96%以上之DMC。此外,固體成分中之BA與CeO2在溶解於丙酮200ml後以過濾器過濾,藉此分離為CeO2與BA及丙酮,BA與丙酮進一步藉由蒸餾而各自分離,成功回收了純度97%以上之BA。 Next, 200 ml of hexane was added to the solid-liquid coexisting material after each test, and the mixture was stirred, extracted with a solvent, and filtered through a filter to separate into a liquid and a solid. The liquid contains DMC, BN, methanol, hexane, and the solid contains BA and CeO 2 . The liquid component extracted by the hexane solvent was separated into DMC, BN, hexane, and methanol by a distillation method in which the temperature was gradually raised to 120 ° C, and DMC having a purity of 96% or more was successfully recovered. Further, BA and CeO 2 in the solid component were filtered in a filter after dissolving in 200 ml of acetone, thereby separating CeO 2 from BA and acetone, and BA and acetone were further separated by distillation, and the purity was more than 97%. BA.

接著,就從所回收之BA再生為BN一事記載於下。將成為載體之SiO2(FUJI SILYSIA CHEMICAL LTD.製,CARiACT,G-6,表面積:535m2/g)整粒到100mesh以下,以700℃預燒成約1小時。之後,為了載持金屬Mo,使用(NH4)6Mo7O24(關東化學製,特級)調整水溶液使Mo金屬載持量最終成為0.5mmol/g,再浸漬到SiO2中。之後,於110℃下乾燥約6小時,再以500℃燒成約3小時而獲得MoO3/SiO2催化劑。於此,於試管中導入磁攪拌器、上述催化劑(0.1g)、生成DMC時副生成之BA及對稱三甲苯(20ml),連接已充填有分子篩4A(已於300℃下事前乾燥1小時)之索氏萃取器、李必氏冷卻器,將冷卻器溫度設定為10℃,磁攪拌裝置設定為約200℃、600rpm。以Ar氣沖洗冷卻器、索氏萃取管及試管內部後,以溶液開始蒸發之時間作為反應開始時間,使其反應500小時。反應後,將試管(溶液)冷卻至室溫,於反應溶液中加入乙醇20ml及內部標準物質之蒽 (0.1g)後,採取樣本並以GC-MS(氣體層析-質量分析計)定性分析及以FID-GC定量分析。以此種方式,如表29所示般進行試驗No.106~112,結果BN分別生成了1.5mmol、2.6mmol、3.3mmol、5.1mmol、6.3mmol、6.0mmol、3.5mmol。任一實驗之副產物皆僅有水,產率為約90%,選擇率大致為100%。 Next, the reproduction from the recovered BA to BN is described below. SiO 2 (CARJI, G-6, surface area: 535 m 2 /g, manufactured by FUJI SILYSIA CHEMICAL LTD.) was granulated to 100 mesh or less, and pre-fired at 700 ° C for about 1 hour. Then, in order to carry the metal Mo, the aqueous solution was adjusted with (NH 4 ) 6 Mo 7 O 24 (manufactured by Kanto Chemical Co., Ltd.) to finally bring the Mo metal loading amount to 0.5 mmol/g, and then immersed in SiO 2 . Thereafter, it was dried at 110 ° C for about 6 hours, and further baked at 500 ° C for about 3 hours to obtain a MoO 3 /SiO 2 catalyst. Here, a magnetic stirrer, the above catalyst (0.1 g), BA formed by DMC and symmetrical trimethylbenzene (20 ml) were formed in a test tube, and the molecular sieve 4A was filled in the test tube (it was dried at 300 ° C for 1 hour) The Soxhlet extractor and the Leipzig cooler were set to a temperature of 10 ° C and the magnetic stirring device was set to about 200 ° C and 600 rpm. After rinsing the cooler, the Soxhlet extraction tube, and the inside of the test tube with Ar gas, the reaction was started for 500 hours as the reaction start time was started. After the reaction, the test tube (solution) was cooled to room temperature, and 20 ml of ethanol and hydrazine (0.1 g) of the internal standard substance were added to the reaction solution, and then the sample was taken and qualitatively analyzed by GC-MS (gas chromatography-mass spectrometry). And quantitative analysis by FID-GC. In this manner, Test Nos. 106 to 112 were carried out as shown in Table 29, and as a result, 1.5 mmol, 2.6 mmol, 3.3 mmol, 5.1 mmol, 6.3 mmol, 6.0 mmol, and 3.5 mmol were produced in BN. The by-product of either experiment was only water, the yield was about 90%, and the selectivity was approximately 100%.

將上述試驗後之固液共存物質於120℃加熱下以過濾器過濾,分離為液體與固體(催化劑)。液體包含BN、水、未反應之BA及對稱三甲苯。使該液體成分藉由使溫度階段性上升到180℃程度之蒸餾而分離為BN、水、未反應之BA及對稱三甲苯,成功回收了純度98%以上之BN。而後,所分離出之未反應之BA與對稱三甲苯可再次循環利用在BA之脫水反應中。 The solid-liquid coexisting substance after the above test was filtered with a filter under heating at 120 ° C to separate into a liquid and a solid (catalyst). The liquid contains BN, water, unreacted BA, and symmetrical trimethylbenzene. The liquid component was separated into BN, water, unreacted BA, and symmetrical trimethylbenzene by distillation at a temperature of about 180 ° C, and BN having a purity of 98% or more was successfully recovered. Then, the separated unreacted BA and symmetrical trimethylbenzene can be recycled again in the dehydration reaction of BA.

使用如此再生之BN進行第2次DMC生成反應。反應條件相同,且為了使BN之量成為50mmol,而於第1次反應中未反應之BN與再生所得BN中追加少量之新品BN。其結果則是,確認可與第1次相同地以高產率獲得DMC,且副產物之BA生成量也與DMC大致同量,完全未檢測到除此之外的副產物。 The second DMC generation reaction was carried out using BN thus regenerated. The reaction conditions were the same, and in order to make the amount of BN 50 mmol, a small amount of new BN was added to the unreacted BN in the first reaction and the BN obtained by regeneration. As a result, it was confirmed that DMC was obtained in a high yield in the same manner as in the first time, and the amount of BA produced as a by-product was also approximately the same as that of DMC, and no by-products were detected at all.

由上述結果可知,雖然反應開始時需要50mmol之新品BN,但藉由再次利用所分離出之未反應BN與從副生成之BA再生而得之BN,而可削減習知生成DMC所必需之BN的絕大部分。此外,BA雖也有供用作醫農藥之中間產物的利用方法,但使用量並非如此多而會大量耗費處分費用, 此種情況可減少9成以上。再者,從BA再生、蒸餾成BN之際,由於使溫度上升到180℃程度,於再次利用到製造DMC之際,可藉由通過已保溫之配管來供給,以利用此一熱能。 From the above results, it was found that 50 mmol of new BN was required at the start of the reaction, but by using the separated unreacted BN and the BN obtained by regeneration from the by-produced BA, the BN necessary for the conventional generation of DMC can be reduced. The vast majority. In addition, although BA also has a method of using it as an intermediate product of medical pesticides, it is not used so much and it will cost a lot of money. This situation can be reduced by more than 90%. In addition, when B is regenerated and distilled into BN, the temperature is raised to 180 ° C, and when it is reused in the production of DMC, it can be supplied by passing through the insulated pipe to utilize the heat energy.

(實施例38) (Example 38)

除了一元醇使用乙醇(100mmol)之外,均與實施例37相同。 The same as Example 37 except that ethanol (100 mmol) was used for the monohydric alcohol.

經由表30之結果可確認,碳酸二乙酯(DEC)的情況雖不若DMC,但乙醇基底下之DEC產率在1MPa時可得13%,5MPa時可得7%。此外,副產物之BA生成量與DEC大致同量,完全未檢測到除此之外的副產物。 From the results of Table 30, it was confirmed that the case of diethyl carbonate (DEC) was not DMC, but the DEC yield under an ethanol substrate was 13% at 1 MPa, and 7% at 5 MPa. Further, the amount of BA produced by-products was approximately the same as that of DEC, and no by-products were detected at all.

接著,與實施例37同樣地於各試驗後之固液共存物質中加入己烷200ml並攪拌,經溶劑萃取後以過濾器過濾而分離為液體與固體。液體包含DEC、BN、乙醇及己烷,固體則包含BA與CeO2。經己烷溶劑萃取後之液體成分藉由使溫度階段性地升溫到130℃程度之蒸餾方式而分離為DEC、BN、己烷及乙醇,成功回收了純度96%以上之DEC。此外,固體成分中之BA與CeO2在溶解於丙酮200ml後以過濾器過濾,藉此分離為CeO2與BA及丙酮,BA與丙酮進一步藉由蒸餾而各自分離,成功回收了純度97%以上之BA。 Then, 200 ml of hexane was added to the solid-liquid coexisting material after each test in the same manner as in Example 37, followed by stirring, solvent extraction, filtration through a filter, and separation into a liquid and a solid. The liquid contains DEC, BN, ethanol and hexane, and the solid contains BA and CeO 2 . The liquid component extracted by the hexane solvent was separated into DEC, BN, hexane, and ethanol by a distillation method in which the temperature was gradually raised to 130 ° C, and DEC having a purity of 96% or more was successfully recovered. Further, BA and CeO 2 in the solid component were filtered in a filter after dissolving in 200 ml of acetone, thereby separating CeO 2 from BA and acetone, and BA and acetone were further separated by distillation, and the purity was more than 97%. BA.

接著,就從所回收之BA再生為BN的部分,也與實施例37同樣地進行。結果,如表30所示般進行試驗No.113~114,BN分別生成了6.0mmol及3.2mmol。任一實驗之副產物皆僅有水,產率為約90%以上,選擇率大致為100%。 Next, the portion which was regenerated from the recovered BA to BN was also carried out in the same manner as in Example 37. As a result, Test Nos. 113 to 114 were carried out as shown in Table 30, and 6.0 mmol and 3.2 mmol were produced in BN, respectively. The by-product of either experiment was only water, the yield was about 90% or more, and the selectivity was approximately 100%.

針對上述試驗後之固液共存物質,也與實施例37同樣地分離各液體及固體,成功回收了純度98%以上之BN。 In the same manner as in Example 37, the liquid and the solid were separated in the same manner as in Example 37, and the BN having a purity of 98% or more was successfully recovered.

使用如此再生之BN進行第2次之DEC生成反應。與實施例37同樣地,反應條件相同,且為了使BN之量成為50mmol,而於未反應之BN與再生所得BN中追加少量新品之BN。其結果則是,確認可與第1次相同地以高產率獲得DEC,且副產物之BA生成量也與DEC大致同量,完全未檢測到除此之外的副產物。 The second DEC formation reaction was carried out using the BN thus regenerated. In the same manner as in Example 37, the reaction conditions were the same, and in order to make the amount of BN 50 mmol, a small amount of new BN was added to the unreacted BN and the BN obtained by regeneration. As a result, it was confirmed that DEC was obtained in a high yield in the same manner as in the first time, and the amount of BA produced as a by-product was also approximately the same as that of DEC, and no by-products were detected at all.

一元醇為乙醇且生成物為DEC的情況下,仍可削減習知生成DEC所必需之BN的絕大部分。可將原本作廢棄處分之BA減少9成以上。再者,從BA再生、蒸餾成BN之際,由於使溫度上升到180℃程度,於再次供用於製造DEC之際,可通過已保溫之配管作供給,以利用該熱能。 When the monohydric alcohol is ethanol and the product is DEC, most of the BN necessary for the formation of DEC can be reduced. The BA that was originally discarded can be reduced by more than 90%. In addition, when B is regenerated and distilled into BN, the temperature is raised to 180 ° C, and when it is used again for the production of DEC, it can be supplied by the insulated pipe to utilize the heat energy.

(實施例39) (Example 39)

除了一元醇使用1-丙醇(100mmol)並反應24小時以外,與實施例37相同。 The same procedure as in Example 37 except that 1-propanol (100 mmol) was used for the reaction for 24 hours.

經由表31之結果可確認,碳酸二丙酯(DPrC)的情況雖不若DMC,但1-丙醇基底下之DPrC產率在1MPa時可得12.4%,5MPa時可得6.4%。此外,副產物之BA生成量與DPrC大致同量,完全未檢測到除此之外的副產物。 From the results of Table 31, it was confirmed that the case of dipropyl carbonate (DPrC) was not DMC, but the DPrC yield under the 1-propanol substrate was 12.4% at 1 MPa, and 6.4% at 5 MPa. Further, the amount of BA produced by-products was approximately the same as that of DPrC, and no by-products were detected at all.

接著,與實施例37同樣地於各試驗後之固液共存物質中加入己烷200ml並攪拌,經溶劑萃取後以過濾器過濾而分離為液體與固體。液體包含DPC、BN、1-丙醇及己烷,固體則包含BA與CeO2。經己烷溶劑萃取後之液體成分藉由使溫度階段性地升溫到170℃程度之蒸餾方式而分離為DPC、BN、己烷及1-丙醇,成功回收了純度96%以上之DPC。此外,固體成分中之2-BA與CeO2在溶解於丙酮200ml後以過濾器過濾,藉此分離為CeO2與BA及丙酮,BA與丙酮進一步藉由蒸餾而各自分離,成功回收了純度97%以上之BA。 Then, 200 ml of hexane was added to the solid-liquid coexisting material after each test in the same manner as in Example 37, followed by stirring, solvent extraction, filtration through a filter, and separation into a liquid and a solid. The liquid contains DPC, BN, 1-propanol and hexane, and the solid contains BA and CeO 2 . The liquid component extracted by the hexane solvent was separated into DPC, BN, hexane, and 1-propanol by a distillation method in which the temperature was gradually raised to 170 ° C, and DPC having a purity of 96% or more was successfully recovered. Further, 2-BA and CeO 2 in the solid component were filtered in a filter after dissolving in 200 ml of acetone, thereby separating into CeO 2 and BA and acetone, and BA and acetone were further separated by distillation, and the purity was successfully recovered. More than % of BA.

接著,就從所回收之BA再生為BN的部分,也與實施例37同樣地進行。結果,如表31所示般進行試驗No.115、116,BN分別生成了5.9mmol、2.8mmol。任一實驗之副產物皆僅有水,產率為約90%以上,選擇率大致為100%。 Next, the portion which was regenerated from the recovered BA to BN was also carried out in the same manner as in Example 37. As a result, Test Nos. 115 and 116 were carried out as shown in Table 31, and 5.9 mmol and 2.8 mmol were produced in BN, respectively. The by-product of either experiment was only water, the yield was about 90% or more, and the selectivity was approximately 100%.

針對上述試驗後之固液共存物質,也與實施例37 同樣地分離各液體及固體,成功回收了純度98%以上之BN。 For the solid-liquid coexisting substance after the above test, also with Example 37 Similarly, each liquid and solid were separated, and BN having a purity of 98% or more was successfully recovered.

使用如此再生之BN進行第2次DPC生成反應。與實施例37相同地,反應條件相同,且為了使BN之量成為50mmol,而於未反應之BN與再生所得BN中追加少量新品之BN。其結果則是,確認可與第1次相同地以高產率獲得DPC,且副產物之BA生成量也與DPC大致同量,完全未檢測到除此之外的副產物。 The second DPC generation reaction was carried out using the BN thus regenerated. In the same manner as in Example 37, the reaction conditions were the same, and in order to make the amount of BN 50 mmol, a small amount of new BN was added to the unreacted BN and the BN obtained by regeneration. As a result, it was confirmed that DPC was obtained in a high yield in the same manner as in the first time, and the amount of BA produced as a by-product was also approximately the same as that of DPC, and no by-products were detected at all.

一元醇為1-丙醇且生成物為DPC的情況下,仍可削減習知生成DPC所必需之BN的絕大部分,而可將原本作廢棄處分之BA減少9成以上。再者,從BA再生、蒸餾成BN之際,由於使溫度上升到180℃程度,於再次供用於製造DPC之際,可通過已保溫之配管作供給,藉以利用該熱能。 When the monohydric alcohol is 1-propanol and the product is DPC, the majority of the BN necessary for the formation of DPC can be reduced, and the BA which was originally discarded can be reduced by 90% or more. In addition, when B is regenerated and distilled into BN, the temperature is raised to 180 ° C, and when it is used again for the production of DPC, it can be supplied by the insulated pipe to utilize the heat energy.

(實施例40) (Embodiment 40)

除了一元醇使用1-丁醇(100mmol)並反應24小時之外,均與實施例37相同。 The same procedure as in Example 37 was carried out except that 1-butanol (100 mmol) was used for the reaction of the monohydric alcohol for 24 hours.

經由表32之結果可確認,碳酸二丁酯(DBC)的情況雖不若DMC,但1-丁醇基底下之DBC產率在1MPa時可得11.4%,5MPa時可得5.8%。此外,副產物之BA生成量與DBC 大致同量,完全未檢測到除此之外的副產物。 From the results of Table 32, it was confirmed that although the case of dibutyl carbonate (DBC) was not DMC, the DBC yield under the 1-butanol substrate was 11.4% at 1 MPa, and 5.8% at 5 MPa. In addition, BA production by-products and DBC Substantially the same amount, no by-products were detected at all.

接著,與實施例37同樣地於各試驗後之固液共存物質中加入己烷200ml並攪拌,經溶劑萃取後以過濾器過濾而分離為液體與固體。液體包含DBC、BN、1-丁醇及己烷,固體則包含BA與CeO2。經己烷溶劑萃取後之液體成分藉由先使溫度階段性地升溫到120℃程度之蒸餾方式而分離出己烷、1-丁醇,之後冷卻至約0℃以使BN析出,成功回收了純度96%以上之DBC。此外,固體成分中之BA與CeO2在溶解於丙酮200ml後以過濾器過濾,藉此分離為CeO2與BA及丙酮,BA與丙酮進一步藉由蒸餾而各自分離,成功回收了純度97%以上之BA。 Then, 200 ml of hexane was added to the solid-liquid coexisting material after each test in the same manner as in Example 37, followed by stirring, solvent extraction, filtration through a filter, and separation into a liquid and a solid. The liquid contains DBC, BN, 1-butanol and hexane, and the solid contains BA and CeO 2 . The liquid component extracted by the solvent of hexane was separated into hexane and 1-butanol by a distillation method in which the temperature was gradually raised to 120 ° C, and then cooled to about 0 ° C to precipitate BN, and the recovered was successfully recovered. DBC with a purity of 96% or more. Further, BA and CeO 2 in the solid component were filtered in a filter after dissolving in 200 ml of acetone, thereby separating CeO 2 from BA and acetone, and BA and acetone were further separated by distillation, and the purity was more than 97%. BA.

接著,就從所回收之BA再生為BN的部分,也與實施例37同樣地進行。結果,如表32所示般進行試驗No.117、118,BN分別生成了5.5mmol、2.6mmol。任一實驗之副產物皆僅有水,產率為約90%以上,選擇率大致為100%。 Next, the portion which was regenerated from the recovered BA to BN was also carried out in the same manner as in Example 37. As a result, Test Nos. 117 and 118 were carried out as shown in Table 32, and BN was produced in an amount of 5.5 mmol and 2.6 mmol, respectively. The by-product of either experiment was only water, the yield was about 90% or more, and the selectivity was approximately 100%.

針對上述試驗後之固液共存物質,也與實施例37同樣地分離各液體及固體,成功回收了純度98%以上之BN。 In the same manner as in Example 37, the liquid and the solid were separated in the same manner as in Example 37, and the BN having a purity of 98% or more was successfully recovered.

使用如此再生之BN進行第2次之DBC生成反應。與實施例37同樣地,反應條件相同,且為了使BN之量成為50mmol,而於未反應之BN與再生所得BN中追加少量新品之BN。其結果則是,確認可與第1次相同地以高產率獲得DBC,且副產物之BA生成量也與DBC大致同量,完全未檢測到除此之外的副產物。 The second DBC generation reaction was carried out using the BN thus regenerated. In the same manner as in Example 37, the reaction conditions were the same, and in order to make the amount of BN 50 mmol, a small amount of new BN was added to the unreacted BN and the BN obtained by regeneration. As a result, it was confirmed that DBC was obtained in a high yield in the same manner as in the first time, and the amount of BA produced as a by-product was also approximately the same as that of DBC, and no by-products were detected at all.

一元醇為1-丁醇且生成物為DBC的情況下,仍可削減習知生成DBC所必需之BN的絕大部分,而可將原本作廢棄處分之BA減少9成以上。再者,從BA再生、蒸餾成BN之際,由於使溫度上升到180℃程度,於再次供用於製造DBC之際,可通過已保溫之配管作供給,藉以利用該熱能。 When the monohydric alcohol is 1-butanol and the product is DBC, the majority of the BN necessary for the formation of DBC can be reduced, and the BA which was originally discarded can be reduced by 90% or more. In addition, when B is regenerated and distilled into BN, the temperature is raised to 180 ° C, and when it is used again for the production of DBC, it can be supplied by the insulated pipe to utilize the heat energy.

(實施例41) (Example 41)

除了一元醇使用苄基醇、烯丙醇及2-丙醇各100mmol且反應24小時以外,均與實施例37相同。 The same procedure as in Example 37 was carried out except that the monohydric alcohol was used in an amount of 100 mmol each of benzyl alcohol, allyl alcohol and 2-propanol for 24 hours.

經由表33之結果可確認,此一連串碳酸酯(EC)的情況雖不若DMC,但苄基醇、烯丙醇、2-丙醇等各醇基底下之EC產率在1MPa時分別可得6.0%、5.6%、13.4%。此外,副產物之BA生成量與各EC大致同量,完全未檢測到除此之外的副產物。 It can be confirmed from the results of Table 33 that although the series of carbonates (EC) are not DMC, the EC yields of the respective alcohol bases such as benzyl alcohol, allyl alcohol, and 2-propanol are respectively 1 MPa. 6.0%, 5.6%, 13.4%. Further, the amount of BA produced as a by-product was approximately the same as that of each EC, and no by-products were detected at all.

接著,與實施例37同樣地於各試驗後之固液共存物質中加入己烷200ml並攪拌,經溶劑萃取後以過濾器過濾而分離為液體與固體。液體包含EC、BN、各醇及己烷,固體則包含BA與CeO2。經己烷溶劑萃取後之液體成分先藉由使溫度階段性地升溫到120℃程度之蒸餾方式而分離出己 烷與各醇,之後冷卻到約0℃使BN析出,成功回收了純度96%以上之EC。此外,固體成分中之BA與CeO2在溶解於丙酮200ml後以過濾器過濾,藉此分離為CeO2與BA及丙酮,BA與丙酮進一步藉由蒸餾而各自分離,成功回收了純度97%以上之BA。 Then, 200 ml of hexane was added to the solid-liquid coexisting material after each test in the same manner as in Example 37, followed by stirring, solvent extraction, filtration through a filter, and separation into a liquid and a solid. The liquid contains EC, BN, each alcohol and hexane, and the solid contains BA and CeO 2 . The liquid component extracted by the solvent of hexane is separated into hexane and each alcohol by a distillation method in which the temperature is gradually raised to 120 ° C, and then cooled to about 0 ° C to precipitate BN, and the purity is 96%. The above EC. Further, BA and CeO 2 in the solid component were filtered in a filter after dissolving in 200 ml of acetone, thereby separating CeO 2 from BA and acetone, and BA and acetone were further separated by distillation, and the purity was more than 97%. BA.

接著,就從所回收之BA再生為BN的部分,也與實施例37同樣地進行。結果,如表33所示般進行試驗No.119~121,BN分別生成了2.6mmol、2.5mmol、6.5mmol。任一實驗之副產物皆僅有水,產率為約90%以上,選擇率大致為100%。 Next, the portion which was regenerated from the recovered BA to BN was also carried out in the same manner as in Example 37. As a result, Test Nos. 119 to 121 were carried out as shown in Table 33, and 2.6 mmol, 2.5 mmol, and 6.5 mmol were produced in BN, respectively. The by-product of either experiment was only water, the yield was about 90% or more, and the selectivity was approximately 100%.

針對上述試驗後之固液共存物質,也與實施例37同樣地分離各液體及固體,成功回收了純度98%以上之BN。 In the same manner as in Example 37, the liquid and the solid were separated in the same manner as in Example 37, and the BN having a purity of 98% or more was successfully recovered.

使用如此再生之BN進行第2次EC生成反應。與實施例37同樣,反應條件相同,且為了使BN之量成為50mmol,而於未反應之BN與再生所得BN中追加少量新品之BN。其結果則是,確認可與第1次相同地以高產率獲得EC,且副產物之BA生成量也與EC大致同量,完全未檢測到除此之外的副產物。 The second EC production reaction was carried out using BN thus regenerated. In the same manner as in Example 37, the reaction conditions were the same, and in order to make the amount of BN 50 mmol, a small amount of new BN was added to the unreacted BN and the BN obtained by regeneration. As a result, it was confirmed that EC can be obtained in a high yield in the same manner as the first time, and the amount of BA produced as a by-product is also approximately the same as that of EC, and no by-products are detected at all.

(實施例42) (Example 42)

從所回收之BA再生為BN的調製催化劑過程中,除了令催化劑為MoO3/TiO2、Re2O7/CeO2、WO3/SiO2、Nb2O5/ZrO2之外,進行與實施例37相同之試驗NO.122~129。此外,催化劑載體使用上述之物,對催化劑載體之載持催化劑的部 分則仿照上述方法進行。 In the process of preparing the catalyst from the recovered BA to BN, in addition to the catalyst being MoO 3 /TiO 2 , Re 2 O 7 /CeO 2 , WO 3 /SiO 2 , Nb 2 O 5 /ZrO 2 , Example 37, the same test No. 122-129. Further, the catalyst carrier is used as described above, and the portion of the catalyst carrier carrying the catalyst is carried out in the same manner as described above.

從表34之結果得知,即使在令金屬元素為Mo、Re、W、Nb的情況下,產率仍為90%左右且選擇率大致為100%。 From the results of Table 34, even in the case where the metal elements were Mo, Re, W, and Nb, the yield was about 90% and the selectivity was approximately 100%.

(實施例43) (Example 43)

從所回收之BA再生為BN的調製催化劑過程中,除了使最終Mo載持量如表35所示且令反應壓力僅為1MPa以外,與實施例37同樣地進行試驗NO.130~135。其結果如表35所示,Mo載持量為0.1~1mmol時顯示出高活性,得知0.6mmol程度為合宜之載持量。另一方面,已確認載持量一旦過多活性將會相對降低,推測這是因為載持多量Mo氧化物而使SiO2載體上之Mo氧化物變成了大凝集物。 In the process of preparing the catalyst from the recovered BA to BN, the test Nos. 130 to 135 were carried out in the same manner as in Example 37 except that the final Mo loading amount was as shown in Table 35 and the reaction pressure was only 1 MPa. As a result, as shown in Table 35, when the Mo loading amount was 0.1 to 1 mmol, high activity was exhibited, and it was found that 0.6 mmol was a suitable carrying amount. On the other hand, it has been confirmed that once the amount of the support is too large, the activity will be relatively lowered, and it is presumed that this is because a large amount of Mo oxide is carried to cause the Mo oxide on the SiO 2 carrier to become a large aggregate.

此外,於上述實施例37~41中,雖然從BA再生為BN之再生反應中使用了MoO3/SiO2催化劑,但即便使用下述催化劑仍可獲得同樣效果:調整水溶液,使W、Re、Nb中之任1種或任2種金屬元素最終成為0.5mmol/g,之後浸漬到SiO2中,於110℃下乾燥約6小時,再於500℃下燒成約3小時所獲得的催化劑。此外,載體除了SiO2以外,使用CeO2、ZrO2、CeO2-ZrO2也可獲得同樣效果。 Further, in the above Examples 37 to 41, although the MoO 3 /SiO 2 catalyst was used for the regeneration reaction from the regeneration of BA to BN, the same effect can be obtained by using the following catalyst: adjusting the aqueous solution to make W, Re, Any one or two of the metal elements of Nb are finally 0.5 mmol/g, and then immersed in SiO 2 , dried at 110 ° C for about 6 hours, and calcined at 500 ° C for about 3 hours to obtain a catalyst. Further, the same effect can be obtained by using CeO 2 , ZrO 2 or CeO 2 -ZrO 2 in addition to SiO 2 .

(實施例44) (Example 44)

從所回收之BA再生為BN之步驟中,除了有機溶劑使用鄰二甲苯(20ml)來取代對稱三甲苯並令反應壓力僅為1MPa以外,均與實施例37相同。結果如表36(NO.136)所示,BN生成了3.2mmol。副產物僅有水,產率為42.7%,選擇率大致為100%。 In the step of regenerating from the recovered BA to BN, the same procedure as in Example 37 was carried out except that o-xylene (20 ml) was used instead of the organic solvent to replace the symmetric toluene and the reaction pressure was only 1 MPa. The results are shown in Table 36 (NO. 136), and BN produced 3.2 mmol. The by-product was only water, the yield was 42.7%, and the selectivity was approximately 100%.

由以上結果得知,即使有機溶劑使用鄰二甲苯,仍是以高產率進行反應。另,間二甲苯、對二甲苯亦可得同樣效果。 From the above results, it was found that even if the organic solvent used o-xylene, the reaction was carried out in a high yield. In addition, the same effect can be obtained for m-xylene and p-xylene.

(比較例25) (Comparative Example 25)

於DMC製造反應中導入乙腈(AN,300mmol)作為水合劑,於150℃下使其反應24小時,除此之外與實施例37相同。 In the DMC production reaction, acetonitrile (AN, 300 mmol) was introduced as a hydrating agent, and the mixture was reacted at 150 ° C for 24 hours, except that it was the same as Example 37.

從表37之結果可以看出,一旦使用AN,與BN的情況相較,DMC生成量降低到約1/10,由於甲醇基底下之DMC產率在0.5MPa時最高為8.2%,得知本發明較具有高效率。此外,副產物之乙醯胺(AA)生成量與DMC大致同量,完全未檢測出除此之外之副產物。 From the results of Table 37, it can be seen that once AN is used, the amount of DMC produced is reduced to about 1/10 compared with the case of BN, and the highest DMC yield under the methanol substrate is 8.2% at 0.5 MPa. The invention is more efficient. Further, the amount of by-product ethyleneamine (AA) produced was approximately the same as that of DMC, and no by-products were detected at all.

接著,與實施例37同樣地於各試驗後之固液共存物質中加入己烷200ml並攪拌,經溶劑萃取後以過濾器過濾而分離為液體與固體。液體包含DMC、未反應之AN、甲醇 及己烷,固體則包含AA與CeO2。由於AN之熔點與沸點分別為-45℃與82℃,經己烷溶劑萃取後之液體成分無法利用蒸餾來分離DMC與AN,可藉由暫時冷卻到-30~0℃使析出之DMC分離。之後,使溫度上升到70℃程度進行蒸餾之際,可分離出甲醇與己烷之混合物及未反應之AN,雖然未反應之AN可再次利用於DMC生成反應,但甲醇與己烷之混合物中所含甲醇濃度較高,難以作為萃取用溶劑來再次利用,必須予以廢棄處理。此外,固體成分中之AA與CeO2在溶解於丙酮100ml後以過濾器過濾,藉此分離為CeO2與AA及丙酮,AA與丙酮進一步藉由加熱到70℃程度之蒸餾而各自分離,成功回收了純度95%以上之AA。 Then, 200 ml of hexane was added to the solid-liquid coexisting material after each test in the same manner as in Example 37, followed by stirring, solvent extraction, filtration through a filter, and separation into a liquid and a solid. The liquid contains DMC, unreacted AN, methanol and hexane, and the solid contains AA and CeO 2 . Since the melting point and boiling point of AN are -45 ° C and 82 ° C, respectively, the liquid component extracted by hexane solvent cannot be separated by distillation to separate DMC and AN, and the precipitated DMC can be separated by temporarily cooling to -30 to 0 ° C. Thereafter, when the temperature is raised to about 70 ° C for distillation, a mixture of methanol and hexane and an unreacted AN can be separated, although the unreacted AN can be reused in the DMC formation reaction, but in a mixture of methanol and hexane. The concentration of methanol contained is high and it is difficult to reuse it as a solvent for extraction, and must be disposed of. Further, AA and CeO 2 in the solid component were filtered through a filter after dissolving in 100 ml of acetone, thereby separating CeO 2 from AA and acetone, and AA and acetone were further separated by distillation to about 70 ° C. AA having a purity of 95% or more was recovered.

接著,就從所回收之AA再生為AN的部分,也與實施例37同樣地進行。結果,如表37所示般進行試驗No.137、138,幾乎未發生反應。可想見的是,相對於固體催化劑呈鹼性,AA呈酸性,因此AA毒化了固體催化劑上之活性點而致使反應不進行。 Next, the portion which was regenerated from the recovered AA to AN was also carried out in the same manner as in Example 37. As a result, Test Nos. 137 and 138 were carried out as shown in Table 37, and almost no reaction occurred. It is conceivable that AA is acidic relative to the solid catalyst, and AA poisons the active sites on the solid catalyst and causes the reaction to proceed.

因此,無法將副生成之AA脫水來再生AN,故而第2次DMC生成反應係在未反應之AN中追加新品之AN使AN量成為300mmol並於150℃下使其反應24小時,除此之外使其與實施例37同樣反應。結果與第1次相同,相較於BN的情況,DMC生成量降低至約1/10,甲醇基底下之DMC產率在0.5MPa時最高為1.7%。 Therefore, the A-formed AA cannot be dehydrated to regenerate the AN. Therefore, in the second DMC generation reaction, a new AN is added to the unreacted AN to make the AN amount 300 mmol, and the reaction is carried out at 150 ° C for 24 hours. Further, it was reacted in the same manner as in Example 37. The results were the same as in the first time, the amount of DMC produced was reduced to about 1/10 compared to the case of BN, and the highest DMC yield under the methanol substrate was 0.5% at 0.5 MPa.

(比較例26) (Comparative Example 26)

除了不進行從BA再生為BN之步驟(及再生步驟後之分 離步驟)之外,在與實施例37同樣條件下進行試驗NO.139、140。其結果則是,雖然成功回收了純度96%以上之DMC與純度97%以上之BA,但副生成之大量BA幾乎不具利用用途,而視為產業廢棄物處理。又,第2次DMC生成反應中,至少需新加入7.7或4.3mmol之BN,也導致了原料成本之增加。 Except for the step of regenerating from BA to BN (and after the regeneration step) Tests Nos. 139 and 140 were carried out under the same conditions as in Example 37 except for the step. As a result, although a DMC having a purity of 96% or more and a BA having a purity of 97% or more were successfully recovered, a large amount of BA produced by the side is hardly utilized, and is regarded as an industrial waste treatment. Further, in the second DMC formation reaction, at least 7.7 or 4.3 mmol of BN was newly added, which also led to an increase in the cost of raw materials.

(比較例27) (Comparative Example 27)

從所回收之BA再生為BN之反應過程中,除了調製出如表39所示之催化劑,將之用作催化劑並令反應壓力僅為1MPa,除此之外與實施例37相同。結果如表39(NO.141~143)所示,BN生成量甚少,活性甚低。 In the reaction from the recovery of the recovered BA to BN, the same procedure as in Example 37 was carried out except that the catalyst shown in Table 39 was prepared and used as a catalyst and the reaction pressure was only 1 MPa. As a result, as shown in Table 39 (NO. 141 to 143), the amount of BN produced was small and the activity was extremely low.

以上,一邊參照檢附之圖式一邊就本發明之較佳 實施形態予以詳細說明,但本發明不受此等例示所侷限。若是本發明所屬技術分野中具有通常知識者,當可在申請專利範圍所載技術思想之範疇內思及各種變形例或修正例,而可理解此等情況自是隸屬於本發明之技術範圍中。 Above, it is preferable to refer to the attached drawings. The embodiments are described in detail, but the invention is not limited by the examples. If there is a general knowledge in the technical field to which the present invention pertains, various modifications or modifications can be considered within the scope of the technical idea contained in the scope of the patent application, and it is understood that such a situation belongs to the technical scope of the present invention. .

1‧‧‧第1反應塔 1‧‧‧1st reaction tower

2‧‧‧第1萃取塔 2‧‧‧1st extraction tower

3‧‧‧第1蒸餾塔 3‧‧‧1st distillation tower

4‧‧‧第2萃取塔 4‧‧‧2nd extraction tower

5‧‧‧第2蒸餾塔 5‧‧‧2nd distillation tower

6‧‧‧催化劑再生塔 6‧‧‧ Catalyst Regeneration Tower

7‧‧‧第2反應塔 7‧‧‧2nd reaction tower

8‧‧‧催化劑分離塔 8‧‧‧ Catalyst separation tower

9‧‧‧第3蒸餾塔 9‧‧‧3rd distillation tower

10‧‧‧CO2昇壓鼓風機 10‧‧‧CO 2 booster blower

11‧‧‧CO2 11‧‧‧CO 2

12‧‧‧一元醇 12‧‧‧ monohydric alcohol

13‧‧‧2-氰吡啶、苯甲腈 13‧‧‧2-Cyanopyridine, benzonitrile

14‧‧‧固體催化劑 14‧‧‧Solid catalyst

15‧‧‧反應液 15‧‧‧Reaction solution

16‧‧‧烷烴 16‧‧‧alkanes

17、21‧‧‧萃取液 17, 21‧‧ ‧ extract

18‧‧‧固相物質 18‧‧‧ Solid phase materials

19‧‧‧碳酸酯 19‧‧‧carbonate

20‧‧‧未反應之2-氰吡啶、未反應之苯甲腈 20‧‧‧Unreacted 2-cyanopyridine, unreacted benzonitrile

22‧‧‧用畢之固體催化劑 22‧‧‧Complete solid catalyst

23‧‧‧2-吡啶甲醯胺、苯甲醯胺 23‧‧‧2-pyridinecarboxamide, benzamide

24‧‧‧親水性溶劑 24‧‧‧Hydrophilic solvent

25‧‧‧固體催化劑 25‧‧‧Solid catalyst

26‧‧‧用畢之固體催化劑 26‧‧‧Complete solid catalyst

27‧‧‧有機溶劑 27‧‧‧Organic solvents

28‧‧‧未反應之2-吡啶甲醯胺、未反應之苯甲醯胺 28‧‧‧Unreacted 2-pyridinecarbamamine, unreacted benzamide

29‧‧‧水 29‧‧‧Water

Claims (43)

一種氰吡啶之製造方法,其特徵在於:在載持有鹼金屬氧化物之催化劑存在下且在有機溶劑存在下,將吡啶甲醯胺加熱使其進行脫水反應,藉以製出氰吡啶。 A method for producing cyanide pyridine, characterized in that pyridine carbenamide is heated in the presence of a catalyst carrying an alkali metal oxide in the presence of an organic solvent to carry out a dehydration reaction, whereby cyanopyridine is produced. 如請求項1之氰吡啶之製造方法,其中前述氰吡啶為2-氰吡啶,且前述吡啶甲醯胺為2-吡啶甲醯胺。 The method for producing cyanide according to claim 1, wherein the cyanopyridine is 2-cyanopyridine, and the pyridine carbenamide is 2-pyridinecarboxamide. 如請求項1或2之氰吡啶之製造方法,其中前述載持有鹼金屬氧化物之催化劑係一在由SiO2、CeO2及ZrO2中任1種或2種以上所構成之催化劑載體上載持有1種或2種以上鹼金屬氧化物的催化劑。 The method for producing a cyanopyridine according to claim 1 or 2, wherein the catalyst supporting the alkali metal oxide is supported on a catalyst carrier composed of one or more of SiO 2 , CeO 2 and ZrO 2 . A catalyst having one or more alkali metal oxides. 如請求項3之氰吡啶之製造方法,其中前述催化劑載體為SiO2The method for producing cyanide according to claim 3, wherein the catalyst carrier is SiO 2 . 如請求項1至4中任一項之氰吡啶之製造方法,其中前述鹼金屬氧化物為Li、K、Na、Rb及Cs中任一者之氧化物。 The method for producing cyanopyridine according to any one of claims 1 to 4, wherein the alkali metal oxide is an oxide of any one of Li, K, Na, Rb and Cs. 如請求項1至5中任一項之氰吡啶之製造方法,其中前述有機溶劑為對稱三甲苯(mesitylene)。 The method for producing a cyanopyridine according to any one of claims 1 to 5, wherein the organic solvent is symmetrical mesitylene. 如請求項1至6中任一項之氰吡啶之製造方法,其在前述脫水反應之際使用脫水劑。 The method for producing cyanopyridine according to any one of claims 1 to 6, wherein a dehydrating agent is used in the dehydration reaction. 一種碳酸酯之製造方法,其特徵在於具有:第1反應步驟,其在CeO2及ZrO2中任一方或雙方之固體催化劑與氰吡啶存在下,使一元醇與二氧化碳反應而生成碳酸酯與水,在此同時,藉由前述氰吡啶與前 述已生成之水的水合反應使吡啶甲醯胺生成;及第2反應步驟,其將源自前述第1反應步驟之前述吡啶甲醯胺分離出後,在載持有鹼金屬氧化物之催化劑存在下且在有機溶劑存在下,將該吡啶甲醯胺加熱並進行脫水反應,藉此而再生為氰吡啶;並且,將前述第2反應步驟所再生之氰吡啶使用於前述第1反應步驟中。 A method for producing a carbonate, characterized by comprising: a first reaction step of reacting a monohydric alcohol with carbon dioxide in the presence of a solid catalyst of either or both of CeO 2 and ZrO 2 in the presence of cyanopyridine to form a carbonate and water At the same time, the pyridine carbenamide is formed by the hydration reaction of the cyanopyridine with the water formed as described above; and the second reaction step of separating the pyridine carbenamide derived from the first reaction step. And the pyridine carbenamide is heated and dehydrated in the presence of an organic metal-containing catalyst in the presence of an organic solvent, thereby being regenerated into cyanide; and the second reaction step is regenerated The cyanopyridine is used in the first reaction step described above. 如請求項8之碳酸酯之製造方法,其具有:第1反應步驟,其將CeO2及ZrO2中任一方或雙方之固體催化劑與一元醇、二氧化碳及氰吡啶混合並使其反應,而生成碳酸酯與吡啶甲醯胺;第1分離步驟,其將自該第1反應步驟排出之碳酸酯、吡啶甲醯胺、未反應之氰吡啶及前述固體催化劑以烷烴實施溶劑萃取,之後施行固液分離而分離為:液相之碳酸酯、未反應之氰吡啶及烷烴以及固相之前述固體催化劑及吡啶甲醯胺;第2分離步驟,其使前述第1分離步驟之固液分離後之液相碳酸酯、未反應之氰吡啶及烷烴各自分離;第3分離步驟,其以親水性溶劑萃取前述第1分離步驟之固液分離後之固相,即固體催化劑及吡啶甲醯胺後,施行固液分離而分離為:液相之吡啶甲醯胺及親水性溶劑以及固相之固體催化劑;第2反應步驟,其在載持有鹼金屬氧化物之催化劑存在下且在有機溶劑存在下,將該第3分離步驟所分離 出之吡啶甲醯胺加熱使其進行脫水反應,而生成氰吡啶;第4分離步驟,其將自該第2反應步驟排出之氰吡啶、未反應之吡啶甲醯胺及載持有鹼金屬氧化物之催化劑予以過濾,而分離出固相之載持有鹼金屬氧化物之催化劑;及第5分離步驟,其使該第4分離步驟分離後殘存之氰吡啶、吡啶甲醯胺、有機溶劑及水各自分離;並且,將前述第5分離步驟所分離出之氰吡啶使用於前述第1反應步驟中。 The method for producing a carbonate according to claim 8, comprising: a first reaction step of mixing and reacting a solid catalyst of either or both of CeO 2 and ZrO 2 with monohydric alcohol, carbon dioxide, and cyanopyridine to form a carbonate and a pyridine carbamide; a first separation step of extracting a carbonate, a pyridine carbenamide, an unreacted cyanopyridine, and the foregoing solid catalyst discharged from the first reaction step by solvent extraction with an alkane, followed by performing a solid solution Separating and separating into: a liquid phase carbonate, an unreacted cyanopyridine and an alkane, and a solid phase of the solid catalyst and pyridine carbenamide; and a second separation step of separating the solid-liquid separation solution of the first separation step The phase carbonate is separated from the unreacted cyanopyridine and the alkane; and the third separation step is performed by extracting the solid phase after the solid-liquid separation in the first separation step, that is, the solid catalyst and the pyridine carbenamide, by a hydrophilic solvent. Solid-liquid separation and separation into: a liquid phase pyridine carbenamide and a hydrophilic solvent and a solid phase solid catalyst; a second reaction step in the presence of a catalyst carrying an alkali metal oxide and In the presence of an organic solvent, the pyridine carbenamide separated by the third separation step is heated to be subjected to a dehydration reaction to form a cyanide pyridine; and a fourth separation step of discharging cyanide from the second reaction step, a reaction of pyridylcarbamide and a catalyst carrying an alkali metal oxide to filter, and separating a solid phase catalyst carrying an alkali metal oxide; and a fifth separation step of separating the fourth separation step The remaining cyanide pyridine, pyridine carbenamide, an organic solvent and water are each separated; and the cyanide pyridine separated in the above fifth separation step is used in the first reaction step. 如請求項9之碳酸酯之製造方法,其更具有一使前述第3分離步驟所分離出之固體催化劑再生的步驟,並且將再生後之催化劑使用於前述第1反應步驟中。 The method for producing a carbonate according to claim 9, further comprising the step of regenerating the solid catalyst separated by the third separation step, and using the regenerated catalyst in the first reaction step. 如請求項9或10之碳酸酯之製造方法,其在前述第1反應步驟中有未反應之一元醇殘留,而在前述第1分離步驟中將自前述第1反應步驟排出之碳酸酯、吡啶甲醯胺、未反應之一元醇、未反應之氰吡啶及前述固體催化劑以烷烴實施溶劑萃取,之後施行固液分離而分離為:液相之碳酸酯、未反應之一元醇、未反應之氰吡啶及烷烴,以及固相之前述固體催化劑及吡啶甲醯胺。 The method for producing a carbonate according to claim 9 or 10, wherein in the first reaction step, the unreacted one of the alcohol remains, and in the first separating step, the carbonate and the pyridine are discharged from the first reaction step. The formamide, the unreacted monohydric alcohol, the unreacted cyanide, and the aforementioned solid catalyst are subjected to solvent extraction with an alkane, followed by solid-liquid separation to be separated into a liquid phase carbonate, an unreacted monohydric alcohol, and an unreacted cyanide. Pyridine and an alkane, and the aforementioned solid catalyst of the solid phase and pyridine carbenamide. 如請求項9至11中任一項之碳酸酯之製造方法,其在前述第1反應步驟中生成吡啶甲酸甲酯及胺甲酸甲酯中之至少任一者作為副產物,且在前述第1分離步驟中,將自前述第1反應步驟排出之碳酸酯、吡啶甲醯胺、未 反應之氰吡啶、吡啶甲酸甲酯、胺甲酸甲酯及前述固體催化劑以烷烴實施溶劑萃取,之後施行固液分離而分離為:液相之碳酸酯、未反應之氰吡啶、吡啶甲酸甲酯、胺甲酸甲酯及烷烴以及固相之前述固體催化劑及吡啶甲醯胺。 The method for producing a carbonate according to any one of claims 9 to 11, wherein in the first reaction step, at least one of methyl picolinate and methyl carbamate is produced as a by-product, and the first In the separation step, the carbonate, pyridine carbenamide, and the solvent discharged from the first reaction step are not The reaction cyanide, methyl pyridine, methyl carbamate and the above solid catalyst are subjected to solvent extraction with an alkane, followed by solid-liquid separation to be separated into a liquid phase carbonate, unreacted cyanide, methyl pyridinecarboxylate, The above-mentioned solid catalyst of methyl carbamate and alkane and a solid phase, and pyridine carbenamide. 如請求項9至12中任一項之碳酸酯之製造方法,其在前述第1反應步驟中有未反應之一元醇殘留,且生成吡啶甲酸甲酯及胺甲酸甲酯中之至少任一者作為副產物,而在前述第1分離步驟中將自前述第1反應步驟排出之碳酸酯、吡啶甲醯胺、未反應之一元醇、未反應之氰吡啶、吡啶甲酸甲酯、胺甲酸甲酯及前述固體催化劑以烷烴實施溶劑萃取,之後施行固液分離而分離為:液相之碳酸酯、未反應之一元醇、未反應之氰吡啶、吡啶甲酸甲酯、胺甲酸甲酯及烷烴以及固相之前述固體催化劑及吡啶甲醯胺。 The method for producing a carbonate according to any one of claims 9 to 12, wherein in the first reaction step, unreacted one of the alcohol remains, and at least one of methyl pyridinecarboxylate and methyl carbamic acid is formed. As a by-product, in the first separation step, the carbonate, the pyridine carbenamide, the unreacted monohydric alcohol, the unreacted cyanide, the methyl pyridinecarboxylate, the methyl carbamate are discharged from the first reaction step. And the solid catalyst is subjected to solvent extraction with an alkane, and then subjected to solid-liquid separation to be separated into: a liquid phase carbonate, an unreacted monohydric alcohol, an unreacted cyanide, a methyl pyridinecarboxylate, a methyl carbamate, an alkane, and a solid. The aforementioned solid catalyst and pyridine carbenamide. 如請求項9至13中任一項之碳酸酯之製造方法,其在前述溶劑萃取之際所使用之烷烴為己烷。 The method for producing a carbonate according to any one of claims 9 to 13, wherein the alkane used in the solvent extraction is hexane. 如請求項9至14中任一項之碳酸酯之製造方法,其中前述親水性溶劑為丙酮。 The method for producing a carbonate according to any one of claims 9 to 14, wherein the hydrophilic solvent is acetone. 如請求項8至15中任一項之碳酸酯之製造方法,其中前述氰吡啶為2-氰吡啶,且前述吡啶甲醯胺為2-吡啶甲醯胺。 The method for producing a carbonate according to any one of claims 8 to 15, wherein the cyanopyridine is 2-cyanopyridine, and the pyridine carbenamide is 2-pyridinecarbamide. 如請求項8至16中任一項之碳酸酯之製造方法,其中前述載持有鹼金屬氧化物之催化劑係一在SiO2、CeO2 及ZrO2中任1種或2種以上所構成之催化劑載體上載持有1種或2種以上鹼金屬氧化物的催化劑。 The method for producing a carbonate according to any one of claims 8 to 16, wherein the catalyst containing an alkali metal oxide is one or more selected from the group consisting of SiO 2 , CeO 2 and ZrO 2 . The catalyst carrier carries a catalyst which holds one or more kinds of alkali metal oxides. 如請求項17之碳酸酯之製造方法,其中前述催化劑載體為SiO2The method for producing a carbonate according to claim 17, wherein the catalyst carrier is SiO 2 . 如請求項8至18中任一項之碳酸酯之製造方法,其中前述鹼金屬氧化物為Li、K、Na、Rb及Cs中任一者之氧化物。 The method for producing a carbonate according to any one of claims 8 to 18, wherein the alkali metal oxide is an oxide of any one of Li, K, Na, Rb and Cs. 如請求項8至19中任一項之碳酸酯之製造方法,其中前述有機溶劑為對稱三甲苯。 The method for producing a carbonate according to any one of claims 8 to 19, wherein the organic solvent is symmetrical trimethylbenzene. 如請求項8至20中任一項之碳酸酯之製造方法,其係於前述脫水反應之際使用脫水劑。 The method for producing a carbonate according to any one of claims 8 to 20, wherein a dehydrating agent is used in the dehydration reaction. 如請求項8至21中任一項之碳酸酯之製造方法,其中前述一元醇為甲醇,且該方法製造碳酸二甲酯作為碳酸酯。 The method for producing a carbonate according to any one of claims 8 to 21, wherein the aforementioned monohydric alcohol is methanol, and the method produces dimethyl carbonate as a carbonate. 如請求項8至22中任一項之碳酸酯之製造方法,其中前述一元醇為乙醇,且該方法製造碳酸二乙酯作為碳酸酯。 The method for producing a carbonate according to any one of claims 8 to 22, wherein the aforementioned monohydric alcohol is ethanol, and the method produces diethyl carbonate as a carbonate. 一種碳酸酯之製造裝置,用於如請求項8至23中任一項之碳酸酯之製造方法,其特徵在於具有:加壓部,其加壓二氧化碳;第1反應部,其在CeO2及ZrO2中任一方或雙方之固體催化劑與氰吡啶存在下,使一元醇與二氧化碳反應而生成碳酸酯與水,在此同時,藉由前述氰吡啶與前述已生成之水的水合反應,使吡啶甲醯胺生成; 第1分離部,其將自該第1反應步驟排出之碳酸酯、吡啶甲醯胺、未反應之氰吡啶及前述固體催化劑以烷烴實施溶劑萃取,之後施行固液分離而分離為:液相之碳酸酯、未反應之氰吡啶及烷烴以及固相之前述固體催化劑及吡啶甲醯胺;第2分離部,其使前述第1分離部施行固液分離後之液相碳酸酯、未反應之氰吡啶及烷烴各自分離第3分離部,其以親水性溶劑萃取前述第1分離步驟施行固液分離後的固體催化劑及吡啶甲醯胺,之後施行固液分離而分離為:液相之吡啶甲醯胺及親水性溶劑以及固相之固體催化劑第2反應部,其在載持有鹼金屬氧化物之催化劑存在下且在有機溶劑存在下,將以前述第3分離部分離之前述吡啶甲醯胺加熱並使其進行脫水反應,而生成氰吡啶;第4分離部,其將自該第2反應部排出之氰吡啶、未反應之吡啶甲醯胺及載持有鹼金屬氧化物之催化劑予以過濾,而分離出固相之載持有鹼金屬氧化物之催化劑;第5分離部,其使該第4分離部施行分離後所殘存之氰吡啶、吡啶甲醯胺、有機溶劑及水各自分離;及輸送部,其將前述第5分離部所分離出之氰吡啶朝前述第1反應部輸送。 A method for producing a carbonate according to any one of claims 8 to 23, characterized by comprising: a pressurizing portion for pressurizing carbon dioxide; and a first reaction portion of CeO 2 and In the presence of a solid catalyst of either or both of ZrO 2 and cyanopyridine, the monohydric alcohol is reacted with carbon dioxide to form a carbonate and water, and at the same time, pyridine is reacted with the aforementioned water by hydration of the cyanopyridine. Formylamine; a first separation unit that extracts carbonate, pyridine carbenamide, unreacted cyanopyridine, and the solid catalyst discharged from the first reaction step by solvent extraction with an alkane, followed by solid-liquid separation to separate Is a liquid phase carbonate, an unreacted cyanopyridine and an alkane, and a solid phase of the solid catalyst and pyridine carbenamide; and a second separation unit that performs liquid-phase carbonate after solid-liquid separation of the first separation unit The unreacted cyanopyridine and the alkane are separated from each other by a third separation unit, which extracts the solid catalyst and the pyridine carbenamide after the solid-liquid separation in the first separation step by a hydrophilic solvent, and then performs solid-liquid separation. And separating into: a liquid phase pyridine carbenamide and a hydrophilic solvent and a solid phase solid catalyst second reaction portion, which is in the presence of a catalyst carrying an alkali metal oxide and in the presence of an organic solvent, 3, the pyridine carbenamide separated by the separation portion is heated and subjected to a dehydration reaction to form cyanide pyridine; a fourth separation portion which discharges cyanide from the second reaction portion, unreacted pyridine carbenamide and A catalyst containing an alkali metal oxide is filtered to separate a solid phase catalyst carrying an alkali metal oxide; and a fifth separation unit is provided to separate the cyanide and the pyridyl group remaining after the separation. The guanamine, the organic solvent, and the water are separated from each other; and the transport unit that transports the cyanopyridine separated by the fifth separation unit toward the first reaction unit. 一種苯甲腈之製造方法,其特徵在於:在催化劑存在下 且在有機溶劑存在下,將苯甲醯胺加熱使其進行脫水反應,藉以製造苯甲腈,並且,該催化劑係在由SiO2、TiO2、CeO2、ZrO2、Al2O3及C中任1種或2種以上所構成之催化劑載體上載持有鉬、鎢、錸、鈦及鈮中任1種或2種以上金屬種之金屬氧化物。 A method for producing benzonitrile, characterized in that benzamide is heated in a dehydration reaction in the presence of a catalyst in the presence of an organic solvent to thereby produce benzonitrile, and the catalyst is based on SiO 2 A catalyst carrier composed of one or more of TiO 2 , CeO 2 , ZrO 2 , Al 2 O 3 and C is supported on one or more of molybdenum, tungsten, tantalum, titanium and niobium. Metal oxides. 如請求項25之苯甲腈之製造方法,其將前述苯甲醯胺加熱並使其在液相狀態下進行脫水反應,藉以製出苯甲腈。 The method for producing benzonitrile according to claim 25, wherein the benzamide is heated and subjected to a dehydration reaction in a liquid phase to thereby produce benzonitrile. 如請求項25或26之苯甲腈之製造方法,其中前述催化劑載體為SiO2A process for producing benzonitrile according to claim 25 or 26, wherein the aforementioned catalyst carrier is SiO 2 . 如請求項25至27中任一項之苯甲腈之製造方法,其中前述催化劑係在SiO2之載體上載持有鉬氧化物。 The method for producing benzonitrile according to any one of claims 25 to 27, wherein the catalyst is a molybdenum oxide supported on a carrier of SiO 2 . 如請求項25至28中任一項之苯甲腈之製造方法,其中前述有機溶劑係由氯苯、二甲苯及對稱三甲苯中任1種或2種以上構成。 The method for producing benzonitrile according to any one of claims 25 to 28, wherein the organic solvent is one or more selected from the group consisting of chlorobenzene, xylene and symmetrical trimethylbenzene. 如請求項25至29中任一項之苯甲腈之製造方法,其在前述脫水反應之際使用脫水劑。 The method for producing benzonitrile according to any one of claims 25 to 29, wherein a dehydrating agent is used in the above dehydration reaction. 一種碳酸酯之製造方法,其特徵在於具有:第1反應步驟,其在CeO2及ZrO2中任一方或雙方之固體催化劑與苯甲腈存在下,使一元醇與二氧化碳反應而生成碳酸酯與水,在此同時,藉由前述苯甲腈與前述已生成之水的水合反應,使苯甲醯胺生成;及第2反應步驟,其將源自前述第1反應步驟之前述苯甲醯胺分離出後,在催化劑存在下且在有機溶劑存在 下,將該苯甲醯胺加熱並進行脫水反應,藉此而再生為苯甲腈,且,該催化劑係於SiO2、TiO2、CeO2、ZrO2、Al2O3及C中任1種或2種以上之催化劑載體上載持有鉬、鎢、錸、鈦及鈮中任1種或2種以上金屬種之金屬氧化物;並且,將前述第2反應步驟所再生之苯甲腈使用於前述第1反應步驟中。 A method for producing a carbonate, characterized by comprising: a first reaction step of reacting a monohydric alcohol with carbon dioxide in the presence of a solid catalyst of either or both of CeO 2 and ZrO 2 in the presence of benzonitrile to form a carbonate and Water, at the same time, by the hydration reaction of the aforementioned benzonitrile with the aforementioned water to form benzamide; and a second reaction step which is derived from the aforementioned benzamide from the first reaction step After separation, the benzamide is heated and dehydrated in the presence of a catalyst in the presence of an organic solvent, thereby regenerating to benzonitrile, and the catalyst is based on SiO 2 , TiO 2 , CeO 2 And a catalyst carrier of one or more of ZrO 2 , Al 2 O 3 and C, and a metal oxide of one or more of the metals of molybdenum, tungsten, niobium, titanium and niobium; and The benzonitrile regenerated in the second reaction step is used in the first reaction step. 如請求項31之碳酸酯之製造方法,其具有:第1反應步驟,其在CeO2及ZrO2中任一方或雙方之固體催化劑與苯甲腈存在下,使一元醇與二氧化碳反應而生成碳酸酯與水,在此同時,藉由前述苯甲腈與前述已生成之水的水合反應,使苯甲醯胺生成;第1分離步驟,其將自前述第1反應步驟排出之碳酸酯、苯甲醯胺、未反應之苯甲腈及前述固體催化劑以烷烴實施溶劑萃取,之後施行固液分離而分離為:液相之碳酸酯、未反應之苯甲腈及烷烴以及固相之前述固體催化劑及苯甲醯胺;第2分離步驟,其使前述固液分離後液相之碳酸酯、未反應苯甲腈及烷烴各自分離;第3分離步驟,其以親水性溶劑萃取前述固液分離後之固體催化劑及苯甲醯胺,並施行固液分離而分離為:液相之苯甲醯胺及親水性溶劑以及固相之固體催化劑;第2反應步驟,其在催化劑存在下且在有機溶劑存 在下將該第3分離步驟分離出之苯甲醯胺加熱並進行脫水反應,藉此而再生為苯甲腈,且該催化劑係在SiO2、TiO2、CeO2、ZrO2、Al2O3及C中任1種或2種以上之催化劑載體上載持有鉬、鎢、錸、鈦及鈮中任1種或2種以上金屬種之金屬氧化物;第4分離步驟,其將自第2反應步驟排出之苯甲腈、未反應之苯甲醯胺及在催化劑載體上載持有金屬氧化物之催化劑予以過濾,而分離出在催化劑載體上載持有金屬氧化物之固相催化劑;及第5分離步驟,其使該分離後殘存之苯甲腈、苯甲醯胺、有機溶劑及水各自分離;並且,將前述分離出之苯甲腈使用於前述第1反應步驟中。 The method for producing a carbonate according to claim 31, comprising: a first reaction step of reacting a monohydric alcohol with carbon dioxide to form carbonic acid in the presence of a solid catalyst of either or both of CeO 2 and ZrO 2 and benzonitrile; And ester and water, at the same time, by the hydration reaction of the benzonitrile with the water formed, the benzamide is formed; the first separation step, which is the carbonate, benzene discharged from the first reaction step The formamide, the unreacted benzonitrile and the solid catalyst are subjected to solvent extraction with an alkane, and then subjected to solid-liquid separation to be separated into a liquid phase carbonate, an unreacted benzonitrile and an alkane, and a solid phase solid catalyst. And a benzidine; a second separation step of separating the liquid phase carbonate, unreacted benzonitrile and an alkane after the solid-liquid separation; and a third separation step of extracting the solid-liquid separation with a hydrophilic solvent The solid catalyst and benzamide are separated by solid-liquid separation into: a liquid phase of benzamide and a hydrophilic solvent and a solid catalyst; a second reaction step in the presence of a catalyst and in an organic The presence of the third separating step of separating an amine of benzoyl heating and dehydration reaction, whereby the regenerated as benzonitrile, and the catalyst system in the SiO 2, TiO 2, CeO 2 , ZrO 2, Al 2 One or two or more kinds of catalyst carriers of O 3 and C are supported by a metal oxide of one or two or more kinds of metal species of molybdenum, tungsten, niobium, titanium, and niobium; and a fourth separation step, which will be carried out The benzonitrile discharged in the second reaction step, the unreacted benzamide and the catalyst carrying the metal oxide on the catalyst carrier are filtered, and the solid phase catalyst carrying the metal oxide on the catalyst carrier is separated; And a fifth separation step of separating benzonitrile, benzamide, an organic solvent and water remaining after the separation; and using the isolated benzonitrile in the first reaction step. 如請求項32之碳酸酯之製造方法,其更具有使前述已分離之固體催化劑再生的步驟,且將再生後之催化劑使用於前述第1反應步驟中。 The method for producing a carbonate according to claim 32, further comprising the step of regenerating the separated solid catalyst, and using the regenerated catalyst in the first reaction step. 如請求項32或33之碳酸酯之製造方法,其在前述溶劑萃取之際所使用的烷烴為己烷。 The method for producing a carbonate according to claim 32 or 33, wherein the alkane used in the solvent extraction is hexane. 如請求項32至34中任一項之碳酸酯之製造方法,其中前述親水性溶劑為丙酮。 The method for producing a carbonate according to any one of claims 32 to 34, wherein the hydrophilic solvent is acetone. 如請求項31至35中任一項之碳酸酯之製造方法,其中前述載持有金屬氧化物之催化劑載體為SiO2、TiO2、CeO2及ZrO2中之任1種或2種以上。 The method for producing a carbonate according to any one of claims 31 to 35, wherein the catalyst carrier carrying the metal oxide is one or more selected from the group consisting of SiO 2 , TiO 2 , CeO 2 and ZrO 2 . 如請求項36之碳酸酯之製造方法,其中前述催化劑載 體為SiO2The method for producing a carbonate according to claim 36, wherein the catalyst carrier is SiO 2 . 如請求項31至37中任一項之碳酸酯之製造方法,其中前述金屬氧化物為鉬氧化物。 The method for producing a carbonate according to any one of claims 31 to 37, wherein the metal oxide is a molybdenum oxide. 如請求項31至38中任一項之碳酸酯之製造方法,其中前述有機溶劑係由氯苯、二甲苯及對稱三甲苯中之任1種或2種以上構成。 The method for producing a carbonate according to any one of claims 31 to 38, wherein the organic solvent is one or more selected from the group consisting of chlorobenzene, xylene and symmetrical trimethylbenzene. 如請求項31至39中任一項之碳酸酯之製造方法,其在前述第2反應步驟中使用脫水劑。 The method for producing a carbonate according to any one of claims 31 to 39, wherein a dehydrating agent is used in the second reaction step. 如請求項31至40中任一項之碳酸酯之製造方法,其中前述一元醇為甲醇,且該製造方法係製造碳酸二甲酯作為碳酸酯。 The method for producing a carbonate according to any one of claims 31 to 40, wherein the monohydric alcohol is methanol, and the production method is to produce dimethyl carbonate as a carbonate. 如請求項31至41中任一項之碳酸酯之製造方法,其中前述一元醇為乙醇,且該製造方法係製造碳酸二乙酯作為碳酸酯。 The method for producing a carbonate according to any one of claims 31 to 41, wherein the monohydric alcohol is ethanol, and the production method is to produce diethyl carbonate as a carbonate. 一種碳酸酯之製造裝置,用於如請求項31至42中任一項之製造方法,其特徵在於具有:加壓部,其加壓二氧化碳;第1反應部,其在CeO2及ZrO2中任一方或雙方之固體催化劑與苯甲腈存在下,使一元醇與二氧化碳反應而生成碳酸酯與水,在此同時,藉由前述苯甲腈與前述已生成之水的水合反應,使苯甲醯胺生成;第1分離部,其將自該第1反應部排出之碳酸酯、苯甲醯胺、未反應之苯甲腈及前述固體催化劑以烷烴實施溶劑萃取,之後施行固液分離而分離為:液相之碳酸 酯、未反應之苯甲腈及烷烴以及固相之前述固體催化劑及苯甲醯胺;第2分離部,其使前述固液分離後液相之碳酸酯、未反應之苯甲腈及烷烴各自分離;第3分離部,其以親水性溶劑萃取前述固液分離後之固體催化劑及苯甲醯胺,之後施行固液分離而分離為:液相之苯甲醯胺及親水性溶劑以及固相之固體催化劑;第2反應部,其在催化劑存在下且在有機溶劑存在下,將該已分離之苯甲醯胺加熱而使其脫水反應並生成苯甲腈,且,該催化劑係於SiO2、TiO2、CeO2、ZrO2、Al2O3及C中任1種或2種以上之催化劑載體上載持有鉬、鎢、錸、釩及鈮中任1種或2種以上金屬種之金屬氧化物;第4分離部,其將該第2反應部所排出之苯甲腈、未反應之苯甲醯胺及在催化劑載體上載持有金屬氧化物之催化劑予以過濾,而分離出固相之載持有金屬氧化物之催化劑;第5分離部,其使該分離後殘存之苯甲腈、苯甲醯胺、有機溶劑及水各自分離;及輸送部,其將前述已分離之苯甲腈朝前述第1反應部輸送。 A manufacturing apparatus of a carbonate according to any one of claims 31 to 42, characterized by having a pressurizing portion that pressurizes carbon dioxide, and a first reaction portion in CeO 2 and ZrO 2 In the presence of either or both of the solid catalyst and benzonitrile, the monohydric alcohol is reacted with carbon dioxide to form a carbonate and water, and at the same time, the benzonitrile is hydrated by the hydration reaction of the aforementioned water to form a benzoic acid. The first separation unit is characterized in that the carbonate, the benzamide, the unreacted benzonitrile, and the solid catalyst discharged from the first reaction unit are subjected to solvent extraction with an alkane, followed by solid-liquid separation and separation. The liquid phase carbonate, the unreacted benzonitrile and the alkane, and the solid catalyst and the benzamide; the second separation unit, which dissolves the liquid phase carbonate after the solid-liquid separation, and the unreacted The benzonitrile and the alkane are each separated; the third separation unit extracts the solid catalyst and the benzamide after the solid-liquid separation by a hydrophilic solvent, and then performs solid-liquid separation to separate into a liquid phase of benzamide and Hydrophilic solvent and solid a solid catalyst; a second reaction portion which, in the presence of a catalyst and in the presence of an organic solvent, heats the separated benzamide to cause dehydration reaction to form benzonitrile, and the catalyst is based on SiO 2. A catalyst carrier of one or more of TiO 2 , CeO 2 , ZrO 2 , Al 2 O 3 and C is supported on one or more of molybdenum, tungsten, rhenium, vanadium and niobium. a metal oxide; a fourth separation unit that separates the benzonitrile discharged from the second reaction unit, the unreacted benzamide, and the catalyst on which the metal oxide is supported on the catalyst carrier a catalyst for holding a metal oxide; a fifth separation portion that separates benzonitrile, benzamide, an organic solvent, and water remaining after the separation; and a transport portion that separates the separated benzene The formonitrile is transported to the first reaction unit.
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