TW201708166A - Method for preparation of 1,4-cyclohexanedialkanol - Google Patents
Method for preparation of 1,4-cyclohexanedialkanol Download PDFInfo
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本發明有關一種1,4-環己烷二烷醇之製法，尤係關於使1,4-環己烷二羧酸二烷酯在低氫氣入料比下進行氫化反應，而製備1,4-環己烷二烷醇之製法。 The invention relates to a process for preparing 1,4-cyclohexaneditanol, in particular to hydrogenating a 1,4-cyclohexanedicarboxylate dialkyl ester at a low hydrogen feed ratio to prepare 1,4 - Process for the preparation of cyclohexane dialkyl alcohol.
1,4-環己烷二烷醇主要係用以取代乙二醇而與對苯二甲酸進行聚縮合反應，而製得聚酯共聚物。藉由1,4-二羥甲基環己烷所製得之聚酯共聚物，比習知聚酯具有更高之阻氣性、較高透明度、及較大之強度及耐熱性。 The 1,4-cyclohexanedialol is mainly used for the polycondensation reaction with terephthalic acid in place of ethylene glycol to obtain a polyester copolymer. The polyester copolymer obtained by 1,4-dimethylolcyclohexane has higher gas barrier properties, higher transparency, and greater strength and heat resistance than conventional polyesters.
此外，1,4-環己烷二烷醇亦可應用在塗料樹脂用途上。據此，已有許多習知技術提出合成1,4-環己烷二烷醇之方法。 In addition, 1,4-cyclohexanedane alcohol can also be used in coating resin applications. Accordingly, many conventional techniques have been proposed for the synthesis of 1,4-cyclohexanedialol.
例如，第1109859A號大陸專利揭示一種對環己二羧酸二烷基酯進行氫化以生產環己二甲醇的方法，該氫化區係使用錳助催化之銅觸媒，其供料溫度範圍為約150至350℃及供料壓力範圍約150至2000psia，該氫氣與1,4-環己烷二甲酸二甲酯的莫耳比為200：1至1000：1，且該1,4-環己烷二甲酸二甲酯與氫氣形成高於露點的蒸汽混合物與觸 媒接觸氫化產生1,4-環己烷二甲醇產物。 For example, Continental Patent No. 1109859A discloses a process for the hydrogenation of a dialkyl cyclohexanedicarboxylate to produce cyclohexanedimethanol using a manganese-promoted copper catalyst having a feed temperature range of about 150 to 350 ° C and a feed pressure range of about 150 to 2000 psia, the molar ratio of the hydrogen to dimethyl 1,4-cyclohexanedicarboxylate is from 200:1 to 1000:1, and the 1,4-cyclohexane Dimethyl alkanedicarboxylate and hydrogen form a vapor mixture and contact with a dew point The vehicle is contacted with hydrogen to produce a 1,4-cyclohexanedimethanol product.
再者，第575544號台灣專利揭示一種環己烷二甲醇之製造方法，係包含將環己烷二羧酸二烷基酯，利用固定層連續反應，在含銅鉻觸媒存在下，於反應溫度225至280℃、氫氣壓力200至250kgf/cm2、及氫氣供給速度為以空塔線速度計為1至40cm/秒之條件下進行氫化反應以產生1,4-環己烷二甲醇產物。 Further, Taiwan Patent No. 575544 discloses a method for producing cyclohexanedimethanol which comprises reacting a dialkyl cyclohexanedicarboxylate with a fixed layer in the presence of a copper-containing chromium catalyst. The hydrogenation reaction is carried out at a temperature of 225 to 280 ° C, a hydrogen pressure of 200 to 250 kgf / cm 2 , and a hydrogen supply rate of 1 to 40 cm / sec in terms of a superficial linear velocity to produce a 1,4-cyclohexane dimethanol product. .
上述該等先前技術所揭示之方法，其反應溫度及壓力皆必須在較嚴苛的條件，以使反應物環己烷二羧酸二烷酯為氣態下與氫氣進行氫化反應，且需使用大量的氫氣進行氫化反應，因此反應時風險高、設備投資成本高，且嚴苛之反應條件易導致觸媒壽命縮短並易形成副產物。尤更甚者，若使用含有鉻毒性金屬之觸媒，將嚴重污染環境並造成職業傷害。 In the methods disclosed in the above prior art, the reaction temperature and pressure must be under relatively severe conditions, so that the reactant cyclohexanedicarboxylic acid dialkyl ester is hydrogenated with hydrogen, and a large amount of the reaction is required. The hydrogen gas undergoes a hydrogenation reaction, so the reaction risk is high, the equipment investment cost is high, and the severe reaction conditions are liable to cause the catalyst life to be shortened and to form by-products. What is more, if you use a catalyst containing chromium toxic metals, it will seriously pollute the environment and cause occupational injuries.
有鑑於此，本發明係提供一種低氫氣入料比之氫化反應，其中以銅/鋁/錳觸媒配合助觸媒之使用，可減少氫氣使用量且於溫和的條件下進行反應，同時為考量到綠色化學且適用於製造1,4-環己烷二烷醇之方法。 In view of the above, the present invention provides a hydrogenation reaction with a low hydrogen feed ratio, wherein the use of a copper/aluminum/manganese catalyst in combination with a catalytic catalyst can reduce the amount of hydrogen used and carry out the reaction under mild conditions, while A method of considering green chemistry and being suitable for the manufacture of 1,4-cyclohexaneditanol.
本發明係提供一種製造1,4-環己烷二烷醇(CHDM)之方法，包括使液態之1,4-環己烷二羧酸二烷酯(DMCD)在銅/錳/鋁觸媒及助觸媒存在之反應器中進行氫化反應，而製備1,4-環己烷二烷醇，其中，該氫氣與1,4-環己烷二羧酸二烷酯的進料莫耳比例為4：1至12：1。 The present invention provides a process for producing 1,4-cyclohexaneditanol (CHDM) comprising liquid 1,4-cyclohexanedicarboxylic acid dialkyl ester (DMCD) in copper/manganese/aluminum catalyst And hydrogenation reaction in a reactor in which a catalyst is present to prepare 1,4-cyclohexanedialol, wherein the molar ratio of the hydrogen to the 1,4-cyclohexanedicarboxylic acid dialkyl ester It is 4:1 to 12:1.
依據本發明之方法，反應所需之氫氣進料量較少，且可在較溫和之壓力條件下進行氫化反應以降低反應副產物，而可顯著增加安全性及節省運轉費用，據此符合工業上之經濟效益。 According to the method of the present invention, the amount of hydrogen required for the reaction is small, and the hydrogenation reaction can be carried out under milder pressure conditions to reduce reaction by-products, which can significantly increase safety and save operating costs, thereby complying with the industry. The economic benefits.
以下實施例用以說明本發明，本發明之申請專利範圍 並不會因此而受限制。本發明亦可藉由其它不同之實施方式加以施行或應用，本說明書中的各項細節亦可基於不同觀點與應用，在不悖離本發明所揭示之精神下進行各種修飾與變更。 The following examples are intended to illustrate the invention, and the scope of the patent application of the present invention It will not be restricted as a result. The present invention may be embodied or applied in various other embodiments, and various modifications and changes can be made without departing from the spirit and scope of the invention.
本發明係提供一種製造1,4-環己烷二烷醇之方法，包括使液態之1,4-環己烷二羧酸二烷酯在銅/錳/鋁觸媒及助觸媒存在之反應器中與氫氣進行氫化反應，而製備1,4-環己烷二烷醇，其中，該氫氣與1,4-環己烷二羧酸二烷酯的進料莫耳比例為4：1至12：1。 The present invention provides a process for producing 1,4-cyclohexaneditanol, which comprises dissolving a liquid dialkyl 1,4-cyclohexanedicarboxylate in a copper/manganese/aluminum catalyst and a catalytic catalyst. The reactor is hydrogenated with hydrogen to prepare 1,4-cyclohexanedialol, wherein the molar ratio of the hydrogen to the 1,4-cyclohexanedicarboxylic acid dialkyl ester is 4:1. Until 12:1.
本發明方法中所用之1,4-環己烷二羧酸二烷酯之烷酯可為C1-6烷酯，該二烷酯之烷基彼此可相同或不同。1,4-環己烷二羧酸二烷酯可為例如1,4-環己烷二羧酸二甲酯、1,4-環己烷二羧酸二乙酯、1,4-環己烷二羧酸二丙酯、1,4-環己烷二羧酸二丁酯、1,4-環己烷二羧酸二戊酯、1,4-環己烷二羧酸二己酯、1,4-環己烷二羧酸甲酯乙酯、1,4-環己烷二羧酸甲酯丙酯、1,4-環己烷二羧酸甲酯丁酯、1,4-環己烷 二羧酸甲酯戊酯、1,4-環己烷二羧酸甲酯己酯、1,4-環己烷二羧酸乙酯丙酯、1,4-環己烷二羧酸乙酯丁酯、1,4-環己烷二羧酸乙酯戊酯1,4-、環己烷二羧酸乙酯己酯、1,4-環己烷二羧酸丙酯丁酯、1,4-環己烷二羧酸丙酯戊酯、1,4-環己烷二羧酸丙酯己酯、1,4-環己烷二羧酸丁酯戊酯、1,4-環己烷二羧酸丁酯己酯以及1,4-環己烷二羧酸戊酯己酯等。 The alkyl ester of the dialkyl 1,4-cyclohexanedicarboxylate used in the process of the present invention may be a C 1-6 alkyl ester, and the alkyl groups of the dialkyl ester may be the same or different from each other. The dialkyl 1,4-cyclohexanedicarboxylate may be, for example, dimethyl 1,4-cyclohexanedicarboxylate, diethyl 1,4-cyclohexanedicarboxylate, 1,4-cyclohexane. Dipropyl alkanedicarboxylate, dibutyl 1,4-cyclohexanedicarboxylate, diamyl 1,4-cyclohexanedicarboxylate, dihexyl 1,4-cyclohexanedicarboxylate, Methyl 1,4-cyclohexanedicarboxylate, methyl propyl 1,4-cyclohexanedicarboxylate, butyl 1,4-cyclohexanedicarboxylate, 1,4-cyclohexane Methyl hexane dicarboxylate, methyl hexyl 1,4-cyclohexanedicarboxylate, ethyl propyl 1,4-cyclohexanedicarboxylate, 1,4-cyclohexanedicarboxylic acid Ethyl butyl acrylate, ethyl 1,4-cyclohexanedicarboxylate 1,4-, ethyl hexyl cyclohexanedicarboxylate, butyl 1,4-cyclohexanedicarboxylate, Amyl 1,4-cyclohexanedicarboxylate, propyl 1,4-cyclohexanedicarboxylate, butyl 1,4-cyclohexanedicarboxylate, 1,4-cyclohexane Butyl hexane dicarboxylate and pentyl 1,4-cyclohexanedicarboxylate and the like.
本發明方法中所用之觸媒為銅/錳/鋁觸媒，該觸媒中銅：錳：鋁之重量比約為2.2：0.3：1至約3.6：0.7：1，此外，該銅/錳/鋁觸媒之形狀無特殊限制，可為顆粒狀、圓柱狀、片狀或不規則狀，該銅/錳/鋁觸媒之粒徑範圍為1至4mm。 The catalyst used in the method of the present invention is a copper/manganese/aluminum catalyst having a weight ratio of copper:manganese:aluminum of about 2.2:0.3:1 to about 3.6:0.7:1, and further, the copper/manganese The shape of the aluminum catalyst is not particularly limited and may be granular, cylindrical, flake or irregular, and the copper/manganese/aluminum catalyst has a particle diameter ranging from 1 to 4 mm.
本發明方法中所用之助觸媒包括VA族元素或VB族元素，其中該VB族元素以釩為佳，該VA族元素則以磷尤佳。基於銅/錳/鋁觸媒之總重，助觸媒之添加量為0.1至6重量%，其中該助觸媒係可為釩氧化物或磷氧化物。 The cocatalyst used in the method of the present invention comprises a group VA element or a group VB element, wherein the group VB element is preferably vanadium, and the VA group element is preferably phosphorus. The amount of the co-catalyst added is 0.1 to 6% by weight based on the total weight of the copper/manganese/aluminum catalyst, wherein the cocatalyst may be vanadium oxide or phosphorus oxide.
本發明方法中，氫化反應之溫度範圍為190至250℃之範圍較佳為195℃至250℃。 In the process of the present invention, the temperature of the hydrogenation reaction is in the range of from 190 to 250 ° C, preferably from 195 ° C to 250 ° C.
本發明方法中，該反應器中之壓力為120至150kgf/cm2。 In the process of the invention, the pressure in the reactor is from 120 to 150 kgf/cm 2 .
於一具體實施例中，在190至250℃進行氫化反應，可較此範圍外進行的反應提升29%以上之轉化率，在120至150kgf/cm2壓力範圍進行反應，可較此範圍外進行的反應提升10%以上的選擇率。 In one embodiment, the hydrogenation reaction is carried out at 190 to 250 ° C, and the reaction carried out outside the range can be increased by more than 29%, and the reaction can be carried out at a pressure of 120 to 150 kgf/cm 2 , which can be carried out outside the range. The response increased by more than 10%.
本發明方法可為連續式或批次反應。本發明之反應器 為固定床(fix-bed)反應器或攪拌式反應器。於一具體實施例中，該氫氣係由固定床反應器之上方饋入反應器。此外，如1,4-環己烷二羧酸二烷酯之液體進料和氫氣係同向進料，流經觸媒固定床進行氫化作用。 The process of the invention can be a continuous or batch reaction. Reactor of the invention It is a fixed-bed reactor or a stirred reactor. In one embodiment, the hydrogen is fed to the reactor from above the fixed bed reactor. Further, a liquid feed such as a 1,4-cyclohexanedicarboxylic acid dialkyl ester and a hydrogen-based co-feed are passed through a catalyst fixed bed for hydrogenation.
根據本發明之方法，可大幅降低氫氣的使用量，並提升反應之安全性。 According to the method of the present invention, the amount of hydrogen used can be greatly reduced, and the safety of the reaction can be improved.
本發明方法中，1,4-環己烷二羧酸二烷酯之每小時液體空間速度(WHSV)為0.1至1.0小時-1。另外，根據本發明之方法，進料之1,4-環己烷二羧酸二烷酯係為液態，更易於進入或接觸該銅/錳/鋁觸媒之表面，以進行氫化反應，並提升轉化率。 In the process of the present invention, the hourly liquid space velocity (WHSV) of the 1,4-cyclohexanedicarboxylic acid dialkyl ester is from 0.1 to 1.0 hr -1 . Further, according to the method of the present invention, the feed dialkyl 1,4-cyclohexanedicarboxylate is in a liquid state, and it is easier to enter or contact the surface of the copper/manganese/aluminum catalyst for hydrogenation reaction, and Increase conversion rates.
1).取70g的Al2O3粉末放入120℃的烘箱乾燥除水12小時。 1). 70 g of Al 2 O 3 powder was placed in an oven at 120 ° C to remove water for 12 hours.
2).提供含有Cu+2鹽：硝酸銅鹽(Cu(NO3)2．3H2O)、Mn+2鹽：硝酸錳鹽(Mn(NO3)2．6H2O)及V2O5混合鹽水溶液，該混合鹽水溶液中Cu+2濃度為6.3mol/L、Mn+2濃度為1.2mol/L及V+5濃度為0.6mol/L，以形成含Cu+2、Mn+2及V+5之混合鹽水溶液(溶於水中)。 2). Providing a salt containing Cu +2 : copper nitrate salt (Cu(NO 3 ) 2 .3H 2 O), Mn +2 salt: manganese nitrate salt (Mn(NO 3 ) 2 .6H 2 O) and V 2 O 5 mixed salt aqueous solution, the mixed salt solution has a Cu +2 concentration of 6.3 mol / L, a Mn + 2 concentration of 1.2 mol / L and a V + 5 concentration of 0.6 mol / L to form Cu + 2 , Mn + 2 And a mixed salt solution of V + 5 (dissolved in water).
3).將該混合鹽水溶液390ml滴加至該乾燥除水後的70g的Al2O3粉末中，並進行攪拌，該混合鹽水溶液滴加完後，Al2O3粉末係含浸於該混合鹽水溶液中，然後置於120℃烘箱乾燥24小時後，自然冷卻造粒。 3). 390 ml of the mixed saline solution was added dropwise to 70 g of the Al 2 O 3 powder after the dry water removal, and the mixture was stirred. After the mixed saline solution was added dropwise, the Al 2 O 3 powder was impregnated into the mixture. The salt solution was then dried in an oven at 120 ° C for 24 hours, and then naturally cooled and granulated.
4).造粒完成後，將其放入高溫爐內，在550℃下鍛燒6小 時。 4). After granulation is completed, put it in a high temperature furnace and calcined at 550 ° C for 6 hours. Time.
1).取35g的Al2O3粉末放入120℃的烘箱乾燥除水12小時。 1). 35 g of Al 2 O 3 powder was placed in an oven at 120 ° C to remove water for 12 hours.
2).提供含有Cu+2鹽：硝酸銅鹽(Cu(NO3)2．3H2O)、Mn+2鹽：硝酸錳鹽(Mn(NO3)2．6H2O)混合鹽水溶液，該混合鹽水溶液中Cu+2濃度為6.3mol/L及Mn+2濃度為1.2mol/L，以形成含Cu+2及Mn+2之混合鹽水溶液(溶於水中)。 2) Providing a mixed salt solution containing Cu + 2 salt: copper nitrate salt (Cu(NO 3 ) 2 .3H 2 O), Mn +2 salt: manganese nitrate salt (Mn(NO 3 ) 2 .6H2O), the mixture The concentration of Cu +2 in the brine solution was 6.3 mol/L and the concentration of Mn +2 was 1.2 mol/L to form a mixed salt solution containing Cu +2 and Mn + 2 (dissolved in water).
3).將該混合鹽水溶液192ml滴加至該乾燥除水後的35g的Al2O3粉末中，並進行攪拌，該混合鹽水溶液滴加完後，Al2O3粉末係含浸於該混合鹽水溶液中，然後置於120℃烘箱乾燥24小時後，自然冷卻造粒。 3). 192 ml of the mixed salt solution was added dropwise to 35 g of the Al 2 O 3 powder after the dry water removal, and the mixture was stirred. After the mixed salt solution was added dropwise, the Al 2 O 3 powder was impregnated into the mixture. The salt solution was then dried in an oven at 120 ° C for 24 hours, and then naturally cooled and granulated.
4).造粒完成後，將其放入高溫爐內，在550℃下鍛燒6小時。 4) After granulation is completed, it is placed in a high temperature furnace and calcined at 550 ° C for 6 hours.
利用管徑為1英吋，材質為不銹鋼316管狀反應器裝入50ml的製備例1所製備之顆粒狀銅/錳/鋁(Cu/Mn/Al2O3)觸媒(A觸媒)。首先分別以含3%、5%及10%氫氣之氮氣混合氣體於約120至230℃溫度下，將銅/錳/鋁觸媒還原成金屬狀態，接著將純度99.9%以上的氫氣自鋼瓶經壓縮機壓縮至反應器。液體進料和氫氣係自反應器上端饋入，同向流動經觸媒固定床進行氫化作用，產物係由反應器下端流出。其中工業級液體進料之1,4-環己烷二甲酸二甲酯為 98.4wt%，液體流速為15g/hr，氫氣以366ml/min之速率經預熱器混合後流經觸媒床反應。分別以表1所列之反應溫度、壓力、1,4-環己烷二羧酸二烷酯之WHSV及氫氣/1,4-環己烷二甲酸二甲酯液體之莫耳比例製備1,4-環己烷二甲醇。 A granular copper/manganese/aluminum (Cu/Mn/Al 2 O 3 ) catalyst (A catalyst) prepared in Preparation Example 1 was charged into a stainless steel 316 tubular reactor using a tube diameter of 1 inch. First, the copper/manganese/aluminum catalyst is reduced to a metal state at a temperature of about 120 to 230 ° C with a nitrogen mixed gas containing 3%, 5%, and 10% hydrogen, and then a hydrogen having a purity of 99.9% or more is passed from the cylinder. The compressor is compressed to the reactor. The liquid feed and hydrogen are fed from the upper end of the reactor, and the cocurrent flow is hydrogenated through a catalyst fixed bed, and the product flows out from the lower end of the reactor. The industrial grade liquid feed dimethyl 1,4-cyclohexanedicarboxylate is 98.4 wt%, the liquid flow rate is 15 g/hr, and the hydrogen gas is mixed at a rate of 366 ml/min through a preheater and then passed through a catalytic bed reaction. . Prepared 1 by the reaction temperature, pressure, WHSV of 1,4-cyclohexanedicarboxylate and dimethyl ratio of hydrogen/dimethyl 1,4-cyclohexanedicarboxylate listed in Table 1, respectively. 4-cyclohexanedimethanol.
當氫化產物以穩定狀態流出後，取樣並以氣相層析儀分析，使用長50公尺，內徑0.2毫米的熔融二氧化矽管柱，內部以0.5微米的交聯甲基矽氧烷膜塗覆之毛細管，及火燄電離偵測器。儀器配備具有高峰積分之軟體及利用已知組成分的試藥級1,4-環己烷二羧酸二甲酯和1,4-二羥甲基環己烷樣品作校準。由結果發現1,4-環己烷二羧酸二甲酯轉化率為99.6%以上，1,4-二羥甲基環己烷選擇率為92.7%以上。 When the hydrogenated product was discharged in a steady state, it was sampled and analyzed by a gas chromatograph using a 50 m long, 0.2 mm inner diameter ruthenium dioxide column with a 0.5 μm crosslinked methyl siloxane film inside. Coated capillary, and flame ionization detector. The instrument was equipped with a software with peak integration and a calibration sample of 1,4-cyclohexanedicarboxylate and 1,4-dimethylolcyclohexane using known components. As a result, it was found that the conversion ratio of dimethyl 1,4-cyclohexanedicarboxylate was 99.6% or more, and the selectivity of 1,4-dimethylolcyclohexane was 92.7% or more.
利用管徑為1英吋，材質為不銹鋼316管狀反應器裝入50ml的製備例2所製備之銅/錳/鋁(Cu/Mn/Al2O3)觸媒成顆粒狀(B觸媒)。首先分別以含3%、5%及10%氫氣之氮氣混合氣體於約120至230℃溫度下，將銅/錳/鋁觸媒還原成金屬狀態，接著將純度99.9%以上的氫氣自鋼瓶經壓縮機壓縮至反應器。液體進料和氫氣係自反應器上端流入，同方向流向下流經觸媒固定床進行氫化作用，產物係由反應器下端流出。其中工業級液體進料之1,4-環己烷二甲酸二甲酯為98.4wt%，液體流速15g/hr，氫氣以366ml/min之速率經預熱器混合後流經觸媒床反應。分別以表2所列之反應溫度、壓力、1,4-環己烷二羧酸二烷酯之WHSV及氫氣/1,4-環己烷二甲酸二甲酯液體之莫耳比例製備1,4-環己烷二甲醇。 A copper/manganese/aluminum (Cu/Mn/Al 2 O 3 ) catalyst prepared in Preparation 2 was prepared into a pellet (B catalyst) using a stainless steel 316 tubular reactor having a diameter of 1 inch. . First, the copper/manganese/aluminum catalyst is reduced to a metal state at a temperature of about 120 to 230 ° C with a nitrogen mixed gas containing 3%, 5%, and 10% hydrogen, and then a hydrogen having a purity of 99.9% or more is passed from the cylinder. The compressor is compressed to the reactor. The liquid feed and hydrogen are fed from the upper end of the reactor, and the same direction flows downward through the catalyst fixed bed for hydrogenation, and the product flows out from the lower end of the reactor. The industrial grade liquid feed dimethyl 1,4-cyclohexanedicarboxylate was 98.4 wt%, the liquid flow rate was 15 g/hr, and the hydrogen was mixed at a rate of 366 ml/min through a preheater and then passed through a catalytic bed to react. Prepared 1 by the reaction temperature, pressure, WHSV of 1,4-cyclohexanedicarboxylate and dimethyl ratio of hydrogen/dimethyl 1,4-cyclohexanedicarboxylate listed in Table 2, respectively. 4-cyclohexanedimethanol.
當氫化產物以穩定狀態流出後，取樣並以氣相層析儀分析，使用長50公尺，內徑0.2毫米的熔融二氧化矽管柱，內部以0.5微米的交聯甲基矽氧烷膜塗覆之毛細管，及火燄電離偵測器。儀器配備具有高峰積分之軟體及利用已知組成分的試藥級1,4-環己烷二羧酸二甲酯和1,4-二羥甲基環己烷樣品作校準。由結果發現1,4-環己烷二羧酸二甲酯轉化率為88.3%以上，1,4-二羥甲基環己烷選擇率為82.1以上。 When the hydrogenated product was discharged in a steady state, it was sampled and analyzed by a gas chromatograph using a 50 m long, 0.2 mm inner diameter ruthenium dioxide column with a 0.5 μm crosslinked methyl siloxane film inside. Coated capillary, and flame ionization detector. The instrument was equipped with a software with peak integration and a calibration sample of 1,4-cyclohexanedicarboxylate and 1,4-dimethylolcyclohexane using known components. As a result, it was found that the conversion ratio of dimethyl 1,4-cyclohexanedicarboxylate was 88.3% or more, and the selectivity of 1,4-dimethylolcyclohexane was 82.1 or more.
本發明之1,4-環己烷二烷醇之製法係在銅/錳/鋁觸媒及助觸媒存在下之反應器中與氫氣進行氫化反應，而製備1,4-環己烷二烷醇，其中該1,4-環己烷二羧酸二烷酯係於液態下進行氫化反應。根據實施例之數據可知，本發明之製法所需要進料之氫氣比例較低，可於溫和的條件下進行氫化反應，且所得之1,4-環己烷二羧酸二甲酯有良好的轉化率及選擇率。 The 1,4-cyclohexanedialol of the present invention is produced by hydrogenating hydrogen with a hydrogen in a reactor in the presence of a copper/manganese/aluminum catalyst and a cocatalyst to prepare 1,4-cyclohexane. An alkanol wherein the dialkyl 1,4-cyclohexanedicarboxylate is subjected to a hydrogenation reaction in a liquid state. According to the data of the examples, the process of the present invention requires a low proportion of hydrogen to be fed, can be hydrogenated under mild conditions, and the obtained dimethyl 1,4-cyclohexanedicarboxylate has good Conversion rate and selection rate.
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