JPH02115138A - Production of phenol and aniline - Google Patents
Production of phenol and anilineInfo
- Publication number
- JPH02115138A JPH02115138A JP63268154A JP26815488A JPH02115138A JP H02115138 A JPH02115138 A JP H02115138A JP 63268154 A JP63268154 A JP 63268154A JP 26815488 A JP26815488 A JP 26815488A JP H02115138 A JPH02115138 A JP H02115138A
- Authority
- JP
- Japan
- Prior art keywords
- catalyst
- aniline
- benzene
- phenol
- ammonia
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 title claims abstract description 92
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 title claims abstract description 51
- 238000004519 manufacturing process Methods 0.000 title claims description 16
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims abstract description 113
- 239000003054 catalyst Substances 0.000 claims abstract description 47
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims abstract description 45
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims abstract description 36
- 229910021529 ammonia Inorganic materials 0.000 claims abstract description 21
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 21
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims abstract description 18
- 238000000034 method Methods 0.000 claims description 30
- 238000006243 chemical reaction Methods 0.000 claims description 28
- 229910019142 PO4 Inorganic materials 0.000 claims description 6
- 239000010452 phosphate Substances 0.000 claims description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 4
- RAOSIAYCXKBGFE-UHFFFAOYSA-K [Cu+3].[O-]P([O-])([O-])=O Chemical group [Cu+3].[O-]P([O-])([O-])=O RAOSIAYCXKBGFE-UHFFFAOYSA-K 0.000 claims description 2
- 239000001506 calcium phosphate Substances 0.000 claims description 2
- 229910000389 calcium phosphate Inorganic materials 0.000 claims description 2
- 235000011010 calcium phosphates Nutrition 0.000 claims description 2
- 229910000151 chromium(III) phosphate Inorganic materials 0.000 claims description 2
- IKZBVTPSNGOVRJ-UHFFFAOYSA-K chromium(iii) phosphate Chemical compound [Cr+3].[O-]P([O-])([O-])=O IKZBVTPSNGOVRJ-UHFFFAOYSA-K 0.000 claims description 2
- 229910000398 iron phosphate Inorganic materials 0.000 claims description 2
- WBJZTOZJJYAKHQ-UHFFFAOYSA-K iron(3+) phosphate Chemical compound [Fe+3].[O-]P([O-])([O-])=O WBJZTOZJJYAKHQ-UHFFFAOYSA-K 0.000 claims description 2
- QORWJWZARLRLPR-UHFFFAOYSA-H tricalcium bis(phosphate) Chemical compound [Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O QORWJWZARLRLPR-UHFFFAOYSA-H 0.000 claims description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 abstract description 20
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 abstract description 11
- 239000001569 carbon dioxide Substances 0.000 abstract description 10
- 229910002092 carbon dioxide Inorganic materials 0.000 abstract description 10
- 239000002994 raw material Substances 0.000 abstract description 10
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 abstract description 8
- 239000007789 gas Substances 0.000 abstract description 8
- 229910052751 metal Inorganic materials 0.000 abstract description 7
- 239000002184 metal Substances 0.000 abstract description 7
- 238000001354 calcination Methods 0.000 abstract description 6
- 239000008187 granular material Substances 0.000 abstract description 6
- 150000003839 salts Chemical class 0.000 abstract description 6
- 229910052814 silicon oxide Inorganic materials 0.000 abstract description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 abstract description 4
- 229910052757 nitrogen Inorganic materials 0.000 abstract description 4
- 239000011230 binding agent Substances 0.000 abstract description 3
- 239000011261 inert gas Substances 0.000 abstract description 3
- 239000000203 mixture Substances 0.000 abstract description 3
- 239000002244 precipitate Substances 0.000 abstract description 3
- 229910052786 argon Inorganic materials 0.000 abstract description 2
- 238000006555 catalytic reaction Methods 0.000 abstract description 2
- 238000001035 drying Methods 0.000 abstract description 2
- 238000001914 filtration Methods 0.000 abstract description 2
- 239000001307 helium Substances 0.000 abstract description 2
- 229910052734 helium Inorganic materials 0.000 abstract description 2
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 abstract description 2
- 239000000243 solution Substances 0.000 abstract description 2
- 150000001875 compounds Chemical class 0.000 abstract 1
- 150000001879 copper Chemical class 0.000 abstract 1
- 239000000047 product Substances 0.000 abstract 1
- 239000012266 salt solution Substances 0.000 abstract 1
- 238000003756 stirring Methods 0.000 abstract 1
- 239000012808 vapor phase Substances 0.000 abstract 1
- 239000006227 byproduct Substances 0.000 description 10
- 238000001556 precipitation Methods 0.000 description 6
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- GQPLMRYTRLFLPF-UHFFFAOYSA-N Nitrous Oxide Chemical compound [O-][N+]#N GQPLMRYTRLFLPF-UHFFFAOYSA-N 0.000 description 4
- 229910052802 copper Inorganic materials 0.000 description 4
- 239000010949 copper Substances 0.000 description 4
- 230000003647 oxidation Effects 0.000 description 4
- 238000007254 oxidation reaction Methods 0.000 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- 239000005909 Kieselgur Substances 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 150000002739 metals Chemical class 0.000 description 3
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 3
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- GXDVEXJTVGRLNW-UHFFFAOYSA-N [Cr].[Cu] Chemical compound [Cr].[Cu] GXDVEXJTVGRLNW-UHFFFAOYSA-N 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- 235000011114 ammonium hydroxide Nutrition 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 229910052791 calcium Inorganic materials 0.000 description 2
- 239000011575 calcium Substances 0.000 description 2
- 239000001913 cellulose Substances 0.000 description 2
- 229920002678 cellulose Polymers 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 229910052804 chromium Inorganic materials 0.000 description 2
- 239000011651 chromium Substances 0.000 description 2
- 238000003780 insertion Methods 0.000 description 2
- 230000037431 insertion Effects 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- 239000001272 nitrous oxide Substances 0.000 description 2
- 235000021317 phosphate Nutrition 0.000 description 2
- 229910052573 porcelain Inorganic materials 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- RZVAJINKPMORJF-UHFFFAOYSA-N Acetaminophen Chemical compound CC(=O)NC1=CC=C(O)C=C1 RZVAJINKPMORJF-UHFFFAOYSA-N 0.000 description 1
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 1
- 239000005751 Copper oxide Substances 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 1
- 239000000292 calcium oxide Substances 0.000 description 1
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 1
- 239000003610 charcoal Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 229910000423 chromium oxide Inorganic materials 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 239000008119 colloidal silica Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 229910000431 copper oxide Inorganic materials 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 238000004868 gas analysis Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 229910000069 nitrogen hydride Inorganic materials 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 230000008092 positive effect Effects 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 239000005297 pyrex Substances 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 238000009834 vaporization Methods 0.000 description 1
- 230000008016 vaporization Effects 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明は、フェノールおよびアニリンの新規な製法に関
するものである。DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to a novel method for producing phenol and aniline.
詳しくはベンゼンと水とアンモニアとを反応させて、１
工程でフェノールおよびアニリンを製造する方法に関す
るものである。In detail, by reacting benzene, water, and ammonia, 1
The present invention relates to a method for producing phenol and aniline in a process.
従来、ベンゼンからフェノールを１工程で製造する方法
としては、触媒の存在下に、ベンゼンと酸素とを反応さ
せる直接酸化法が知られている。Conventionally, as a method for producing phenol from benzene in one step, a direct oxidation method in which benzene and oxygen are reacted in the presence of a catalyst is known.
しかしながら、この場合、ベンゼンの完全酸化が起こり
フェノールの選択率が大変低い（特開昭５６−８７５２
７号）。However, in this case, complete oxidation of benzene occurs and the selectivity of phenol is very low (Japanese Patent Application Laid-Open No. 8752-1999)
No. 7).
また、ベンゼンと亜酸化窒素とを触媒の存在下に反応さ
せて、フェノールを製造する方法も知られている。しか
しながら、この場合、原料の亜酸化窒素は高価である上
に、フェノールの収率は低い（特開昭５８−１４６５２
２） 。Furthermore, a method for producing phenol by reacting benzene and nitrous oxide in the presence of a catalyst is also known. However, in this case, the raw material nitrous oxide is expensive, and the yield of phenol is low (Japanese Patent Application Laid-Open No. 14652-1982).
2).
また、従来、ベンゼンとアンモニアとからアニリンが生
成する反応は知られている（ＤＴ−Ｏ５２，４６０，２
１２，２，４６０，２３３（１９７５） ）が、発生し
た水素が触媒の一部ＮｉＯを還元するので、触媒の再生
が必要である。Furthermore, the reaction of producing aniline from benzene and ammonia has been known (DT-O52,460,2
12, 2, 460, 233 (1975)), regeneration of the catalyst is necessary because the hydrogen generated reduces some of the NiO in the catalyst.
そのため、ベンゼンから１工程でフェノールまたはアニ
リンを製造する方法が望まれていたが、いまだ工業化さ
れていない、また、ベンゼンから１工程でフェノールお
よびアニリンを製造する方法もいまだ工業化されていな
い。Therefore, a method for producing phenol or aniline from benzene in one step has been desired, but it has not yet been industrialized, and a method for producing phenol and aniline from benzene in one step has not yet been industrialized.
本発明の’；ＭＢは、高収率でベンゼンからフェノール
およびアニリンを１工程で製造する工業的方法を提供す
ることである。すなわち、従来、ベンゼンからフェノー
ルを、そして、フェノールとアンモニアとを反応させて
アニリンを製造していたが、本発明の課題は、ベンゼン
から１工程でフェノールおよびアニリンを製造する方法
を提供することである。The MB of the present invention is to provide an industrial process for producing phenol and aniline from benzene in one step with high yield. That is, conventionally, aniline was produced by reacting phenol from benzene and then phenol and ammonia, but the object of the present invention is to provide a method for producing phenol and aniline from benzene in one step. be.
［課題を解決するための手段〕
本発明者らは、上記課題に関して種々検討した結果、触
媒の存在下に、ベンゼンと水とアンモニアとを気相接触
反応させることにより、ｌ工程でベンゼンからフェノー
ルおよびアニリンが選択率よく得られることを見出し、
本発明の方法に至った。[Means for Solving the Problems] As a result of various studies regarding the above-mentioned problems, the present inventors have determined that phenol can be converted from benzene in step 1 by carrying out a gas phase contact reaction between benzene, water, and ammonia in the presence of a catalyst. and aniline can be obtained with good selectivity,
The method of the present invention has been achieved.
すなわち、本発明は、
触媒の存在下に、ベンゼンと水とアンモニアとを気相接
触反応させることを特徴とするフェノールおよびアニリ
ンの製法である。That is, the present invention is a method for producing phenol and aniline, which is characterized by subjecting benzene, water, and ammonia to a gas phase catalytic reaction in the presence of a catalyst.
その反応は、次式のように進行するものと考えられる。The reaction is thought to proceed as shown in the following equation.
ＣｈＨｈ 、＋ ＨｔＯ→ ＣａＨｓＯＨ＋ Ｈｚ
（１）ＣａＨｓＯｆｌ ＋ ＮＨ３→ Ｃｂ Ｈ
ｓ Ｎ Ｈｚ ＋ Ｈｚ Ｏ（２）すなわち、触媒の存
在下に、ベンゼンと水とを反応させれば、（１）式のよ
うに、フェノールと水素が生成するのである。さらに（
１）式で生成したフェノールがアンモニアと反応すれば
、（２）式のように、アニリンと水が生成するのである
。ChHh, + HtO→ CaHsOH+ Hz
(1) CaHsOfl + NH3→ Cb H
s N Hz + Hz O (2) That is, when benzene and water are reacted in the presence of a catalyst, phenol and hydrogen are produced as shown in equation (1). moreover(
When the phenol produced in equation 1) reacts with ammonia, aniline and water are produced as shown in equation (2).
すなわち、本発明による方法で、ベンゼンからフェノー
ルが住成し、そのフェノールからアニリンが生成すると
考えられる。それ故、本発明による方法でベンゼンから
フェノールおよびアニリンが１工程で製造できるのであ
る。また、本発明による反応では、水は強力な酸化剤で
はないので、ベンゼンが完全酸化してＣＯ□になること
は極力制御できる。That is, it is thought that in the method according to the present invention, phenol is formed from benzene, and aniline is formed from the phenol. Therefore, with the process according to the invention, phenol and aniline can be produced from benzene in one step. Furthermore, in the reaction according to the present invention, since water is not a strong oxidizing agent, complete oxidation of benzene to CO□ can be controlled as much as possible.
本発明に用いられる触媒は、リン酸またはリン酸塩であ
る。また、本発明に用いられる触媒は、リン酸またはリ
ン酸塩を含有する触媒である。更に、本発明に用いられ
る触媒は、中でも特にリン酸、リン酸銅、リン酸クロム
、リン酸鉄、リン酸カルシウム等の少なくとも１種以上
を含有する触媒である。これらは単独または組み合わせ
で使用され、かつ、シリカ、アルミナ、シリカ−アルミ
ナ、ゼオライト、ケイソウ土、活性白土、酸化チタン、
酸化マグネシウム、活性炭などの担体に担持して使用し
てもよい。The catalyst used in the present invention is phosphoric acid or a phosphate salt. Further, the catalyst used in the present invention is a catalyst containing phosphoric acid or a phosphate salt. Further, the catalyst used in the present invention is a catalyst containing at least one of phosphoric acid, copper phosphate, chromium phosphate, iron phosphate, calcium phosphate, etc., among others. These are used alone or in combination, and include silica, alumina, silica-alumina, zeolite, diatomaceous earth, activated clay, titanium oxide,
It may be used by being supported on a carrier such as magnesium oxide or activated carbon.
また、触媒物質を造粒するために、バインダーとしてケ
イソウ土、コロイダルシリカ等の酸化珪素を触媒物質の
中に混合して使用してもよい本発明の方法において用い
られるリン酸触媒は、通常、金属、金属酸化物等にリン
酸を含浸させた後、電気炉で３００〜５００°Ｃで焼成
して触媒を鋼製する１本発明に用いられる金属は銅、ク
ロム、鉄、カルシウム等である。また本発明に用いられ
る金属酸化物は酸化銅、酸化クロム、酸化鉄、酸化カル
シウム等である。In addition, in order to granulate the catalyst material, silicon oxide such as diatomaceous earth or colloidal silica may be mixed into the catalyst material as a binder and used in the method of the present invention. After impregnating metals, metal oxides, etc. with phosphoric acid, the catalyst is made of steel by firing at 300 to 500°C in an electric furnace.1 The metals used in the present invention are copper, chromium, iron, calcium, etc. . Further, metal oxides used in the present invention include copper oxide, chromium oxide, iron oxide, calcium oxide, and the like.
本発明において用いられるリン酸塩触媒は、沈澱法また
は浸漬法で調製することができる。The phosphate catalyst used in the present invention can be prepared by a precipitation method or a dipping method.
沈澱法による場合はたとえば銅等の金属塩を水に熔解し
た後、リン酸またはリン酸含有溶液を添カロし、アンモ
ニア等を添加してｐｎを５〜７に調節し、数時間攪拌し
た後、沈澱を濾過し、沈澱を８００°Ｃに満たない温度
で焼成した後、粉砕粒化し、通常、バインダーとして酸
化珪素を加えて造粒乾燥焼成して触媒を調製することが
できる。When using the precipitation method, for example, after dissolving a metal salt such as copper in water, phosphoric acid or a phosphoric acid-containing solution is added, ammonia etc. are added to adjust the pn to 5 to 7, and the mixture is stirred for several hours. The catalyst can be prepared by filtering the precipitate, calcining the precipitate at a temperature below 800°C, pulverizing it into granules, adding silicon oxide as a binder, granulating, drying and calcining.
また、浸漬法による場合は、たとえば、担体として酸化
珪素を銅等の金属塩の水溶液に浸漬した後、リン酸を添
加し、アンモニア等を添加してｐＨを５〜７に調節した
後、リン酸塩を担持した酸化珪素を濾過し、乾燥した後
、８００°Ｃ以下で数時間焼成して触媒を調製する。In addition, when using the immersion method, for example, silicon oxide as a carrier is immersed in an aqueous solution of a metal salt such as copper, phosphoric acid is added, ammonia etc. are added to adjust the pH to 5 to 7, and then phosphoric acid is added. The silicon oxide supporting the acid salt is filtered, dried, and then calcined at 800° C. or lower for several hours to prepare a catalyst.
また、セルローズ、澱粉、その他の有機化合物や炭等の
粉末、粒、繊維等を触媒の中に混合し、触媒の前処理の
時に焼却し、空洞を残し、多孔貿の触媒を製造すれば、
触媒の性能、とくにフェノールおよびアニリンの収率向
上に良い効果がある。In addition, if powders, grains, fibers, etc. of cellulose, starch, other organic compounds, charcoal, etc. are mixed into the catalyst and incinerated during the pretreatment of the catalyst, leaving cavities to produce a porous catalyst.
It has a positive effect on catalyst performance, especially improving the yield of phenol and aniline.
また、銅、クロム、鉄、カルシウム等の金属、酸化物、
金属塩とリン酸および／またはリン酸塩を組み合わせて
、触媒として使用することもできる。In addition, metals such as copper, chromium, iron, calcium, oxides,
Combinations of metal salts and phosphoric acid and/or phosphates can also be used as catalysts.
また、リン酸を反応器または反応管の中へ原料と共にま
たは別々に添加することもできる。It is also possible to add phosphoric acid into the reactor or reaction tube together with the raw materials or separately.
本発明に用いられるベンゼンおよび水の使用量は、特に
限定されるものではないが、すべてのベンゼンが対応す
るフェノールに変化するためには、（１）式に示すよう
に、ベンゼンに対して等モル以上の水が必要である。ま
た、本発明に用いられるアンモニアの使用量は特に限定
されるものではないが、使用するベンゼンに対して等モ
ル以上のアンモニアを添加すれば、生成したフェノール
がアニリンに変化し易いと考えられる。また、アンモニ
アの使用量が増加すれば、アニリンの生成量も増加する
。また、通常、アンモニア水としてアンモニアと水を同
時に供給すると便利である。The amounts of benzene and water used in the present invention are not particularly limited, but in order to convert all benzene into the corresponding phenol, as shown in equation (1), it is necessary to More than mol of water is required. Further, although the amount of ammonia used in the present invention is not particularly limited, it is thought that if ammonia is added in an amount equal to or more than the same mole relative to the benzene used, the generated phenol is likely to be converted into aniline. Furthermore, as the amount of ammonia used increases, the amount of aniline produced also increases. Further, it is usually convenient to supply ammonia and water at the same time as aqueous ammonia.
本発明の方法においては、反応は、通常、不活性ガス雰
囲気中、常圧または加圧下において実施される。不活性
ガスとしては、窒素、ヘリウム、アルゴン、二酸化炭素
等があげられる。In the method of the present invention, the reaction is usually carried out in an inert gas atmosphere under normal pressure or increased pressure. Examples of the inert gas include nitrogen, helium, argon, carbon dioxide, and the like.
本発明の方法において、反応温度は２００〜６００゛Ｃ
１好ましくは３００〜５５０°Ｃの範囲である。２００
°Ｃ未満では本発明による反応が起こらず、６００°Ｃ
を越えると副生物が多く生成する。In the method of the present invention, the reaction temperature is 200 to 600°C.
1 Preferably, the temperature is in the range of 300 to 550°C. 200
The reaction according to the present invention does not occur below 600°C.
Exceeding this will produce many by-products.
本発明の方法は気相で実施することができる。The method of the invention can be carried out in the gas phase.
すなわち、固定層、流動層または移動層反応器のいずれ
でも実施できる。また、反応器または反応管中で、前記
触媒の存在下に、ベンゼン、水およびアンモニアを加熱
することにより、本発明の方法は実施される。この際、
場合によっては原料莫気中に、本発明の触媒の一種であ
るリン酸を添加して本発明の方法は実施することができ
る。That is, it can be carried out in a fixed bed, fluidized bed or moving bed reactor. The process of the invention is also carried out by heating benzene, water and ammonia in the presence of the catalyst in a reactor or reaction tube. On this occasion,
In some cases, the method of the present invention may be carried out by adding phosphoric acid, which is one of the catalysts of the present invention, to the raw material gas.
本発明の方法において、フェノールおよびアニリンは、
反応生成物から適当な方法、たとえば、蒸留のような常
法によって、容易に分離精製できる。In the method of the invention, phenol and aniline are
It can be easily separated and purified from the reaction product by an appropriate method, for example, a conventional method such as distillation.
以下、実施例により本発明の詳細な説明する。 Hereinafter, the present invention will be explained in detail with reference to Examples.
実施例１
試Ｎ Ｃｕ５（ＰＯ４）ｔ −３Ｈ！０３３．Ｏｇ、
Ｃａ３（ＰＯａ’）ｔ ２２．６ｇおよび東洋濾紙■製
の濾紙粉末（セルローズＢ）６．０ｇを混合した後、水
２５ｇを添加して泥状とした後、磁製器に入れ、電炉中
に入れ、空気雰囲気中で１５０”ＣＸ２時間、３００°
ＣＸ５時間および４００°ＣＸ２時間焼成して触媒を調
製した。Example 1 Trial N Cu5(PO4)t -3H! 033. Og,
After mixing 22.6 g of Ca3(POa')t and 6.0 g of filter paper powder (cellulose B) manufactured by Toyo Roshi ■, 25 g of water was added to form a slurry, which was then placed in a porcelain vessel and placed in an electric furnace. 150"CX 2 hours, 300° in air atmosphere
A catalyst was prepared by calcining at CX for 5 hours and at 400°C for 2 hours.
この触媒５ｄを内径１５ｍｍのパイレックスガラス製流
通型反応管に充填した。その反応管を窒素中４００°Ｃ
で１時間焼成した。This catalyst 5d was packed into a Pyrex glass flow-through reaction tube having an inner diameter of 15 mm. The reaction tube was heated to 400°C in nitrogen.
Baked for 1 hour.
この反応管の前部は、原料挿入管およびガス導入管に連
結され、原料気化部を構成し、後部は空冷部を経て受器
と連結されていた。この反応管の内温を４５０°Ｃに保
ち、液空間速度１．５ｍＱ／ｈｒでベンゼン、２ 、０
ｍｌ ／ ｈ ｒで２８％アンモニア水を別々に原料
挿入管より反応部に供給し、これと同時に窒素３０ｇ＋
１／蒙ｉｎを常圧下で通じた。The front part of this reaction tube was connected to a raw material insertion pipe and a gas introduction pipe to constitute a raw material vaporization part, and the rear part was connected to a receiver via an air cooling part. The internal temperature of this reaction tube was maintained at 450°C, and benzene, 2,0
28% ammonia water was separately supplied to the reaction section from the raw material insertion tube at a rate of ml/hr, and at the same time 30 g of nitrogen +
1/meng was passed under normal pressure.
反応管を出て凝縮した反応生成物をガスクロマトグラフ
にて分析すると、ベンゼン転化率６．２％、フェノール
選択率６６．４％、アニリン選択率３１．０％、フェノ
ール収率４．１％、アニリン収率１．９％でフェノール
およびアニリンが得られた。副生物はほとんど得られな
かった。また、ガス分析の結果、二酸化炭素の生成はほ
とんど観察されなかった。When the reaction product condensed after exiting the reaction tube was analyzed using a gas chromatograph, the benzene conversion rate was 6.2%, the phenol selectivity was 66.4%, the aniline selectivity was 31.0%, and the phenol yield was 4.1%. Phenol and aniline were obtained with an aniline yield of 1.9%. Almost no by-products were obtained. Furthermore, as a result of gas analysis, almost no carbon dioxide production was observed.
実施例２
実施例１の触媒の代わりに粒状の銅クロム触媒（日揮化
学Ｎ−２０１、Ｃｕ０３７％、ＣｒｚＯｉ ４６％、Ｍ
ｎ０ｚ ４％）２０ｇに、８５％リン酸水溶液！（ｓ
Ｐ０４４ｇを含浸させ、４００°Ｃで５時間焼成して触
媒を調製した。Example 2 A granular copper chromium catalyst (JGC N-201, Cu0 37%, CrzOi 46%, M
n0z 4%) 20g, 85% phosphoric acid aqueous solution! (s
A catalyst was prepared by impregnating 44 g of P0 and calcining at 400°C for 5 hours.
以下、実施例１と同様に実施した結果、ベンゼン転化率
５．３％、フェノール選択率６３．２％、アニリン選択
率２５．１％、フェノール収率３，３％、アニリン収率
１．３％でフェノールおよびアニリンを得た。他に不明
の副生物が少量生成した。また、少量の二酸化炭素の生
成も観察された。The following results were carried out in the same manner as in Example 1. The benzene conversion rate was 5.3%, the phenol selectivity was 63.2%, the aniline selectivity was 25.1%, the phenol yield was 3.3%, and the aniline yield was 1.3. % of phenol and aniline were obtained. Small amounts of other unknown by-products were also produced. Also, a small amount of carbon dioxide production was observed.
比較例１
実施例２の方法において、リン酸を使用せず、触媒とし
て粒状の銅クロム触媒（８揮化学ＮＮ−２０１）Ｌｏを
使用して、以下実施例２と同様に実施した結果、フェノ
ールおよびアニリンの生成は全く観察されず、二酸化炭
素は多量に生成した。Comparative Example 1 The method of Example 2 was carried out in the same manner as in Example 2 except that phosphoric acid was not used and a granular copper chromium catalyst (8volatile chemical NN-201) Lo was used as the catalyst. No production of aniline was observed, and a large amount of carbon dioxide was produced.
実施例３
実施例１の触媒の代わりに、試薬
Ｃｕ５ＣＰＯａ）ｚ ’ ３ＨｚＯ２０，Ｏｇ、ケイソ
ウ土１０．０ｇを混合した後、水２５ｇを添加して泥状
とした後、磁製皿に入れ、電炉中に入れ、空気雰囲気中
で１５０°ＣＸ２時間、４００°ＣＸ２時間焼成して触
媒を調製した。Example 3 Instead of the catalyst in Example 1, the reagent Cu5CPOa)z'3HzO20,0g and 10.0 g of diatomaceous earth were mixed, and then 25 g of water was added to make a slurry, which was then placed in a porcelain dish and heated in an electric furnace. The catalyst was then calcined at 150° C. for 2 hours and at 400° C. for 2 hours in an air atmosphere to prepare a catalyst.
以下、実施例１と同様に実施した結果、ベンゼン転化率
６．０％、フェノール選択率６５．２％、アニリン選択
率２８．３％、フェノール収率３．９％、アニリン収率
１．７％でフェノールおよびアニリンを得た。他に不明
の副生物が少量生成した。また、少量の二酸化炭素の生
成も観察された。The following results were carried out in the same manner as in Example 1. The benzene conversion rate was 6.0%, the phenol selectivity was 65.2%, the aniline selectivity was 28.3%, the phenol yield was 3.9%, and the aniline yield was 1.7. % of phenol and aniline were obtained. Small amounts of other unknown by-products were also produced. Also, a small amount of carbon dioxide production was observed.
実施例４
実施例１の触媒の代わりに、沈澱法で調製し粒状に成形
したＣｕｚ（ＰＯａ）ｚ Ｈ３ＬＯの５ｄを反応管に充
填し、以下実施例１と同様に実施した結果、ベンゼン転
化率６．１％、フェノール選択率６３．６％、アニリン
選択率２７．５％、フェノール収率３．９％、アニリン
収率１，７％でフェノールおよびアニリンを得た。他に
不明の副生物が少量生成した。また、少量の二酸化炭素
の生成も観察された。Example 4 In place of the catalyst in Example 1, 5d of Cuz(POa)zH3LO prepared by the precipitation method and formed into granules was filled into the reaction tube, and the same procedure as in Example 1 was carried out. As a result, the benzene conversion rate was Phenol and aniline were obtained with a phenol selectivity of 63.6%, an aniline selectivity of 27.5%, a phenol yield of 3.9%, and an aniline yield of 1.7%. Small amounts of other unknown by-products were also produced. Also, a small amount of carbon dioxide production was observed.
実施例５
実施例】の触媒の代わりに、沈澱法で調製し粒状に成形
したＣｒＰＯａ・６Ｈ２０の５−を反応管に充填し、以
下実施例１と同様に実施した結果、ベンゼン転化率３．
３％、フェノール選択率６１．５％、アニリン選択率２
１．７％、フェノール収率２．０％、アニリン収率０．
７％でフェノールおよびアニリンを得た。他に不明の副
生物が少量生成した。Example 5 The reaction tube was filled with CrPOa.6H20 5- prepared by the precipitation method and formed into granules instead of the catalyst in Example 1, and the same procedure as in Example 1 was carried out. As a result, the benzene conversion rate was 3.
3%, phenol selectivity 61.5%, aniline selectivity 2
1.7%, phenol yield 2.0%, aniline yield 0.
Phenol and aniline were obtained at 7%. Small amounts of other unknown by-products were also produced.
実施例６
実施例１の触媒の代わりに、沈澱法で調製し粒状に成形
したＦｅＰＯ４・４Ｈ１Ｏの５ｄを反応管に充填し、以
下実施例１と同様に実施した結果、ベンゼン転化率２．
１％、フェノール選択率４０．６％、アニリン選択率１
３．１％、フェノール収率０．９％、アニリン収率０．
３％でフェノールおよびアニリンを得た。他に不明の副
生物と二酸化炭素が少量生成した。Example 6 Instead of the catalyst of Example 1, the reaction tube was filled with 5d of FePO4.4H1O prepared by the precipitation method and formed into granules, and the same procedure as in Example 1 was carried out. As a result, the benzene conversion rate was 2.
1%, phenol selectivity 40.6%, aniline selectivity 1
3.1%, phenol yield 0.9%, aniline yield 0.
Phenol and aniline were obtained at 3%. Other unknown by-products and small amounts of carbon dioxide were also produced.
実施例７ 実施例１の触媒の代わりに、沈澱法で調製し粒。Example 7 In place of the catalyst in Example 1, particles were prepared by a precipitation method.
状に成形したＣａｚ（ＰＯａ）ｚの５１ｄを反応管に充
填し、以下実施例１と同様に実施した結果、ベンゼン転
化率１，２％、フェノール選択率３８．７％、アニリン
選択率１３，０％、フェノール収率０．５％、アニリン
収率０．２％でフェノールおよびアニリンを得た。A reaction tube was filled with 51d of Caz(POa)z molded into a shape, and the following procedure was carried out in the same manner as in Example 1. As a result, the benzene conversion rate was 1.2%, the phenol selectivity was 38.7%, the aniline selectivity was 13, Phenol and aniline were obtained with a phenol yield of 0.5% and an aniline yield of 0.2%.
他に不明の副生物と二酸化炭素が少量生成した。Other unknown by-products and small amounts of carbon dioxide were also produced.
本発明の方法では、触媒の存在下に、ベンゼンと水とア
ンモニアとを気相接触反応させて、１工程でフェノール
とアニリンを製造することができる。In the method of the present invention, phenol and aniline can be produced in one step by subjecting benzene, water, and ammonia to a gas phase contact reaction in the presence of a catalyst.
本発明の方法によれば、次のような利点がある。According to the method of the present invention, there are the following advantages.
（１）原料がベンゼンと水とアンモニアのような安価な
ものである。(1) The raw materials are inexpensive such as benzene, water, and ammonia.
（２）１工程でベンゼンからフェノールおよびアニリン
が製造される。(2) Phenol and aniline are produced from benzene in one step.
（３）フェノールおよびアニリンの収率が良い。(3) Good yields of phenol and aniline.
（４）副生物が少なく、選択率が良く、したがって高純
度のフェノールおよびアニリンを得ることができる。(4) There are few by-products, the selectivity is good, and therefore highly pure phenol and aniline can be obtained.
（５）二酸化炭素の生成が少なく、完全酸化を抑制する
ことができる。(5) Less carbon dioxide is produced, and complete oxidation can be suppressed.
（６）副生ずる水素は他に利用することができる。(6) Hydrogen produced by-product can be used for other purposes.
（７）原料がベンゼンと水とアンモニアであるので反応
装置の腐食は少ない。(7) Since the raw materials are benzene, water and ammonia, there is little corrosion of the reactor.
特許出願人 三井東圧化学株式会社Patent applicant Mitsui Toatsu Chemical Co., Ltd.
Claims (1)
相接触反応させることを特徴とするフェノールおよびア
ニリンの製法。 ２）触媒がリン酸および／またはリン酸塩、またはリン
酸および／またはリン酸塩を含有する触媒である請求項
１に記載の製法。 ３）リン酸塩がリン酸銅、リン酸クロム、リン酸鉄また
はリン酸カルシウムである請求項２に記載の製法。 ４）触媒が多孔質の触媒である請求項２または３に記載
の製法。[Claims] 1) A method for producing phenol and aniline, which comprises carrying out a gas phase contact reaction of benzene, water and ammonia in the presence of a catalyst. 2) The method according to claim 1, wherein the catalyst is phosphoric acid and/or a phosphate, or a catalyst containing phosphoric acid and/or a phosphate. 3) The method according to claim 2, wherein the phosphate is copper phosphate, chromium phosphate, iron phosphate or calcium phosphate. 4) The method according to claim 2 or 3, wherein the catalyst is a porous catalyst.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63268154A JPH02115138A (en) | 1988-10-26 | 1988-10-26 | Production of phenol and aniline |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63268154A JPH02115138A (en) | 1988-10-26 | 1988-10-26 | Production of phenol and aniline |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH02115138A true JPH02115138A (en) | 1990-04-27 |
Family
ID=17454648
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP63268154A Pending JPH02115138A (en) | 1988-10-26 | 1988-10-26 | Production of phenol and aniline |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH02115138A (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5861536A (en) * | 1997-07-31 | 1999-01-19 | Sun Company, Inc. (R&M) | Oxidative ammination of benzene to aniline using molecular oxygen as the terminal oxidant |
| US5952532A (en) * | 1997-07-31 | 1999-09-14 | Sunoco, Inc. | Hydroxylation of aromatics using molecular oxygen as the terminal oxidant without coreductant |
| US5962752A (en) * | 1997-07-31 | 1999-10-05 | Sun Company, Inc. | Leached alumina vanadyl catalysts for hydroxylation of aromatics using molecular oxygen as the terminal oxidant without coreductant |
| US5981424A (en) * | 1997-07-31 | 1999-11-09 | Sunoco, Inc. (R&M) | Catalysts for hydroxylation and ammination of aromatics using molecular oxygen as the terminal oxidant without coreductant |
| JP2009249332A (en) * | 2008-04-04 | 2009-10-29 | Univ Of Tokyo | Method for producing phenol by direct oxidation of benzene |
| JP2018515430A (en) * | 2015-04-02 | 2018-06-14 | ハンツマン・インターナショナル・エルエルシー | Direct amination of hydrocarbons |
-
1988
- 1988-10-26 JP JP63268154A patent/JPH02115138A/en active Pending
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5861536A (en) * | 1997-07-31 | 1999-01-19 | Sun Company, Inc. (R&M) | Oxidative ammination of benzene to aniline using molecular oxygen as the terminal oxidant |
| US5952532A (en) * | 1997-07-31 | 1999-09-14 | Sunoco, Inc. | Hydroxylation of aromatics using molecular oxygen as the terminal oxidant without coreductant |
| US5962752A (en) * | 1997-07-31 | 1999-10-05 | Sun Company, Inc. | Leached alumina vanadyl catalysts for hydroxylation of aromatics using molecular oxygen as the terminal oxidant without coreductant |
| US5981424A (en) * | 1997-07-31 | 1999-11-09 | Sunoco, Inc. (R&M) | Catalysts for hydroxylation and ammination of aromatics using molecular oxygen as the terminal oxidant without coreductant |
| JP2009249332A (en) * | 2008-04-04 | 2009-10-29 | Univ Of Tokyo | Method for producing phenol by direct oxidation of benzene |
| JP2018515430A (en) * | 2015-04-02 | 2018-06-14 | ハンツマン・インターナショナル・エルエルシー | Direct amination of hydrocarbons |
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