JPS62204848A - Production of catalyst for hydrogenating carbon-carbon double bond, nitro group and aldehyde group in aliphatic andaromatic compound - Google Patents
Production of catalyst for hydrogenating carbon-carbon double bond, nitro group and aldehyde group in aliphatic andaromatic compoundInfo
- Publication number
- JPS62204848A JPS62204848A JP61045146A JP4514686A JPS62204848A JP S62204848 A JPS62204848 A JP S62204848A JP 61045146 A JP61045146 A JP 61045146A JP 4514686 A JP4514686 A JP 4514686A JP S62204848 A JPS62204848 A JP S62204848A
- Authority
- JP
- Japan
- Prior art keywords
- catalyst
- membrane
- zinc
- carbon
- layer
- 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
- 239000003054 catalyst Substances 0.000 title claims description 64
- 125000003172 aldehyde group Chemical group 0.000 title claims description 7
- 238000004519 manufacturing process Methods 0.000 title claims description 7
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 title claims description 7
- 239000011203 carbon fibre reinforced carbon Substances 0.000 title description 9
- 150000001875 compounds Chemical class 0.000 title description 3
- 125000001931 aliphatic group Chemical group 0.000 title 1
- 239000012528 membrane Substances 0.000 claims description 54
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 39
- 229910052725 zinc Inorganic materials 0.000 claims description 39
- 239000011701 zinc Substances 0.000 claims description 39
- 238000005984 hydrogenation reaction Methods 0.000 claims description 28
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 24
- 229910052751 metal Inorganic materials 0.000 claims description 24
- 239000002184 metal Substances 0.000 claims description 24
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 23
- 229910045601 alloy Inorganic materials 0.000 claims description 23
- 239000000956 alloy Substances 0.000 claims description 23
- 238000000034 method Methods 0.000 claims description 21
- 229910052763 palladium Inorganic materials 0.000 claims description 11
- 150000002739 metals Chemical class 0.000 claims description 9
- 150000007824 aliphatic compounds Chemical class 0.000 claims description 8
- 150000001491 aromatic compounds Chemical class 0.000 claims description 8
- 229910052703 rhodium Inorganic materials 0.000 claims description 8
- 239000010948 rhodium Substances 0.000 claims description 8
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 claims description 8
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims description 7
- 229910052707 ruthenium Inorganic materials 0.000 claims description 7
- 229910052799 carbon Inorganic materials 0.000 claims description 4
- 239000000126 substance Substances 0.000 claims description 4
- 238000011084 recovery Methods 0.000 claims description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims 1
- 239000010410 layer Substances 0.000 description 53
- 229910052739 hydrogen Inorganic materials 0.000 description 31
- 239000001257 hydrogen Substances 0.000 description 30
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 27
- 239000011888 foil Substances 0.000 description 26
- 230000035699 permeability Effects 0.000 description 19
- LQNUZADURLCDLV-UHFFFAOYSA-N nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC=C1 LQNUZADURLCDLV-UHFFFAOYSA-N 0.000 description 14
- 239000000203 mixture Substances 0.000 description 13
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 10
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 10
- 239000011148 porous material Substances 0.000 description 10
- 230000003197 catalytic effect Effects 0.000 description 7
- 239000007795 chemical reaction product Substances 0.000 description 7
- GOUHYARYYWKXHS-UHFFFAOYSA-N 4-formylbenzoic acid Chemical compound OC(=O)C1=CC=C(C=O)C=C1 GOUHYARYYWKXHS-UHFFFAOYSA-N 0.000 description 5
- 229910052786 argon Inorganic materials 0.000 description 5
- 238000006555 catalytic reaction Methods 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 4
- 150000002431 hydrogen Chemical class 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 229910001252 Pd alloy Inorganic materials 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 238000009792 diffusion process Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- MCSAJNNLRCFZED-UHFFFAOYSA-N nitroethane Chemical compound CC[N+]([O-])=O MCSAJNNLRCFZED-UHFFFAOYSA-N 0.000 description 3
- IKHGUXGNUITLKF-UHFFFAOYSA-N Acetaldehyde Chemical compound CC=O IKHGUXGNUITLKF-UHFFFAOYSA-N 0.000 description 2
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 239000002638 heterogeneous catalyst Substances 0.000 description 2
- 150000002828 nitro derivatives Chemical class 0.000 description 2
- LPNBBFKOUUSUDB-UHFFFAOYSA-N p-toluic acid Chemical compound CC1=CC=C(C(O)=O)C=C1 LPNBBFKOUUSUDB-UHFFFAOYSA-N 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- PMJHHCWVYXUKFD-SNAWJCMRSA-N (E)-1,3-pentadiene Chemical compound C\C=C\C=C PMJHHCWVYXUKFD-SNAWJCMRSA-N 0.000 description 1
- QMMOXUPEWRXHJS-HYXAFXHYSA-N (z)-pent-2-ene Chemical compound CC\C=C/C QMMOXUPEWRXHJS-HYXAFXHYSA-N 0.000 description 1
- DYNFCHNNOHNJFG-UHFFFAOYSA-N 2-formylbenzoic acid Chemical compound OC(=O)C1=CC=CC=C1C=O DYNFCHNNOHNJFG-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 1
- 101100126329 Mus musculus Islr2 gene Proteins 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- IKHGUXGNUITLKF-XPULMUKRSA-N acetaldehyde Chemical compound [14CH]([14CH3])=O IKHGUXGNUITLKF-XPULMUKRSA-N 0.000 description 1
- 238000010306 acid treatment Methods 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 238000004061 bleaching Methods 0.000 description 1
- FGNLEIGUMSBZQP-UHFFFAOYSA-N cadaverine dihydrochloride Chemical compound Cl.Cl.NCCCCCN FGNLEIGUMSBZQP-UHFFFAOYSA-N 0.000 description 1
- 238000001311 chemical methods and process Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 230000002860 competitive effect Effects 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 125000000753 cycloalkyl group Chemical group 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000001493 electron microscopy Methods 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 238000002386 leaching Methods 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- BSIDXUHWUKTRQL-UHFFFAOYSA-N nickel palladium Chemical compound [Ni].[Pd] BSIDXUHWUKTRQL-UHFFFAOYSA-N 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- PMJHHCWVYXUKFD-UHFFFAOYSA-N piperylene Natural products CC=CC=C PMJHHCWVYXUKFD-UHFFFAOYSA-N 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000009331 sowing Methods 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 239000002344 surface layer Substances 0.000 description 1
- 229930195735 unsaturated hydrocarbon Natural products 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 description 1
- 229960001763 zinc sulfate Drugs 0.000 description 1
- 229910000368 zinc sulfate Inorganic materials 0.000 description 1
Classifications
-
- B01J35/59—
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
- B01J23/46—Ruthenium, rhodium, osmium or iridium
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C5/00—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms
- C07C5/22—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by isomerisation
- C07C5/27—Rearrangement of carbon atoms in the hydrocarbon skeleton
- C07C5/31—Rearrangement of carbon atoms in the hydrocarbon skeleton changing the number of rings
Abstract
(57)【要約】本公報は電子出願前の出願データであるた
め要約のデータは記録されません。(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.
Description
【発明の詳細な説明】
本発明は、触媒の９１造方法に関し、特に、脂肪族及び
芳香族化合物中の炭素−炭素二重結合、ニトロ基及びア
ルデヒド基の水素化用触媒の製造方法に関する。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for preparing a catalyst, and in particular to a method for preparing a catalyst for the hydrogenation of carbon-carbon double bonds, nitro groups and aldehyde groups in aliphatic and aromatic compounds.
先行技術
今日、知られている触媒化学は、例えば、脂肪族及び芳
香族化合物中の炭素−炭素二重結合、ニトロ基及びアル
デヒド基の水素化に使用されるよく発達した表面（ｗｅ
ｌｌ−ｃ！ｅｖｅｌｏｐｅｃｌｎｕｒ ｆａｃｅ）を有
する金属触媒の製造方法である。これらの方法は、キャ
リヤ（ｃａｒｒｉｅｒ）に高分散形態で金属を適用する
ことを含む、更に、よく発達した表面を有する金属触媒
（スケルトン型触媒）も、例えば、触媒活性金属の合金
をアルミニウム、シリコン等で浸出して製造される。PRIOR ART The catalytic chemistry known today is based on well-developed surfaces (we
ll-c! This is a method for producing a metal catalyst having an evolved face. These methods involve applying the metal in highly dispersed form to a carrier; furthermore, metal catalysts with well-developed surfaces (skeleton-type catalysts) can also be prepared, for example alloys of catalytically active metals such as aluminum, silicon, etc. It is manufactured by leaching with etc.
〔シー、エヌ、セターフイールド「実際における異質の
触媒」マグロ−ヒル、インコーホレーテッド、、二ｚ−
”Ｊ−り（１９８０）参照（ｃｆ。[C, N., Setterfield, “Heterogeneous Catalysts in Practice,” McGraw-Hill, Incorporated, 2z-
"See J. Ri (1980) (cf.
Ｃ，Ｎ、５ｅｔｔｅｒｆ １ｅｌｄ。C, N, 5etterf 1eld.
”ＨｅｔｅｒｏｇｅｎｅｏｕｓＣａｔａｌｙｓｔｓ＋
ｎ Ｐｒａｃｔ ｉｃｅ” ＭｃＧｒａｗ Ｈ
ｉ ｌ’ＩＩｎｃ、、Ｎｅｗ Ｙｏｒｋ、１９８０
））これらの触媒の製造方法では、よく発達した表面を
有し、また、水素の選択的透過性及び高い機械的強度を
所有する膜触媒を製造することは不可能なことである６
パラジウム ブラック（ｐａｌｌａｃＪｉｕｍｂｌａｃ
ｋ）の屑のパラノウム基礎合金（例えば銀或はニッケル
）或は他の多くの触媒活性金属〆 ｊブラックの合金で
作られた箔或は管の如く形成されたａ表面に化学的或は
電気化学的沈積物を含み、ｆ飽和炭化水素の水素化工程
に使用しうるよく発達した表面を有する膜触媒を’ＪＩ
Ｈする方法は、既に公知である。〔ゲイ。エム、グリャ
ズノ７、ゲイ。ニス、スミル／７、エル、ケイ、イヴア
／ヴＴ１エイ、ビイ、ミシェンコによるドクレディ７ン
ニスニスニスアル（ｃ ｆ、Ｖ、Ｍ。“Heterogeneous Catalysts+
McGraw H
i l'IInc, New York, 1980
)) With these catalyst production methods, it is impossible to produce membrane catalysts that have a well-developed surface and also possess hydrogen selective permeability and high mechanical strength6 Palladium Black (pallacJiumblac
k) Scrap paranoum base alloy (such as silver or nickel) or many other catalytically active metals. Membrane catalysts containing chemical deposits and having well-developed surfaces that can be used in the hydrogenation process of f-saturated hydrocarbons are
The method for H is already known. [Gay. M, Gryazno7, gay. Nis, Smil/7, El, Kay, Ivua/VT1 Dokredi 7n Nis Nis Nisal (c f, V, M.
Ｇｒｙａｚｎｏｖ、Ｖ、Ｓ、Ｓｍ ｉ ｒｎｏｖ、Ｌ。Gryaznov, V. S., Sm i rnov, L.
Ｋ、 Ｉｖａｎｏｖａ、 Ａ、Ｐ＋Ｍｉｓｃｈｅｎ
ｋｏ。K, Ivanova, A, P+Mischen
ko.
Ｄｏｋｌａｃｌｙ ΔＮ ５ＳＳＲ，１９７０）
、Ｖｏｌ、１９０．Ｐ、１４４参照〕
しかしながら、この先行技術の方法は、パラノウムブラ
ック或は他の金属ブラック（ｍｅｔａｌｌ）ｌａｃｋ）
を有する膜の耐久性被覆を保証しない、更にパラジウム
合金からの膜表面のがなりの部分が、水素分子及び有機
物質にとって利用され難いので、膜被覆のためのもう一
つの触媒活性金属の使用は、しばしば水素に対する膜触
媒の低透過性をもたらす、水素、空気及び炭化水素の雰
囲気下の長時間操業で、ブラックレイヤー（ｂｌａｃｋ
ｌａｙｅｒ）は、破壊され、剥Ｂされる。Doklacly ΔN 5SSR, 1970)
, Vol., 190. See P. P., 144] However, this prior art method does not allow the use of paranoum black or other metal racks.
The use of another catalytically active metal for membrane coatings does not guarantee a durable coating of membranes with palladium alloys, and also because the loose portion of the membrane surface from palladium alloys is less available for hydrogen molecules and organic substances. , the black layer (black
layer) is destroyed and stripped.
また、不飽和炭化水素の水素化触媒の製造方法が、その
表面に設けられたニッケルパラジウム或は白金のような
触媒活性金属の多孔質層を有する構造金属材料で作られ
た基質を含むことは公知である。Additionally, the method for producing an unsaturated hydrocarbon hydrogenation catalyst may include a substrate made of a structural metallic material having a porous layer of a catalytically active metal, such as nickel palladium or platinum, disposed on its surface. It is publicly known.
この方法は、触媒活性金属が基質表面に適用され、それ
から亜鉛或はアルミニウムの如き触媒的に不活性な金属
層で被覆され、触媒活性金属と触媒的に不活性な金属と
の内部拡散のために、３００〜ｉ、ｏ ｏ ｏ℃の範囲
内の温度に保持され、続いて水酸化ナトリッム或は水酸
化カリウムで漂白して、触媒活性金属から亜鉛或はアル
ミニウムを化学的に回収するものである。In this method, a catalytically active metal is applied to the substrate surface and then coated with a layer of a catalytically inactive metal such as zinc or aluminum, allowing for internal diffusion of the catalytically active metal and the catalytically inactive metal. The zinc or aluminum is chemically recovered from the catalytically active metal by being maintained at a temperature in the range of 300°C to 300°C, followed by bleaching with sodium hydroxide or potassium hydroxide. be.
触媒的に不活性な金属層の厚さは、触媒活性金属層の厚
さと等しいが、または１０倍までの厚さである。〔ソ連
発明者証（ＵＳＳＲＩｎｖｅｎｔｏｒ’ｓ Ｃｅｒｔ
ｉｆｉｃａｔｅ）Ｎｏ。The thickness of the catalytically inactive metal layer is equal to or up to 10 times the thickness of the catalytically active metal layer. [USSR Inventor's Cert
ificate)No.
２１８８３０、Ｉｎｔ、ＣＩ、ＢＯＩＪ２５１００、発
明公告公報（ｐｕｂｌｉｓｈｅｄｉｎ Ｂｕｌｌｅｔ
ｉｎ Ｉｎｖｅｎｔｉｏｎｓ）Ｎｏ、２４，１９６７
参＠）
水素化工程が、膜を通って拡散する活性（元素状）水素
を使用することにより起こるから、この先行技術の方法
では、膜触媒を製造することができない。218830, Int, CI, BOIJ25100, Invention Bulletin
Inventions) No. 24, 1967
This prior art method does not allow membrane catalysts to be produced because the hydrogenation step occurs by using active (elemental) hydrogen that diffuses through the membrane.
この方法で製造された触媒においては、該工程は、試薬
と水素の競争的吸着で、分子状水素の使用により進行す
るので、水素化速度及び工程の選択性は低下する。この
ような触媒において、大気圧下のニトロ化合物の水素化
は、実質的には、殆んど進行しない。それは、触媒表面
上へのニトロ化合物の強力な吸着のためであり、触媒の
活性中心への水素の接近を妨げることになる。In catalysts prepared by this method, the hydrogenation rate and selectivity of the process are reduced because the process proceeds with the use of molecular hydrogen, with competitive adsorption of hydrogen with the reagent. In such catalysts, the hydrogenation of nitro compounds under atmospheric pressure does not substantially proceed. It is due to the strong adsorption of nitro compounds on the catalyst surface, which will prevent the access of hydrogen to the active centers of the catalyst.
発明が解決しようとする問題点
本発明は、通し孔ではなく、よく発達した多孔質表面を
もち、脂肪族及び芳香族化合物中の炭素−炭素二重結合
、ニド四基及びアルデヒド基の水素化工程において、水
素に対する向上した選択的透過性を有し、同様に、該多
孔質層の高い機械的強度を有する触媒の製造方法を提供
する。Problems to be Solved by the Invention The present invention has a well-developed porous surface rather than through-pores, and is capable of hydrogenating carbon-carbon double bonds, nido tetragroups, and aldehyde groups in aliphatic and aromatic compounds. A process is provided for producing a catalyst having an improved selective permeability to hydrogen, as well as a high mechanical strength of the porous layer.
問題点を解決するための手段
本発明の目的は、触媒活性金属上へ亜鉛を沈積させ、こ
れらの金属を相互拡散を確実にする温度に保持し、続い
て触媒活性金属から亜鉛を化学的に回収することによっ
て、脂肪族及び芳香族化合物中の炭素−炭素二重結合、
ニトロ基及びアルデヒド基の水素化用触媒を製造する方
法によって達成される。本発明によれば、触媒活性金属
は、８０〜９５賀量％のパラジウムと５〜２０質量％の
ルテニウムまたはロジウムとから成る合金の膜形状にお
いて使用される。亜鉛は、亜鉛の１５１部材１こ大・す
するＲ１４１！７．比が１＝１０〜１００において、膜
表面の片面または両面に適用される。亜鉛層が適用さ枕
た膜部材は、２０〜２５０℃の範囲内の温度に保持され
、膜部材からの亜鉛の化学的回収は、塩酸で、該膜部材
を処理することによって行われる。Means for Solving the Problems The object of the present invention is to deposit zinc onto the catalytically active metals, hold these metals at a temperature that ensures interdiffusion, and then chemically remove the zinc from the catalytically active metals. By recovering carbon-carbon double bonds in aliphatic and aromatic compounds,
This is achieved by a method for producing a catalyst for the hydrogenation of nitro and aldehyde groups. According to the invention, the catalytically active metal is used in the form of a membrane of an alloy consisting of 80-95% by weight palladium and 5-20% by weight ruthenium or rhodium. Zinc is Zinc 151 member 1 size R141!7. When the ratio is 1=10 to 100, it is applied to one or both sides of the membrane surface. The membrane element to which the zinc layer has been applied is maintained at a temperature in the range of 20-250<0>C and chemical recovery of zinc from the membrane element is carried out by treating the membrane element with hydrochloric acid.
本発明による方法によって、９５〜８０質量％のパラジ
ウムと５〜２０質量％のルテニウム又はロジウムから成
る合金で作られており、また、非多孔質層と該非孔質層
の片側又は両側に位置する多孔ｆｆ層を包含する膜部材
を有する触媒を製造することができる６多孔質の表面の
面積は単位α２の膜表面に対して１５０〜１，５００口
２の気孔（ρｏｓｅ）に等しく、多孔質層の非孔質層に
対する厚さの比は、それぞれに１ ： ５．７〜１００
である１本発明による模触媒は、通し孔のないよく発達
した多孔性表面を有し、元素状水素の使用による水素化
工程処理において、触媒の生産性を向上させるものであ
る。水素の選択的透過性ががなり増加する。したがって
、室温（１８〜２５℃）において、本発明による方法で
Ｓｔ造された膜触媒の水素透過性は、公知の膜触媒の水
素透過性より約５〜１０倍高い。そして該水素透過性は
、低温（２０〜４０℃の範囲内）での脂肪族及び芳香族
化合物中の炭素−炭素二重結合、ニトロ基又はアルデヒ
ド基の水素化工程を行うために、本発明による方法で製
造された膜触媒を使用することを可能にする。made by the method according to the invention of an alloy consisting of 95-80% by weight of palladium and 5-20% by weight of ruthenium or rhodium; The area of the porous surface is equal to 150 to 1,500 pores (ρose) for the membrane surface of unit α2, and the porous The thickness ratio of the layers to the non-porous layer is 1:5.7 to 100, respectively.
The simulated catalyst according to the present invention has a well-developed porous surface without through holes, which improves the productivity of the catalyst in hydrogenation process treatment using elemental hydrogen. The selective permeability of hydrogen increases. Therefore, at room temperature (18-25° C.), the hydrogen permeability of the membrane catalyst produced by the method according to the invention is about 5-10 times higher than that of known membrane catalysts. And the hydrogen permeability is determined by the present invention in order to carry out the hydrogenation process of carbon-carbon double bonds, nitro groups or aldehyde groups in aliphatic and aromatic compounds at low temperatures (within the range of 20-40°C). This makes it possible to use membrane catalysts produced by the method.
更に、本発明による方法で製造された触媒は、膜触媒の
操業及び再生中に破壊されない多孔Ｙ！Ｊ層の高いは械
的強度を特色とする。Furthermore, the catalyst produced by the method according to the invention has pores Y! which are not destroyed during operation and regeneration of the membrane catalyst. The high J layer is characterized by high mechanical strength.
すでに、上述したように、触媒活性金属として用いられ
るものは、８０〜９５質量％のパラジウム及び５〜２０
’ｆｊ量％のルテニウム或はロジウム ゛から成る合金
で作られる。パラノウム含量が少い（８０ｆｆｆ１％以
下）合金を使用することは、該合金を通過する水素透過
性が非常に低いので不適当である。一方、９５ｆｆｆ１
％を越えるパラノウム含量の場合には、該合金は、水ｉ
雰囲気中で不安定となり、容易に破壊される。As already mentioned above, those used as catalytically active metals include 80-95% by weight of palladium and 5-20% by weight of palladium.
It is made of an alloy consisting of fj% ruthenium or rhodium. The use of alloys with low paranoum content (less than 80 fff1%) is unsuitable because the hydrogen permeability through the alloys is very low. On the other hand, 95fff1
In case of paranoum content exceeding %, the alloy is
It becomes unstable in the atmosphere and is easily destroyed.
多量の亜鉛は、収に通し孔を形成する結果となるので、
亜鉛の膜に対する層厚比が１：１０以上のものを使用す
ることは、いづれも適当でない。Large amounts of zinc will result in the formation of pores in the
It is not appropriate to use a film having a layer thickness ratio of zinc to film of 1:10 or more.
層厚比が１：１００以下では、高活性の水素化触媒を得
ることができない膜表面の不十号な弛み（Ｉｏｓｓｅｎ
ｉｎＨ）を生ずる。If the layer thickness ratio is less than 1:100, a highly active hydrogenation catalyst cannot be obtained due to excessive slack on the membrane surface (Iossen et al.
inH).
高温では、パラゾ・クム表面層内に亜鉛の深い拡散が起
こり、次の塩酸処理に於いで、亜鉛を十分に分離するこ
とができず、模触媒の活性に悪影響を与えるので、亜鉛
層を有する膜の滞溜温度は、２５０℃を越えるべきでな
い、２０℃以下では、 ２パラジウム合金中への亜鉛の
拡散は、非常におそく、塩酸で亜鉛を溶解する際に、多
孔質層は実質的に形成されない。At high temperatures, deep diffusion of zinc occurs within the surface layer of parazocum, and in the subsequent hydrochloric acid treatment, zinc cannot be separated sufficiently and has a negative effect on the activity of the mock catalyst, so it is necessary to have a zinc layer. The residence temperature of the membrane should not exceed 250°C; below 20°C, the diffusion of zinc into the palladium alloy is very slow, and when dissolving zinc with hydrochloric acid, the porous layer is virtually Not formed.
作用
本発明による脂肪族及び芳香族化合物中の炭素−炭素二
重結合、ニトロ基及びアルデヒド基の水素化ｍ膜触媒を
製造する方法は、次の方法Ｃｈｔ了われる。Operation The method for producing the membrane catalyst for hydrogenation of carbon-carbon double bonds, nitro groups and aldehyde groups in aliphatic and aromatic compounds according to the present invention is as follows.
まず第１に、８０〜９５貿量％のパッジ１ンム及び５〜
２０質量％のルテニウム又はロジウムから成る合金で作
られた箔または管の如き膜の清浄な２層２面に、亜鉛の
１層が、亜鉛層の膜に対する厚さの比が１：１０〜１０
０で、片側又は両側へ電気化学的に析出される。析出さ
れた亜鉛層を有する膜を、２０〜２５０℃の範囲内の温
度に保持し、ソノ後、１０〜３７％の濃度の塩酸に入れ
る。乾燥後、得られた欣触媒は、原料と同一組成の合金
に準じ、そして非孔質層と多孔質層から成る。すなわち
多孔質層は、非多孔′Ｉ！層の両側又は片側のいづれか
に設けてもよい。後者の場合は、水素化工程は、多孔質
層側に°導がれる。First of all, 80-95% trade volume pad 1mm and 5-95% trade volume
A layer of zinc is applied on two sides of two clean layers of a membrane, such as a foil or tube, made of an alloy consisting of 20% by weight of ruthenium or rhodium, with a thickness ratio of the zinc layer to the membrane of 1:10 to 10.
0, electrochemically deposited on one or both sides. The membrane with the deposited zinc layer is kept at a temperature in the range of 20-250° C. and, after sowing, placed in hydrochloric acid with a concentration of 10-37%. After drying, the resulting catalyst corresponds to an alloy of the same composition as the raw material and consists of a non-porous layer and a porous layer. That is, the porous layer is non-porous 'I! It may be provided either on both sides or on one side of the layer. In the latter case, the hydrogenation step is conducted on the porous layer side.
本発明による方法で製？Ｌされた膜触媒は、熱伝導度セ
ンサーすなわちカサロメーターを使用して直接流動法に
より、水素透過性を試験する。Made by the method according to the invention? The treated membrane catalysts are tested for hydrogen permeability by the direct flow method using a thermal conductivity sensor or casalometer.
炭素−炭素二重結合、ニトロ基及ｖアルデヒド基を有す
る脂肪族及び芳香族化合物、例えば１゜３−ペンタノエ
ン、ニドミニタン、アセトアルデヒド、ニトロベンゼン
、カルボキシベンズアルデヒド、スチレンの水素化工程
を行うために、反応器の内部空間を２つの区画に分割す
る如き様式の反応器へ脱触媒を配置する。A reactor is used to carry out the hydrogenation process of aliphatic and aromatic compounds having carbon-carbon double bonds, nitro groups and v-aldehyde groups, such as 1°3-pentanoene, nidominitan, acetaldehyde, nitrobenzene, carboxybenzaldehyde, styrene. The decatalyst is placed in a reactor in such a way that the interior space of the reactor is divided into two compartments.
一方の区画室には水素を供給し、同時に他方には、水素
化される化合物が供給される。水素は、他の区画室へ脱
触媒を通って拡散し、所望の製品の形成と共に、脱触媒
の多孔質表面上で、活性元素形態において、水素化され
る化合物と相互に作用する。触媒組成は、クロマトグラ
フィによって決定されろ。触媒の多孔質層及び非孔質層
の厚さは、電子顕微鏡によって決定される。One compartment is supplied with hydrogen, while the other is supplied with the compound to be hydrogenated. Hydrogen diffuses through the decatalyst to other compartments and interacts with the compound to be hydrogenated in active element form on the porous surface of the decatalyst with the formation of the desired product. Catalyst composition will be determined by chromatography. The thickness of the porous and non-porous layers of the catalyst is determined by electron microscopy.
〆〆
一込−
１，／−
一／゛
、／−
、／
実施例
本発明のより良き理解のために、その特別の実施例を示
すいくつかの特定の例を以下に与える。EXAMPLES For a better understanding of the present invention, some specific examples are given below to illustrate special embodiments thereof.
例１
９０．２［１％のパラジウムおよび９．８質量％のルテ
ニウムからなる合金から遺られた１００肩の箔を脱脂し
、蒸留水ですすぎ、水１１中に硫酸亜鉛１３０ｇを溶解
した溶液を含んでなる電解液中に置いた０次いで、亜鉛
７）−ドを用いて、２０℃の温度、３．５Ａ／ｃ１ｍ２
の電ｔｉＬ密度および１．５の電解′ｌ＆ｐ Ｉ（にお
いて、１２分間、箔表面の片面上に亜鉛を析出せしめた
。Example 1 A 100-shoulder foil left over from an alloy consisting of 90.2 [1% palladium and 9.8% by weight ruthenium] was degreased, rinsed with distilled water and treated with a solution of 130 g of zinc sulfate in 11 parts of water. At a temperature of 20°C, 3.5A/c1m2 was placed in an electrolyte comprising
Zinc was deposited on one side of the foil surface for 12 minutes at an electric density of TiL and an electrolysis of 1&p I of 1.5.
１〇−厚さの亜鉛層が析出した箔を２５０ ’Ｃの温度
に加熱し、この温度に２時間保持した６次いで、箔を冷
却し、沸騰２０％塩酸内にｉさ、水素気泡の発生の停止
によって制御される亜鉛の完全な除去まで箔を塩酸内に
保持し、そして塩素イオンに基づく反応が存在しなくな
るまで水で洗浄した。かくして、上記合金から造られか
つ９０／Ｊｌ厚さの非孔質層と９１厚さの多孔質層とか
らなる箔の形の脱触媒が得られた。多孔質表面を、ＢＥ
Ｔテラー イー＋ （Ｂｒｕｎａｕｅｒ Ｓ、＋Ｅｍ
ｍｅｔ Ｐ、Ｈ，、Ｔｅ１ｌｅｒ Ｅ、））法によ
って測定した。得られたデータは、１５００ｃｍ２の気
孔（ｐｏｒｅｓ）が膜表面１ｃ＊”内に存在しているこ
とを示している。The foil on which a 10-thick zinc layer was deposited was heated to a temperature of 250'C and held at this temperature for 2 hours.The foil was then cooled and soaked in boiling 20% hydrochloric acid, producing hydrogen bubbles. The foil was kept in hydrochloric acid until complete removal of zinc, controlled by cessation of the reaction, and washed with water until no chloride ion-based reaction existed. A decatalyst in the form of a foil was thus obtained made of the above alloy and consisting of a non-porous layer of 90/Jl thickness and a porous layer of 91/Jl thickness. BE the porous surface
T-Terror E+ (Brunauer S, +Em
It was measured by the met P,H,,Teller E,)) method. The data obtained show that 1500 cm2 of pores are present within the membrane surface 1c*''.
上記のようにして製ｎされた脱触媒の水素透過度（Ｊ）
を第１表に示す。Hydrogen permeability (J) of decatalyzed catalyst produced as above
are shown in Table 1.
ｍｉ表
初めの箔（すなわち処理を受けていない箔）の水素透過
度は、２５℃の温度において４．７×１０−６Ｃ１１２
・ｓ−’ ・ＭＰａ−”、１００℃において−５，２１
Ｘｌ ０−５ｔｘ２・ｓ−’ ・ＭＰａ−”であった、
上記データから明らかなように、上記したようにして製
造された脱触媒の透過度は１００℃の温度において１５
倍だけ増加し、室温において１３０倍だけ増加した。The hydrogen permeability of the foil at the beginning of the mi table (i.e. the untreated foil) is 4.7 x 10-6C112 at a temperature of 25°C.
・s-'・MPa-'', -5,21 at 100℃
Xl 0-5tx2・s-'・MPa-'',
As is clear from the above data, the permeability of the decatalyzed product produced as described above is 15 at a temperature of 100°C.
130-fold increase at room temperature.
例２
前記例１記載のようにして、例１と同じ組成を有す為合
金の箔を用いて脱触媒を製造した。１０樗厚さの亜鉛層
が適用された箔を２０℃の温度に１日間保持した６次い
で、３０％塩酸中で亜鉛を溶解して除去し、上記合金か
ら遺られかつ８５牌厚さの非孔質層と１５／ＪＩＦｇ、
さの多孔質層とからなる箔として成形された脱触媒を得
た。脱触媒の多孔質表面の面積は、膜表面ＩＣ１１２当
たり気孔１．２００α２であった。脱触媒の水素透過度
を次のｔＪＳ２表に示す。Example 2 A decatalyst was prepared as described in Example 1 above using an alloy foil having the same composition as Example 1. The foil to which a 10 cm thick layer of zinc was applied was kept at a temperature of 20°C for 1 day.The zinc was then removed by dissolving in 30% hydrochloric acid and the non-alloy remaining from the above alloy and 85 cm thick was kept at a temperature of 20 °C for 1 day. Porous layer and 15/JIFg,
A decatalyzed film formed as a foil consisting of a porous layer and a thin porous layer was obtained. The area of the decatalyzed porous surface was 1.200 α2 pores per 112 membrane surface ICs. The hydrogen permeability after decatalyst is shown in the following tJS2 table.
第 ２ 表
温度、’Ｃ５４９４１０５１４４
ＭＰａ−０Ｊ５ ２．９５ ４．５２ ４，２７ ４
．０８上記第２表のデータから推して、例１に示された
初めの箔の透過度に対するデータとの比較により、本発
明に従って、製造された触媒の水素透過度はかなり高い
（１００℃の温度において約８倍だけ高い。）
例３
９４質荒％のパラジウムお上び６’ｊｔｆｉ％のルテニ
ウムからなる合金から造られた、外径１ｍ、肉Ｆｒｊ−
１００ｎの管の外表面上に、前記例１に記載したように
して、１−厚さになるまで亜鉛層を析出せしめた１次い
で、管を２３０℃の温度に加熱し、この温度に３０分間
保持し、次いで冷却し、その後、２５％塩酸を用いて亜
鉛を除去した。かくして、管として成形された脱触媒が
得られた。この管は、上記合金から遣られかつ９９／４
Ｊ１７さの非孔質内層とｌ Ｉｎｘ厚さの多孔質外層と
からなってし・た。Table 2 Temperature, 'C5494105144 MPa-0J5 2.95 4.52 4,27 4
．． 08 Inferred from the data in Table 2 above and by comparison with the data for the permeability of the initial foil given in Example 1, the hydrogen permeability of the catalyst prepared according to the invention is considerably higher (at a temperature of 100°C (about 8 times higher in diameter than 1 m).) Example 3 A steel plate with an outer diameter of 1 m, made of an alloy consisting of 94% palladium and 6'tfi% ruthenium.
On the outer surface of the 100 nm tube, a layer of zinc was deposited as described in Example 1 above, up to a thickness of 1. The tube was then heated to a temperature of 230 DEG C. and kept at this temperature for 30 minutes. It was held and then cooled, after which the zinc was removed using 25% hydrochloric acid. A decatalyst shaped as a tube was thus obtained. This tube is made from the above alloy and is 99/4
It consisted of a non-porous inner layer of J17 thickness and a porous outer layer of lInx thickness.
脱触媒の多孔質表面の面積は、膜表面１ｃＲ２当たり気
孔１５０α２であった。２４℃の温度における脱触媒の
水素透過度は５．０２ Ｘ １０−５α２ ・Ｓ−１・
ＭＰａ−”であり、すなわち初めの管の透過度より６１
オーダーの大きさだけ高かった。The area of the decatalyzed porous surface was 150 α2 pores per 1 cR2 of membrane surface. The hydrogen permeability of decatalyst at a temperature of 24°C is 5.02 X 10-5α2 ・S-1・
MPa-”, i.e. 61 from the initial tube permeability.
It was expensive because of the size of the order.
例４
８０質量％のパラジウムおよび２０質量％のロジウムか
らなる合金から遣られた１００陣の箔の両面上に、それ
ぞれが４岸の亜鉛層を適用した。Example 4 Four banks of zinc layers were each applied on both sides of 100 strips of foil made from an alloy consisting of 80% by weight palladium and 20% by weight rhodium.
亜鉛層の適用された箔を１５０℃の温度に４時間保持し
た。箔を冷却し、その後２０％塩酸中で煮沸することに
よって亜鉛を除去した。上記合金から遺られかつ９８纜
厚さの非孔質層と非孔質層の両面に置かれ、それぞれが
３−厚さの表面多孔質層とからなる箔として、脱触媒が
得られた。脱触媒の多孔ｓ２表面の面積は、膜表面１ｃ
Ｒ２当たり気孔４７０ｃｍ２であった。この触媒の１２
５℃の温度における水素透過度は、２．８２ Ｘ １０
−’α２・ｓ−’ ・ＭＰａ−”であった。The foil to which the zinc layer was applied was kept at a temperature of 150° C. for 4 hours. Zinc was removed by cooling the foil and then boiling in 20% hydrochloric acid. Decatalysis was obtained as a foil left from the above alloy and consisting of a 98-thick non-porous layer and a superficially porous layer, each 3-thick, placed on both sides of the non-porous layer. The area of the decatalytic porous s2 surface is the membrane surface 1c
The pores were 470 cm2 per R2. 12 of this catalyst
The hydrogen permeability at a temperature of 5°C is 2.82 x 10
−'α2・s−′・MPa−”.
例５
９５ｒＩ量％のパラジウムおよびＳｆｆ量％のロジウム
からなる合金から造られた５０／Ｊ１の笛から、脱触媒
を製造した。前記例１に記載したようにして、４．７趨
厚さの亜鉛層を宿の片面に析出せしめた。亜鉛層の析出
した箔を２５０℃の温度に加熱し、この温度に５時間保
持した。３７％塩酸で膜を処理して亜鉛を除去した。か
くして、上記合金から遺られかつ４９．ｒｉ、さの非孔
質層と２４厚さの多孔質層とからなる箔の形の脱触媒が
得られた。Example 5 A decatalyst was produced from a 50/J1 whistle made from an alloy consisting of 95rI% palladium and Sff% rhodium. A 4.7 inch thick layer of zinc was deposited on one side of the inlet as described in Example 1 above. The foil on which the zinc layer had been deposited was heated to a temperature of 250° C. and kept at this temperature for 5 hours. Zinc was removed by treating the membrane with 37% hydrochloric acid. Thus, 49. A decatalyst in the form of a foil was obtained, consisting of a non-porous layer of ri and a porous layer of 24 mm thickness.
脱触媒の多孔質表面の面積は、膜表面１ｃｖ２当たり気
孔５４０Ｇ１１２であった。触媒の水素透過度は、２４
℃において７．９４ Ｘ １０−’ｃｍ２・ｓ−’ ・
ＭＰａ−” 、１２０℃においで−１０，２Ｘ１０”ｃ
ｍ２ ・ｓ−’−ＭＰａ−Ｏｊであった。The area of the decatalyzed porous surface was 540 G112 pores per 1 cv2 of membrane surface. The hydrogen permeability of the catalyst is 24
7.94 x 10-'cm2・s-' at °C
MPa-", -10.2X10"c at 120℃
m2·s-'-MPa-Oj.
例６
９５質量％のパラジウムおよび５質量％のロジウムから
なる合金から造られた１００．厚さの苗土に、例１に記
載したようにして、６陣厚さの亜鉛層を析出せしめた。Example 6 100.6% made from an alloy consisting of 95% by weight palladium and 5% by weight rhodium. A 6-layer thick layer of zinc was deposited on the seedling soil as described in Example 1.
次いで、箔を２００℃の温度に３時間保持し、１０％塩
酸中で煮沸して亜鉛を除去した。上記合金から造られか
つ９６ｘＪ！７さの非孔質層と４／Ｊ１厚さの多孔質層
とからなる箔として、脱触媒が得られた。脱触媒の多孔
質表面の面積は、膜表面１α２当たり気孔８１０α２で
あった。この触媒の１２５℃における水素透過度は１．
０ＸＩＯ−’ｃｕｅｓ−’−ＭＰａ−”であった。The foil was then held at a temperature of 200° C. for 3 hours and boiled in 10% hydrochloric acid to remove zinc. Made from the above alloy and 96xJ! The decatalyst was obtained as a foil consisting of a non-porous layer of thickness 7 and a porous layer of thickness 4/J1. The area of the decatalyzed porous surface was 810α2 pores per 1α2 of membrane surface. The hydrogen permeability of this catalyst at 125°C is 1.
0XIO-'cues-'-MPa-''.
発明の効果
上記データから推しで、前記例１〜６記載のようにして
ｇＩ遺された脱触媒は高い水素透過度を示している。こ
れは、水素化工程における触媒の高い生産性を可能にす
る。Effects of the Invention From the above data, it can be inferred that the decatalyzed gI catalysts described in Examples 1 to 6 above exhibit high hydrogen permeability. This allows high productivity of the catalyst in the hydrogenation process.
例１〜６に従って、！ｌ！遺された脱触媒により、１．
３ペンタジエン、ニトロベンゼン、パラ−カルボキシベ
ンズアルデヒド
エタン、スチレンを水素化する方法を示している例７〜
１２を以下に与える。According to Examples 1-6,! l! By removing the remaining catalyst, 1.
Example 7 showing a method for hydrogenating 3-pentadiene, nitrobenzene, para-carboxybenzaldehyde ethane, and styrene.
12 is given below.
例７
前記例１に記載されたようにして笛の形に製造された膜
触媒の触媒特性の研究を、上記触媒によって２つのチャ
ンバーに分割された反応器内で１゜３−ペンタノエンを
水素化することによって行なった。一方のチャンバー内
へ、膜触媒の非孔質層の側で、水素を３０ｄ／分の速度
で通し、他方のチャンバー内へ、膜触媒の多孔質層の側
で、アルゴンと１，３−ペンタジェンとの混合物を、１
０寵■２の１，３−ペンタノエン蒸気の圧力下、１０ｄ
／分の速度で供給した。Example 7 A study of the catalytic properties of a membrane catalyst produced in the form of a whistle as described in Example 1 above was carried out for the hydrogenation of 1°3-pentanoene in a reactor divided into two chambers by said catalyst. It was done by doing. Into one chamber, on the side of the non-porous layer of membrane catalyst, hydrogen was passed at a rate of 30 d/min and into the other chamber, on the side of the porous layer of membrane catalyst, argon and 1,3-pentadiene were passed. a mixture of 1
10d under the pressure of 1,3-pentanoene vapor of 2
It was fed at a rate of /min.
種々の温度の水素化工程で得られた接触反応生成物の組
成を以下の第３表に示す。The composition of the catalytic reaction products obtained in the hydrogenation step at various temperatures is shown in Table 3 below.
／′−
／′
比較のために、初めの箔により１，３−ペンタノエンを
水素化して得られた接触反応生成物の組成をｉ＠４表に
示す。/'- /' For comparison, the composition of the catalytic reaction product obtained by hydrogenating 1,3-pentanoene with the initial foil is shown in Table i@4.
ｔＩＳ４ 表
温度、”ｃ −、−−、、−、、−−−−−、、、、
、、−−−、、、、−−−、、−、、、＝ペンタン １
−２−１．３−
ペンテン ペンテン ペンタジェン
１００ １．０ １３．０ ３６，０ ５
０．０１５０ １．９ ２３．３ ４９，７
２５．１／゛′
／′
、／”’
７、／
／′
第３表および第４表に与えられたデータかられかるよう
に、本発明の膜触媒を用いて達成された水素化の深さは
かなり高い。かくして、１００℃の温度において、ペン
タンの収率は１モル％から９５モル％へ増大した。水素
化工程の選択率もまた環状炭化水素の形成に対して変化
した。tIS4 Table temperature, "c -, --,, -,, -----,,,,
,,---,,,,---,,-,,,=pentane 1
-2-1.3- Pentene Pentene Pentagene 100 1.0 13.0 36,0 5
0.0150 1.9 23.3 49,7
25.1/''/' , /'' 7, / /' As can be seen from the data given in Tables 3 and 4, the depth of hydrogenation achieved using the membrane catalyst of the present invention Thus, at a temperature of 100° C., the yield of pentane increased from 1 mol% to 95 mol%. The selectivity of the hydrogenation step also changed towards the formation of cyclic hydrocarbons.
例８
前記例２におけるように箔として製造された膜触媒の触
媒特性の研究を、上記膜触媒によって２つのチャンバー
に分割された反応器内でスチレンを水素化することによ
って打なった。一方のチャンバー内へ、膜触媒の非孔質
層の側で、水素を５０ｄ２分の速度で供給し、また別の
チャンバー内へ、触媒の多孔質層の側で、スチレンをア
ルゴンとの混合物で、１５０ ｗＨｇのスチレン蒸気の
圧力下、５ｏｄ１分の速度で通した。種々の温度の水素
化工程で得られた接触反応生成物の組成が以下の第５表
に与える。Example 8 A study of the catalytic properties of a membrane catalyst produced as a foil as in Example 2 above was carried out by hydrogenating styrene in a reactor divided into two chambers by the membrane catalyst. Into one chamber, on the side of the non-porous layer of membrane catalyst, hydrogen was fed at a rate of 50 d2 min, and in the other chamber, on the side of the porous layer of catalyst, styrene was fed in a mixture with argon. , 150 wHg of styrene vapor at a rate of 5 od 1 min. The composition of the catalytic reaction products obtained in the hydrogenation step at various temperatures is given in Table 5 below.
第 ５ 表
ンゼン ヘキサン
ｆ３０ ２５，６ − ７４．４１０
０ ４５．３ １２，１ ４２．６１８
０ ３８．７ ３３．５ ２７．８２５
０ ２３．４ ２８，１ ４８．５第４
表および第５表に示されたデータかられかるように、本
発明により製造された膜触媒は、脂肪族および芳香族化
合物の炭素−炭素二重結合の水素化において活性である
。Table 5 Hexane f30 25,6 - 74.410
0 45.3 12.1 42.618
0 38.7 33.5 27.825
0 23.4 28,1 48.5 4th
As can be seen from the data presented in Tables and Table 5, the membrane catalysts prepared according to the invention are active in the hydrogenation of carbon-carbon double bonds of aliphatic and aromatic compounds.
例９
前記例３におけるように管として９１ｉされた膜触媒の
触媒特性の研究を、パラ−カルボキシベンズアルデヒド
の水素化により行なった。水素化は、かかる管の東を含
む反応器内で行なわれた。Ｗの内部に、水素を５０ｄ／
分の速度で６ＭＰａの圧力下供給し、−万骨の間の空間
に、１０％パラ−カルボキシベンズアルデヒド水溶液を
供給した。Example 9 A study of the catalytic properties of the membrane catalyst 91i as in Example 3 above was carried out by hydrogenation of para-carboxybenzaldehyde. Hydrogenation was carried out in a reactor containing the east of such a tube. 50d/ of hydrogen inside W
A 10% aqueous solution of para-carboxybenzaldehyde was supplied into the space between the ribs at a rate of 1.5 min under a pressure of 6 MPa.
反応器内の温度を２５４℃に上昇させ、５．４ ＭＰａ
の圧力下、１時開、水素化を行なった６得られた触媒の
分析によれば、パラ−カルボキシベンズアルデヒドは、
パラ−トルイル酸へ実質的に完全に転化した。未転化パ
ラ−カルボキシベンズアルデヒドの量は、その初めの量
の０．０４％であった。The temperature inside the reactor was increased to 254°C and 5.4 MPa
According to the analysis of the catalyst obtained by hydrogenation under the pressure of 1 hour, para-carboxybenzaldehyde was
Substantially complete conversion to para-toluic acid was achieved. The amount of unconverted para-carboxybenzaldehyde was 0.04% of its initial amount.
例１０
例４におけるように箔として製ｉされた膜触媒の触媒特
性の研究を、この狡触媒によって２つのチャンバーに分
割された反応器内で７セトアルデビドを水素化すること
によって行なった。一方のチャンバー内に、水素流を６
０ｄ／分の速度で供給し、また他方のチャンバー内へ、
アセトアルデヒドの蒸気を、アルゴンとの混合物として
４００ｆｌ ｏｇの７七トアルデヒド蒸気の圧力下、３
０ｎ／分の速度で供給した。Example 10 A study of the catalytic properties of a membrane catalyst made as a foil as in Example 4 was carried out by hydrogenating 7cetaldevide with this catalyst in a reactor divided into two chambers. In one chamber, a hydrogen flow of 6
feeding at a rate of 0 d/min and into the other chamber;
Acetaldehyde vapor was mixed with argon under the pressure of 400 fl og of 77-taldehyde vapor, 3
It was fed at a rate of 0 n/min.
種々の温度の水素化工程で製造された接触反応生成物の
組成をｔＪＳＧ表に示す。The composition of the catalytic reaction products produced in the hydrogenation process at various temperatures is shown in the tJSG table.
第 ６ 表
５０ − ５ 、７ ９４ 、３１００
− １５．７ ８４．０２００ ４．３
５６．７ ３９．０２５０ １３．２ ２４，
２ ６２．６例１１
前記例５におけるように箔として製造された膜触媒の触
媒特性の研究を、該膜触媒によって２つのチャンバーに
仕切られた反応器内でニトロベンゼンを水素化すること
によって行なった。一方のチャンバー内へ、膜触媒の非
孔ＹＸＭの側で、水素を４５ｄ／分の速度で通し、また
他方のチャンバー内へ、触媒の多孔１！ｌ屑の側で、ニ
トロベンゼンの蒸気を、アルゴンとの混合物として、１
００ｆｉ−のニトロベンゼン蒸気の圧力下、３０ｄ１分
の速度で供給した。２５０℃、２７２℃およ１３１０℃
の温度において、ニトロベンゼンのアニリンへの十分な
転化が観測された。１７０℃の温度において、反応生成
物中に０．５％未反応ニトロベンゼンが含まれていた。Table 6 50-5, 794, 3100
- 15.7 84.0200 4.3
56.7 39.0250 13.2 24,
2 62.6 Example 11 A study of the catalytic properties of a membrane catalyst prepared as a foil as in Example 5 above was carried out by hydrogenating nitrobenzene in a reactor partitioned into two chambers by the membrane catalyst. . Hydrogen is passed into one chamber on the non-porous YXM side of the membrane catalyst at a rate of 45 d/min and into the other chamber on the non-porous YXM side of the catalyst. On the side of the scrap, nitrobenzene vapor was added in a mixture with argon to
00fi- of nitrobenzene vapor was fed at a rate of 30d1 min. 250℃, 272℃ and 1310℃
At a temperature of , sufficient conversion of nitrobenzene to aniline was observed. At a temperature of 170°C, the reaction product contained 0.5% unreacted nitrobenzene.
例１２
例６におけるように箔の形で製造された膜触媒の触媒特
性の研究を、該膜触媒によって、２つのチャンバーに仕
切られた反応器内でニトロエタンを水素化することによ
って行なった。一方のチャンバー内へ、触媒の非孔質層
の側で、水素を５０ｄ／分の速度で供給し、また他方の
チャンバー内へ、ニトロエタン蒸気を、アルゴンとの混
合物として、４００ ｍ ）Ｉｇのニトロエタン蒸気の
圧力下、４０ｄ１分の速度で供給した。種々の温度の水
素化工程で得られた接触反応生成物の組成を以下の第７
表に与える（接触反応生成物の組成は水を計算せずに示
す。）
第 ７ 表
６５ ９６．４ ３．６ −１２０ １０
０．０ − −２１０ １００．０
− −３００ ９７．１ １．０ １
．９３５０ Ｂ３．６ １０，４ ６．０
上記例８〜１２から推して、本発明に従う方法によって
製造された膜触媒は、種々の有機化合物中の炭素−炭素
二重結合の水素化工程において大いに活性である。これ
により、種々の化学的方法において上記膜触媒を広く用
いることが可能になる。Example 12 A study of the catalytic properties of a membrane catalyst produced in the form of a foil as in Example 6 was carried out by hydrogenating nitroethane with the membrane catalyst in a reactor partitioned into two chambers. Into one chamber, on the side of the non-porous layer of catalyst, hydrogen was fed at a rate of 50 d/min, and in the other chamber, nitroethane vapor was fed as a mixture with argon at 400 m ) Ig of nitroethane. It was fed under steam pressure at a rate of 40 d1 min. The composition of the catalytic reaction product obtained in the hydrogenation process at various temperatures was determined as follows.
(The composition of the contact reaction product is shown without calculating water.) Table 7 65 96.4 3.6 -120 10
0.0 - -210 100.0
- -300 97.1 1.0 1
．． 9350 B3.6 10,4 6.0
It can be inferred from Examples 8 to 12 above that the membrane catalysts prepared by the method according to the invention are highly active in hydrogenation processes of carbon-carbon double bonds in various organic compounds. This allows the membrane catalyst to be widely used in various chemical processes.
Claims (1)
散を確実にする温度に保持し、続いて触媒活性金属から
亜鉛を化学的に回収することによって、脂肪族及び芳香
族化合物中の炭素−炭素二重結合、ニトロ基及びアルデ
ヒド基の水素化用触媒を製造する方法であって、前記触
媒活性金属が８０〜９５質量％のパラジウム及び５〜２
０質量％のルテニウム或はロジウムから成る合金の膜と
して使用され、亜鉛は、膜表面の片側又は両側に、亜鉛
層の厚さの膜厚に対する比が１：１０〜１００で適用さ
れ、そしてこの亜鉛を適用された膜は、２０〜２５０℃
の範囲内の温度に保持され、そして該膜から亜鉛の化学
的回収が該膜を塩酸で処理することによって達成される
ことを特徴とする水素化用触媒の製造方法。Carbon in aliphatic and aromatic compounds is removed by applying zinc onto the catalytically active metals, holding these metals at a temperature that ensures interdiffusion, and subsequently chemically recovering the zinc from the catalytically active metals. - A method for producing a catalyst for the hydrogenation of carbon double bonds, nitro groups and aldehyde groups, wherein the catalytically active metal is 80-95% by mass of palladium and 5-2% by mass of palladium.
Used as an alloy membrane consisting of 0% by weight of ruthenium or rhodium, zinc is applied on one or both sides of the membrane surface in a ratio of zinc layer thickness to membrane thickness of 1:10 to 100; Membranes applied with zinc can be heated at 20-250℃
A process for producing a hydrogenation catalyst, characterized in that the chemical recovery of zinc from the membrane is achieved by treating the membrane with hydrochloric acid.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| FR8602943A FR2595056B1 (en) | 1986-03-03 | 1986-03-03 | PROCESS FOR THE PREPARATION OF A CATALYST FOR HYDROGENATION BY HYDROGEN OF THE C = C DOUBLE BINDING, NITRO- AND ALDEHYDE GROUPS IN ALIPHATIC AND AROMATIC COMPOUNDS |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPS62204848A true JPS62204848A (en) | 1987-09-09 |
Family
ID=9332695
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP61045146A Pending JPS62204848A (en) | 1986-03-03 | 1986-02-28 | Production of catalyst for hydrogenating carbon-carbon double bond, nitro group and aldehyde group in aliphatic andaromatic compound |
Country Status (4)
| Country | Link |
|---|---|
| JP (1) | JPS62204848A (en) |
| DE (1) | DE3609264A1 (en) |
| FR (1) | FR2595056B1 (en) |
| GB (1) | GB2187759B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH07188066A (en) * | 1993-12-28 | 1995-07-25 | Nec Corp | Device for reductive hydrogenation, method therefor and material for reductive hydrogenation |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2850665B1 (en) | 2003-01-31 | 2006-06-30 | Inst Francais Du Petrole | TOTAL HYDROGENATION PROCESS USING HYDROGEN SELECTIVE MEMBRANE CATALYST REACTOR |
| FR2850664B1 (en) | 2003-01-31 | 2006-06-30 | Inst Francais Du Petrole | SELECTIVE HYDROGENATION PROCESS USING A CATALYTIC REACTOR WITH SELECTIVE HYDROGEN MEMBRANE |
| GB0614909D0 (en) | 2006-07-27 | 2006-09-06 | Johnson Matthey Plc | Catalyst |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| USRE31104E (en) * | 1973-01-31 | 1982-12-14 | Alloy Surfaces Company, Inc. | Catalytic structure |
| DE2431510C3 (en) * | 1974-07-01 | 1981-05-21 | Institut neftechimičeskogo sinteza imeni A.V. Topčieva Akademii Nauk SSSR | Process for the production of cycloolefins |
-
1986
- 1986-02-28 JP JP61045146A patent/JPS62204848A/en active Pending
- 1986-03-03 FR FR8602943A patent/FR2595056B1/en not_active Expired
- 1986-03-10 GB GB8605812A patent/GB2187759B/en not_active Expired - Lifetime
- 1986-03-19 DE DE19863609264 patent/DE3609264A1/en not_active Withdrawn
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH07188066A (en) * | 1993-12-28 | 1995-07-25 | Nec Corp | Device for reductive hydrogenation, method therefor and material for reductive hydrogenation |
Also Published As
| Publication number | Publication date |
|---|---|
| GB2187759B (en) | 1990-04-18 |
| FR2595056A1 (en) | 1987-09-04 |
| DE3609264A1 (en) | 1987-09-24 |
| GB2187759A (en) | 1987-09-16 |
| FR2595056B1 (en) | 1988-06-24 |
| GB8605812D0 (en) | 1986-04-16 |
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