JPH0229053B2 - - Google Patents
Info
- Publication number
- JPH0229053B2 JPH0229053B2 JP59058656A JP5865684A JPH0229053B2 JP H0229053 B2 JPH0229053 B2 JP H0229053B2 JP 59058656 A JP59058656 A JP 59058656A JP 5865684 A JP5865684 A JP 5865684A JP H0229053 B2 JPH0229053 B2 JP H0229053B2
- Authority
- JP
- Japan
- Prior art keywords
- ruthenium
- weight
- catalyst
- silica gel
- copper
- 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.)
- Expired - Lifetime
Links
- 239000003054 catalyst Substances 0.000 claims description 21
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 18
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 15
- 238000000034 method Methods 0.000 claims description 15
- 229910052707 ruthenium Inorganic materials 0.000 claims description 15
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims description 14
- 238000005984 hydrogenation reaction Methods 0.000 claims description 14
- 239000000741 silica gel Substances 0.000 claims description 13
- 229910002027 silica gel Inorganic materials 0.000 claims description 13
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 8
- -1 alkyl phosphate esters Chemical class 0.000 claims description 8
- 229910052802 copper Inorganic materials 0.000 claims description 8
- 239000010949 copper Substances 0.000 claims description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 7
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 14
- 238000006243 chemical reaction Methods 0.000 description 14
- HGCIXCUEYOPUTN-UHFFFAOYSA-N cyclohexene Chemical compound C1CCC=CC1 HGCIXCUEYOPUTN-UHFFFAOYSA-N 0.000 description 8
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 6
- 229910052710 silicon Inorganic materials 0.000 description 6
- 239000010703 silicon Substances 0.000 description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- XCEAGAJKBRACAD-UHFFFAOYSA-N [Cu].[Ru] Chemical compound [Cu].[Ru] XCEAGAJKBRACAD-UHFFFAOYSA-N 0.000 description 4
- 150000004678 hydrides Chemical class 0.000 description 4
- 150000003304 ruthenium compounds Chemical class 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 239000005749 Copper compound Substances 0.000 description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 150000001880 copper compounds Chemical class 0.000 description 3
- 230000007062 hydrolysis Effects 0.000 description 3
- 238000006460 hydrolysis reaction Methods 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 2
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 2
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical compound CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000004817 gas chromatography Methods 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 150000003303 ruthenium Chemical class 0.000 description 2
- YBCAZPLXEGKKFM-UHFFFAOYSA-K ruthenium(iii) chloride Chemical compound [Cl-].[Cl-].[Cl-].[Ru+3] YBCAZPLXEGKKFM-UHFFFAOYSA-K 0.000 description 2
- 150000005846 sugar alcohols Polymers 0.000 description 2
- PGGZAZHZNVKDLG-UHFFFAOYSA-N 1,4-dioxane;hexane Chemical compound CCCCCC.C1COCCO1 PGGZAZHZNVKDLG-UHFFFAOYSA-N 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 1
- ROFVEXUMMXZLPA-UHFFFAOYSA-N Bipyridyl Chemical group N1=CC=CC=C1C1=CC=CC=N1 ROFVEXUMMXZLPA-UHFFFAOYSA-N 0.000 description 1
- 229910021591 Copper(I) chloride Inorganic materials 0.000 description 1
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 1
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 1
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- DGEZNRSVGBDHLK-UHFFFAOYSA-N [1,10]phenanthroline Chemical compound C1=CN=C2C3=NC=CC=C3C=CC2=C1 DGEZNRSVGBDHLK-UHFFFAOYSA-N 0.000 description 1
- VFAHXTJRZRHGDN-UHFFFAOYSA-N [Ru].[C]=O Chemical class [Ru].[C]=O VFAHXTJRZRHGDN-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000002738 chelating agent Substances 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000007810 chemical reaction solvent Substances 0.000 description 1
- 229910000152 cobalt phosphate Inorganic materials 0.000 description 1
- 229910000361 cobalt sulfate Inorganic materials 0.000 description 1
- 229940044175 cobalt sulfate Drugs 0.000 description 1
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 description 1
- ZBDSFTZNNQNSQM-UHFFFAOYSA-H cobalt(2+);diphosphate Chemical compound [Co+2].[Co+2].[Co+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O ZBDSFTZNNQNSQM-UHFFFAOYSA-H 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 description 1
- 229940045803 cuprous chloride Drugs 0.000 description 1
- 230000005674 electromagnetic induction Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 235000011187 glycerol Nutrition 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- FBAFATDZDUQKNH-UHFFFAOYSA-M iron chloride Chemical compound [Cl-].[Fe] FBAFATDZDUQKNH-UHFFFAOYSA-M 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 239000004570 mortar (masonry) Substances 0.000 description 1
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 description 1
- RFYYQFJZJJCJNT-UHFFFAOYSA-N pentane-2,4-dione;ruthenium Chemical compound [Ru].CC(=O)CC(C)=O RFYYQFJZJJCJNT-UHFFFAOYSA-N 0.000 description 1
- 239000003495 polar organic solvent Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- WYRXRHOISWEUST-UHFFFAOYSA-K ruthenium(3+);tribromide Chemical compound [Br-].[Br-].[Br-].[Ru+3] WYRXRHOISWEUST-UHFFFAOYSA-K 0.000 description 1
- FZHCFNGSGGGXEH-UHFFFAOYSA-N ruthenocene Chemical compound [Ru+2].C=1C=C[CH-]C=1.C=1C=C[CH-]C=1 FZHCFNGSGGGXEH-UHFFFAOYSA-N 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- 239000008096 xylene 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
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Description
【発明の詳細な説明】
本発明は芳香族炭化水素の部分核水素化法に関
するものである。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for partial nuclear hydrogenation of aromatic hydrocarbons.
芳香族炭化水素の部分核水素化物、例えば、シ
クロヘキセンやアルキルシクロヘキセン等は、合
成原料として重要な化合物であり、その工業的に
有利な製法の開発が望まれている。しかしなが
ら、このような芳香族炭化水素の部分核水素化物
の製造は困難であり、芳香族炭化水素を通常の方
法で水素化すると、芳香族は部分水素化されずに
完全水素化され、シクロパラフインを与える。 Partial nuclear hydrides of aromatic hydrocarbons, such as cyclohexene and alkylcyclohexene, are important compounds as raw materials for synthesis, and it is desired to develop an industrially advantageous method for producing them. However, it is difficult to produce such partial nuclear hydrides of aromatic hydrocarbons, and when aromatic hydrocarbons are hydrogenated by the usual method, aromatics are completely hydrogenated without being partially hydrogenated, resulting in cycloparaffin give.
従来、このような部分核水素化に関する方法と
しては、アルカリ金属の存在下、液体アンモニア
を溶媒として水素化を行う方法（西ドイツ特許第
1443377号及び1793757号明細書）が知られてい
る。この方法は、比較的良好な部分核水素化物の
収率を与えるものの、複雑な反応操作を必要とす
るため工業的方法としては不適当である。 Conventionally, as a method for such partial nuclear hydrogenation, a method of hydrogenation using liquid ammonia as a solvent in the presence of an alkali metal (West German Patent No.
1443377 and 1793757) are known. Although this method provides a relatively good yield of partial nuclear hydrides, it is unsuitable as an industrial method because it requires complicated reaction operations.
一方、工業的に見て比較的興味ある方法とし
て、水の存在下において、ルテニウム触媒を用い
て水素化を行う方法が知られている（特開昭53−
46938号、53−65849号、53−63350号等）。この場
合のルテニウム触媒は、シリカやアルミナ等の多
孔質担体にルテニウムを担持させたものである
が、部分核水素化物の収率は低く、工業的見地か
らは末だ満足し得るものではなかつた。 On the other hand, a method of hydrogenation using a ruthenium catalyst in the presence of water is known as a relatively interesting method from an industrial point of view (Japanese Patent Application Laid-Open No. 1983-1993-1).
No. 46938, No. 53-65849, No. 53-63350, etc.). The ruthenium catalyst used in this case is one in which ruthenium is supported on a porous carrier such as silica or alumina, but the yield of partial nuclear hydrides is low and is far from satisfactory from an industrial standpoint. .
本発明者らは、芳香族炭化水素の部分核水素化
において、工業的に有利な方法を開発すべく種々
研究を重ねた結果、本発明を完成するに到つた。 The present inventors have completed the present invention as a result of various studies aimed at developing an industrially advantageous method for partial nuclear hydrogenation of aromatic hydrocarbons.
即ち、本発明によれば、芳香族炭化水素を、水
及び水素化触媒の存在下、水素ガスと反応させて
部分核水素化する方法において、該水素化触媒と
して、ケイ素アルコキシドの加水分解生成物から
誘導されたシリカゲル中に分散されたルテニウ
ム・銅触媒を用いることを特徴とする芳香族炭化
水素の部分核水素化法が提供される。 That is, according to the present invention, in a method of partially hydrogenating an aromatic hydrocarbon by reacting it with hydrogen gas in the presence of water and a hydrogenation catalyst, a hydrolysis product of silicon alkoxide is used as the hydrogenation catalyst. A method for partial nuclear hydrogenation of aromatic hydrocarbons is provided, which is characterized in that it uses a ruthenium-copper catalyst dispersed in silica gel derived from silica gel.
本発明においては、水素化触媒として、ケイ素
アルコキシドの加水分解生成物から誘導されたシ
リカゲル中に分散されたルテニウム・銅触媒を用
いることを特徴とする。 The present invention is characterized in that a ruthenium/copper catalyst dispersed in silica gel derived from a hydrolysis product of silicon alkoxide is used as a hydrogenation catalyst.
本発明において用いる触媒は、前記ケイ素アル
コキシドの加水分解物の持つゲル化作用を利用し
て製造される。例えば、一価又は多価アルコール
から誘導されたケイ素アルコキシドとルテニウム
化合物及び銅化合物を溶解させた有機溶媒溶液に
水を加えて加熱撹拌する。この加熱撹拌操作によ
り、ケイ素アルコキシドは加水分解されると同時
に、次第にゲル化され、ゲル状物質を生成する。
このゲル状物質を加熱乾燥すると、内部にルテニ
ウム化合物と銅化合物が均一に分散したシリカゲ
ルが得られる。 The catalyst used in the present invention is produced by utilizing the gelling effect of the silicon alkoxide hydrolyzate. For example, water is added to an organic solvent solution in which a silicon alkoxide derived from a monohydric or polyhydric alcohol, a ruthenium compound, and a copper compound are dissolved, and the mixture is heated and stirred. By this heating and stirring operation, the silicon alkoxide is hydrolyzed and at the same time is gradually gelled to produce a gel-like substance.
When this gel-like substance is heated and dried, a silica gel in which a ruthenium compound and a copper compound are uniformly dispersed is obtained.
前記ルテニウム化合物の有機溶媒溶液として
は、塩化ルテニウムや臭化ルテニウム等のルテニ
ウム塩や、アセチルアセトンルテニウム等の他、
エチレンジアミン、フエナンスロリン、ビピリジ
ル等のキレート化剤と結合したルテニウムアンミ
ン錯体、及びカルボニルルテニウム錯体やルテノ
セン等の有機ルテニウム錯体、あるいはルテニウ
ムアルコキシド等のルテニウム化合物をメタノー
ル、エタノール等の一価アルコールや、エチレン
グリコール、プロピレングリコール、グリセリン
等の多価アルコール、アセチルアセトン等の極性
有機溶媒に溶解させた溶液を用いることができ
る。また、銅化合物の溶媒についても、前記と同
様にして得ることができる。 Examples of the organic solvent solution of the ruthenium compound include ruthenium salts such as ruthenium chloride and ruthenium bromide, ruthenium acetylacetone, etc.
Ruthenium ammine complexes combined with chelating agents such as ethylenediamine, phenanthroline, and bipyridyl, organic ruthenium complexes such as carbonylruthenium complexes and ruthenocene, or ruthenium compounds such as ruthenium alkoxides are mixed with monohydric alcohols such as methanol, ethanol, ethylene glycol, etc. A solution dissolved in a polyhydric alcohol such as propylene glycol or glycerin, or a polar organic solvent such as acetylacetone can be used. Further, the solvent for the copper compound can also be obtained in the same manner as described above.
本発明で用いる前記シリカゲル中に分散させた
ルテニウム銅触媒において、ルテニウム担持量
は、金属換算で0.01〜50重量％、好ましくは0.1
〜20重量％、銅担持量は金属換算でルテニウム担
持量の２〜20重量％である。 In the ruthenium copper catalyst dispersed in the silica gel used in the present invention, the amount of ruthenium supported is 0.01 to 50% by weight in terms of metal, preferably 0.1% by weight.
~20% by weight, and the amount of copper supported is 2 to 20% by weight of the amount of ruthenium supported in terms of metal.
本発明において用いる触媒は、使用に際し、通
常の水素ガス流通還元法で、還元処理を行う。こ
の場合の還元処理温度は50〜900℃、好ましくは
200〜600℃である。本発明の触媒はこの還元処理
後に反応器に充填使用する。 Before use, the catalyst used in the present invention is subjected to a reduction treatment using a conventional hydrogen gas flow reduction method. In this case, the reduction treatment temperature is 50 to 900℃, preferably
The temperature is 200-600℃. After this reduction treatment, the catalyst of the present invention is charged into a reactor and used.
本発明における芳香族炭化水素の部分核水素化
法は、水と前記ルテニウム・銅触媒の存在下にお
いて、芳香族炭化水素と水素ガスとを反応させる
ことによつて実施される。この場合、水の使用量
は、芳香族炭化水素１重量部に対して0.01〜20重
量部、好ましくは0.1〜５重量部であり、触媒の
使用量は芳香族炭化水素に対し、0.01〜50重量
％、好ましくは0.1〜１重量％である。反応温度
は０〜300℃、好ましくは50〜220℃であり、反応
圧力は0.01〜500Kg／cm2、好ましくは１〜200Kg／
cm2である。 The partial nuclear hydrogenation method of aromatic hydrocarbons in the present invention is carried out by reacting aromatic hydrocarbons with hydrogen gas in the presence of water and the ruthenium/copper catalyst. In this case, the amount of water used is 0.01 to 20 parts by weight, preferably 0.1 to 5 parts by weight, based on 1 part by weight of aromatic hydrocarbons, and the amount of catalyst used is 0.01 to 50 parts by weight, based on 1 part by weight of aromatic hydrocarbons. % by weight, preferably 0.1-1% by weight. The reaction temperature is 0 to 300°C, preferably 50 to 220°C, and the reaction pressure is 0.01 to 500Kg/ cm2 , preferably 1 to 200Kg/cm2.
cm2 .
本発明の方法を実施する場合、反応は連続式又
は回分式で行うことができ、必要に応じ、補助添
加物、例えば、リン酸コバルト、硫酸コバルト、
塩化ニツケル、塩化鉄などの金属塩やNaOH，
KOH等のアルカリ、HClなどの酸を反応系に添
加することができる。本発明においては反応溶媒
の使用は特に必要とされないが、エタノールイソ
プロピルアルコール、ジオキサンヘキサン、ジメ
チルホルムアミド、ジメチルスルホキシド等の溶
媒を用いることができる。本発明で原料として用
いる芳香族炭化水素の具体例としては、例えば、
ベンゼン、トルエン、キシレン等が挙げられる。 When carrying out the process of the invention, the reaction can be carried out continuously or batchwise, and if necessary, auxiliary additives, such as cobalt phosphate, cobalt sulfate,
Metal salts such as nickel chloride and iron chloride, NaOH,
An alkali such as KOH or an acid such as HCl can be added to the reaction system. Although the use of a reaction solvent is not particularly required in the present invention, solvents such as ethanol isopropyl alcohol, dioxane hexane, dimethylformamide, and dimethyl sulfoxide can be used. Specific examples of aromatic hydrocarbons used as raw materials in the present invention include, for example:
Examples include benzene, toluene, xylene and the like.
次に本発明を実施例によりさらに詳細に説明す
る。 Next, the present invention will be explained in more detail with reference to Examples.
なお、実施例において示した転化率及び選択率
はいずれも反応により生成した有機液層をガスク
ロマトグラフイーで分析してそれぞれ指定する物
質について次式によつて求めた値である。 It should be noted that the conversion rates and selectivities shown in the Examples are both values obtained by analyzing the organic liquid layer produced by the reaction by gas chromatography and using the following formula for each designated substance.
転化率（モル％）＝〔１−（Ａ／Ｂ）〕×100
Ａ……反応液中の芳香族炭化水素モル数
Ｂ……原料芳香族炭化水素モル数
選択率（モル％）＝〔１−（Ｃ／Ｄ〕×100
Ｃ……シクロヘキセンのモル数
Ｄ……反応生成物の全モル数
参考例 （触媒調製法）
550mlのナス型フラスコに塩化ルテニウム1.0ｇ
を取り、エチレングリコール100mlを加えて60℃
で２時間撹拌する。この液にケイ素テトラエトキ
シド（ケイ酸テトラエチル）132.5ｇ、塩化第一
銅0.1ｇを加えて60℃で２時間撹拌する。この混
合溶液に、水100mlを加えて60℃で10〜48時間撹
拌を続けると、黒緑のゲル状の物質が生成してく
る。Conversion rate (mol%) = [1-(A/B)] x 100 A...Number of moles of aromatic hydrocarbon in the reaction solution B...Number of moles of raw material aromatic hydrocarbon Selectivity (mol%) = [1 -(C/D] x 100 C... Number of moles of cyclohexene D... Total number of moles of reaction products Reference example (Catalyst preparation method) 1.0 g of ruthenium chloride in a 550 ml eggplant-shaped flask
Add 100ml of ethylene glycol and heat at 60℃.
Stir for 2 hours. To this liquid were added 132.5 g of silicon tetraethoxide (tetraethyl silicate) and 0.1 g of cuprous chloride, and the mixture was stirred at 60°C for 2 hours. When 100 ml of water is added to this mixed solution and stirring is continued at 60°C for 10 to 48 hours, a black-green gel-like substance is formed.
このゲル状物質をエバボレーターで80℃で真空
乾燥すると粒状物が得られ、これを乳鉢で細粉化
することにより、ルテニウム含量２重量％銅含量
0.2重量％のシリカゲル(A)約77ｇ得られる。 By vacuum drying this gel-like substance at 80°C in an evaporator, a granular material is obtained, which is finely powdered in a mortar and has a ruthenium content of 2% by weight and a copper content of 2% by weight.
Approximately 77 g of 0.2% by weight silica gel (A) is obtained.
実施例 １
前記で得たルテニウム含量２重量％、銅0.2重
量％のシリカゲル２ｇを毎時６の水素気流中
400℃で８時間還元処理し活性化した。Example 1 2 g of the silica gel with a ruthenium content of 2% by weight and a copper content of 0.2% by weight obtained above was added to a hydrogen stream of 6% per hour.
It was activated by reduction treatment at 400°C for 8 hours.
次に、内容積500mlのオートクレーブに、ベン
ゼン160ml、水100mlを仕込み、さらに前記の活性
化したルテニウム銅含有シリカゲル２ｇを加えた
後、容器内部空間を十分に水素ガスと置換し、水
素圧力70Kg／cm2、温度180℃の条件下で反応を行
つた。この場合、電磁誘導回転式により、800回
転／分で撹拌を行つた。反応荷を適宜抜出してガ
スクロマトグラフイーで、分析した結果、反応時
間１時間で、ベンゼン転化率76.5モル％、シクロ
ヘキセン収率29.4％の成績を得た。 Next, in an autoclave with an internal volume of 500 ml, 160 ml of benzene and 100 ml of water were charged, and after adding 2 g of the activated ruthenium copper-containing silica gel, the interior space of the container was sufficiently replaced with hydrogen gas, and the hydrogen pressure was 70 kg/ The reaction was carried out under conditions of cm 2 and temperature of 180°C. In this case, stirring was performed at 800 revolutions/minute using an electromagnetic induction rotation system. As a result of appropriately extracting the reaction charge and analyzing it by gas chromatography, a benzene conversion rate of 76.5 mol% and a cyclohexene yield of 29.4% were obtained in a reaction time of 1 hour.
比較例
実施例１において、ルテニウム含量２重量％銅
0.2重量％の本発明によるシリカゲル触媒の代り
に、同様の方法で調製した銅の含有しない、ルテ
ニウム含量２重量％シリカゲルを用いた以外は同
様にして実験を行つた。その結果、ベンゼン転化
率68.3モル％におけるシクロヘキセン収率は26.9
モル％であり、本発明の反応成績に比較して著し
く劣つたものであつた。このことから、本発明に
よるケイ素アルコキシドの加水分解生成物から誘
導されたシリカゲル中に分散されたルテニウム銅
触媒は、部分核水素化に対する触媒としてすぐれ
た効果を示すことがわかる。Comparative Example In Example 1, copper with a ruthenium content of 2% by weight
Experiments were carried out in the same manner, except that instead of 0.2% by weight of the silica gel catalyst according to the invention, a copper-free silica gel with a ruthenium content of 2% by weight, prepared in a similar manner, was used. As a result, the cyclohexene yield was 26.9 at a benzene conversion rate of 68.3 mol%.
% by mole, which was significantly inferior to the reaction results of the present invention. This shows that the ruthenium copper catalyst dispersed in silica gel derived from the hydrolysis product of silicon alkoxide according to the present invention exhibits excellent effects as a catalyst for partial nuclear hydrogenation.
Claims (1)
素ガスと反応させて部分核水素化する方法におい
て、核水素化触媒として、シリカゲル中に分散さ
れたルテニウム・銅触媒を用いると共に、反応系
にアルキルリン酸エステルを存在指せたことを特
徴とするベンゼンの部分核水素化法。1 In a method of partially nuclear hydrogenating benzene by reacting it with hydrogen gas in the presence of water and a hydrogenation catalyst, a ruthenium/copper catalyst dispersed in silica gel is used as the nuclear hydrogenation catalyst, and a ruthenium/copper catalyst dispersed in silica gel is used. A method for partial nuclear hydrogenation of benzene, which is characterized by being able to identify the presence of alkyl phosphate esters.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP59058656A JPS60202829A (en) | 1984-03-26 | 1984-03-26 | Method for partial nuclear hydrogenation of aromatic hydrocarbon |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP59058656A JPS60202829A (en) | 1984-03-26 | 1984-03-26 | Method for partial nuclear hydrogenation of aromatic hydrocarbon |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS60202829A JPS60202829A (en) | 1985-10-14 |
| JPH0229053B2 true JPH0229053B2 (en) | 1990-06-27 |
Family
ID=13090629
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP59058656A Granted JPS60202829A (en) | 1984-03-26 | 1984-03-26 | Method for partial nuclear hydrogenation of aromatic hydrocarbon |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS60202829A (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5180871A (en) * | 1987-11-11 | 1993-01-19 | Mitsui Petrochemical Industries, Ltd. | Process for producing phenols |
| DE19735770C1 (en) * | 1997-08-18 | 1999-05-27 | Bayer Ag | Process for the preparation of diaryl carbonates |
-
1984
- 1984-03-26 JP JP59058656A patent/JPS60202829A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS60202829A (en) | 1985-10-14 |
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