JPS60202829A - Method for partial nuclear hydrogenation of aromatic hydrocarbon - Google Patents
Method for partial nuclear hydrogenation of aromatic hydrocarbonInfo
- Publication number
- JPS60202829A JPS60202829A JP59058656A JP5865684A JPS60202829A JP S60202829 A JPS60202829 A JP S60202829A JP 59058656 A JP59058656 A JP 59058656A JP 5865684 A JP5865684 A JP 5865684A JP S60202829 A JPS60202829 A JP S60202829A
- Authority
- JP
- Japan
- Prior art keywords
- catalyst
- ruthenium
- aromatic hydrocarbon
- 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.)
- Granted
Links
- 150000004945 aromatic hydrocarbons Chemical class 0.000 title claims abstract description 17
- 238000000034 method Methods 0.000 title claims abstract description 17
- 238000005984 hydrogenation reaction Methods 0.000 title claims abstract description 15
- 239000003054 catalyst Substances 0.000 claims abstract description 24
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000000741 silica gel Substances 0.000 claims abstract description 13
- 229910002027 silica gel Inorganic materials 0.000 claims abstract description 13
- -1 silicon alkoxide Chemical class 0.000 claims abstract description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 11
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 10
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 9
- 239000010703 silicon Substances 0.000 claims abstract description 9
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims description 15
- 229910052707 ruthenium Inorganic materials 0.000 claims description 15
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 7
- 229910052802 copper Inorganic materials 0.000 claims description 7
- 239000010949 copper Substances 0.000 claims description 7
- 230000007062 hydrolysis Effects 0.000 claims description 4
- 238000006460 hydrolysis reaction Methods 0.000 claims description 4
- 238000006243 chemical reaction Methods 0.000 abstract description 15
- HGCIXCUEYOPUTN-UHFFFAOYSA-N cyclohexene Chemical compound C1CCC=CC1 HGCIXCUEYOPUTN-UHFFFAOYSA-N 0.000 abstract description 9
- 239000000126 substance Substances 0.000 abstract description 7
- 239000005749 Copper compound Substances 0.000 abstract description 5
- 150000001880 copper compounds Chemical class 0.000 abstract description 5
- 150000003304 ruthenium compounds Chemical class 0.000 abstract description 5
- 238000003756 stirring Methods 0.000 abstract description 5
- XCEAGAJKBRACAD-UHFFFAOYSA-N [Cu].[Ru] Chemical compound [Cu].[Ru] XCEAGAJKBRACAD-UHFFFAOYSA-N 0.000 abstract description 4
- 238000010438 heat treatment Methods 0.000 abstract description 3
- 239000001257 hydrogen Substances 0.000 abstract description 3
- 229910052739 hydrogen Inorganic materials 0.000 abstract description 3
- 239000002994 raw material Substances 0.000 abstract description 3
- 150000005846 sugar alcohols Polymers 0.000 abstract description 3
- 150000001875 compounds Chemical class 0.000 abstract description 2
- 238000001035 drying Methods 0.000 abstract 1
- 239000000463 material Substances 0.000 abstract 1
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 12
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 6
- 239000000243 solution Substances 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 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
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 150000004678 hydrides Chemical class 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 150000003303 ruthenium Chemical class 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
- 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
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- YBCAZPLXEGKKFM-UHFFFAOYSA-K ruthenium(iii) chloride Chemical compound [Cl-].[Cl-].[Cl-].[Ru+3] YBCAZPLXEGKKFM-UHFFFAOYSA-K 0.000 description 2
- IYWJIYWFPADQAN-LNTINUHCSA-N (z)-4-hydroxypent-3-en-2-one;ruthenium Chemical compound [Ru].C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O IYWJIYWFPADQAN-LNTINUHCSA-N 0.000 description 1
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- UZIBPOIXTCIHBH-UHFFFAOYSA-N 1-chlorohex-1-ene Chemical compound CCCCC=CCl UZIBPOIXTCIHBH-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
- 101100494773 Caenorhabditis elegans ctl-2 gene Proteins 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical class [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 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
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-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
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 229910000831 Steel Inorganic materials 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
- 239000002253 acid Substances 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 150000001298 alcohols Chemical class 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
- 125000003118 aryl group Chemical group 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 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
- HISOCSRUFLPKDE-KLXQUTNESA-N cmt-2 Chemical compound C1=CC=C2[C@](O)(C)C3CC4C(N(C)C)C(O)=C(C#N)C(=O)[C@@]4(O)C(O)=C3C(=O)C2=C1O HISOCSRUFLPKDE-KLXQUTNESA-N 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 229910000152 cobalt phosphate Inorganic materials 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
- 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
- 239000008187 granular material Substances 0.000 description 1
- FBAFATDZDUQKNH-UHFFFAOYSA-M iron chloride Chemical compound [Cl-].[Fe] FBAFATDZDUQKNH-UHFFFAOYSA-M 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000004570 mortar (masonry) Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000010298 pulverizing process 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
- 150000003839 salts Chemical class 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000010959 steel 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)
Abstract
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ｒｔｉ 、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、？のＦＰｒ外、を禾
匍用什索査の部へ眩索査什物のお造は困難であり、芳香
族炭化水素を通常の方法で水素化すると、芳香核は部分
水素化されずに完全水素化され、シクロパラフィンを与
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 create a product other than FPr, and when aromatic hydrocarbons are hydrogenated by the usual method, the aromatic nucleus is not partially hydrogenated but completely hydrogenated. to give cycloparaffins.
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, methods for such partial nuclear hydrogenation include:
A method of hydrogenation using liquid ammonia as a solvent in the presence of an alkali metal (West German Patent Nos. 1443377 and 1793757) is known. Although this method gives relatively good yields 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（％開昭５３−４６９３８号、５３−
６５８４９号、５３−６３３５０号等）。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 perspective (% 1983-46938, 53-
No. 65849, No. 53-63350, etc.).
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
得るものではなかった。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った。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１．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
分散さね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１、
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。That is, according to the present invention, in the method of partially hydrogenating an aromatic hydrocarbon by reacting it with hydrogen gas in the presence of water and a hydrogenation catalyst, 1. A method for partial nuclear hydrogenation of aromatic hydrocarbons is provided, which is characterized by using a ruthenium copper catalyst dispersed in silica gel derived from a hydrolysis product of silicon alkoxide. As catalysts, they were derived from hydrolysis products of silicon alkoxides. It is characterized by using a ruthenium/copper catalyst dispersed in silica gel.
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。The catalyst used in the present invention is produced by utilizing the gelling effect of the silicon alkoxide hydrolyzate.
例えば、−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攪拌する。この加熱
攪拌操作により、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。For example, water is added to an organic solvent solution in which a silicon alkoxide derived from a -hydric 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.
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
。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ｄ、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、フェ
ナンスロリン、ビピリジル等のキレート化剤と結合した
ルテニウムアンミツｇ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
テニウムアルコギ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、フロピレンゲリコール、クリセリン等ノ多価アル
コール、アセチルアセトン等の極性有機シ末媒に溶解さ
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。The organic solvent solution of the ruthenium compound includes d, ruthenium salts such as ruthenium chloride and ruthenium bromide, ruthenium acetylacetonate, etc., as well as ruthenium ammitsuganate bonded with a chelating agent such as ethylenediamine, phenanthroline, bipyridyl, and carbonyl. Ruthenium complexes, organic ruthenium complexes such as lute and nocene, or ruthenium compounds such as ruthenium alkogides are mixed with monohydric alcohols such as methanol and ethanol, polyhydric alcohols such as ethylene glycol, phlopylene gellicol, and chrycerin, and acetylacetone. A solution dissolved in a polar organic powder medium 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、ルテニウム相持量は、金属換算で
０．０１〜５０重搦係、重相しくけ０１〜２゜重相％、
銅担持量は金属換算でルテニウム相持量の２−２００重
量部ある。In the ruthenium/copper catalyst dispersed in the silica gel used in the present invention, the amount of ruthenium supported in terms of metal is 0.01 to 50 heavy phase ratio, 01 to 2° heavy phase ratio,
The amount of copper supported is 2-200 parts 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°Ｃ１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°C, preferably 200 to 600°C.
It is ℃. 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って実施され
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重葉部、好ましくは０１〜５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重量襲、好ましくり０，１〜１重量％であ
る。反応温度は０〜３００°Ｃ１好ましくは５０〜２２
０℃であり、反応圧力は０．０１〜５００ｋｇ／ＣＴＬ
２、好ましくは１〜２００ｋｇ／ｌｓ２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 01 to 5 parts by weight, per 1 part by weight of the aromatic hydrocarbon, and the amount of catalyst used is 0
．． 0.01 to 50% by weight, preferably 0.1 to 1% by weight. The reaction temperature is 0 to 300°C, preferably 50 to 22°C.
0℃, reaction pressure 0.01-500kg/CTL
2, preferably 1 to 200 kg/ls2.
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、補助添す口吻、例えば
、リン酸コバルｌ−１＋ｉｍコバルト、塩化二ソケル、
塩化鉄などの金属塩やＮ ａ Ｏ］−１、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
ンきキサン、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。本発明で原町とし
て用いる芳香族炭化水素の具体例と１〜では、例えば、
ベンゼン、トルエン、キシレン等が挙ケラれる。When carrying out the method of the present invention, the reaction can be carried out continuously or batchwise, and if necessary, auxiliary additives such as cobalt phosphate l-1+im cobalt, disokel chloride,
Metal salts such as iron chloride, alkalis such as NaO]-1, KOH, and acids 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 xane, dimethylformamide, and dimethyl sulfoxide can be used. Specific examples of aromatic hydrocarbons used as Haramachi in the present invention and 1 to 1 include, for example,
Examples include benzene, toluene, xylene, etc.
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ィ
ーで分析してそ扛ぞれ指定する物質について次式によっ
てめた値である。It should be noted that the conversion rates and selectivities shown in the Examples are values determined by the following equations for each designated substance by analyzing the organic liquid layer produced by the reaction by gas chromatography.
八
転化率（モル％）＝ （１−（−））ｘ１００３
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（モル係） −Ｃ
１−（−））ｘｌｏ。Eight conversion rate (mol%) = (1-(-)) x 1003 A... Number of moles of aromatic hydrocarbon in the reaction solution B...
... Raw material aromatic hydrocarbon mole selectivity (mole ratio) -C
1-(-))xlo.
Ｄ
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１００ｍ１を加えて６０℃
で２時間攪拌する。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．］
、９を加えて６０℃で２時間攪拌する。この混合溶液に
、水１００ ｍｌを加えて６０°Ｃで１０〜４８時間攪
拌を続けると、黒縁色のゲル状の物質が生成してくる。D 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 to 60°C.
Stir for 2 hours. Add silicon tetraethoxide (
(tetraethyl silicate) 132.5g, cuprous chloride 0. ]
, 9 and 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 gel-like substance with a black border is formed.
このゲル状物質をエバポレーターで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重量裂銅含量０２重量俤のシリカ
ゲル（Ａ、）約７７９得られる。By vacuum drying this gel-like substance at 80°C in an evaporator, a granular material is obtained, and by pulverizing this in a mortar, a silica gel (A,) with a ruthenium content of 2 weights and a copper content of 0.2 weights is obtained. .
実施例１
前記で得たルテニウム含量２重置部、銅０．２重置部の
シリカゲル２ｇを毎時６１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 obtained above in which the ruthenium content was double stacked and the copper content was 0.2 stacked was activated by reduction treatment at 400° C. for 8 hours in a hydrogen flow of 61/hr.
次に、内容積５００１１１１１！のオートクレーブに、
ベンゼン１６０ ｍｌ、水１００ ｍｌ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（−１
水素圧力フ０ｋｇ／ｃｍｔ２、温度１．８０℃の条件下
で反応を行った。この場合、電磁誘導回転式により、８
００回転／分で攪拌を行った。反応液を適宜抜出してガ
スクロマトグラフィーで、分析した結果、反応時間１時
間で、ベンゼン転化率７６５モル係、／クロヘキセン収
率２９．４％の成績を得た。Next, the internal volume is 50011111! In the autoclave of
After charging 160 ml of benzene and 100 ml of water and further adding 2 g of the activated ruthenium copper-containing silica gel, the inner space of the container was sufficiently replaced with hydrogen gas (-1
The reaction was carried out under the conditions of a hydrogen pressure of 0 kg/cmt2 and a temperature of 1.80°C. In this case, by electromagnetic induction rotation type, 8
Stirring was performed at 00 revolutions/min. The reaction solution was extracted as appropriate and analyzed by gas chromatography. As a result, a benzene conversion rate of 765 mol and a chlorohexene yield of 29.4% were obtained in 1 hour of reaction time.
比較例
実施例１において、ルテニウム含量２重量φ鋼０．２重
置部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重量係
シリカゲルを用いた以外は同様にして実験を行った。そ
の結果、ベンゼン転化率６８．３モル係におけるシクロ
ヘキセン収率は２６．９モル係であり、本発明の反応族
ＭＫ比較して著しく劣ったものであった。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-free silica gel with a ruthenium content of 2 weight, which was prepared in the same manner, was used instead of the silica gel catalyst according to the present invention in the overlapping part of the ruthenium content of 2 weight φ steel. conducted an experiment in the same manner. As a result, the cyclohexene yield at a benzene conversion rate of 68.3 moles was 26.9 moles, which was significantly inferior to the reaction group MK of the present invention. This shows that the ruthenium copper catalyst derived from the hydrolysis product of silicon alkoxide and dispersed in silica gel according to the present invention exhibits excellent effects as a catalyst for partial nuclear hydrogenation.
Claims (1)
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。(11 aromatic hydrocarbons in the presence of water and a hydrogenation catalyst,
In the method of partial nuclear hydrogenation by reacting with hydrogen gas,
A method for partial nuclear hydrogenation of aromatic hydrocarbons, characterized in that a ruthenium/copper catalyst dispersed in silica gel derived from a hydrolysis product of silicon alkoxide is used as the hydrogenation catalyst.
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 true JPS60202829A (en) | 1985-10-14 |
| JPH0229053B2 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) |
Cited By (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 |
| WO1999008787A1 (en) * | 1997-08-18 | 1999-02-25 | Bayer Aktiengesellschaft | Catalysts containing a platinum group metal and produced in a sol-gel method, as well as method for producing diarylcarbonates |
-
1984
- 1984-03-26 JP JP59058656A patent/JPS60202829A/en active Granted
Cited By (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 |
| WO1999008787A1 (en) * | 1997-08-18 | 1999-02-25 | Bayer Aktiengesellschaft | Catalysts containing a platinum group metal and produced in a sol-gel method, as well as method for producing diarylcarbonates |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0229053B2 (en) | 1990-06-27 |
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