JPS641452B2 - - Google Patents
Info
- Publication number
- JPS641452B2 JPS641452B2 JP61149253A JP14925386A JPS641452B2 JP S641452 B2 JPS641452 B2 JP S641452B2 JP 61149253 A JP61149253 A JP 61149253A JP 14925386 A JP14925386 A JP 14925386A JP S641452 B2 JPS641452 B2 JP S641452B2
- Authority
- JP
- Japan
- Prior art keywords
- mmol
- ethylene glycol
- reaction
- ethanol
- methanol
- 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
Links
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 168
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 95
- 238000006243 chemical reaction Methods 0.000 claims description 45
- 239000003054 catalyst Substances 0.000 claims description 15
- 229910052703 rhodium Inorganic materials 0.000 claims description 9
- 239000010948 rhodium Substances 0.000 claims description 9
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 claims description 9
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims description 7
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 7
- 229910002091 carbon monoxide Inorganic materials 0.000 claims description 7
- 239000001257 hydrogen Substances 0.000 claims description 7
- 229910052739 hydrogen Inorganic materials 0.000 claims description 7
- RWRDLPDLKQPQOW-UHFFFAOYSA-N Pyrrolidine Chemical compound C1CCNC1 RWRDLPDLKQPQOW-UHFFFAOYSA-N 0.000 claims description 6
- 125000000217 alkyl group Chemical group 0.000 claims description 6
- 238000004519 manufacturing process Methods 0.000 claims description 6
- 125000002768 hydroxyalkyl group Chemical group 0.000 claims description 4
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 2
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 90
- TZIHFWKZFHZASV-UHFFFAOYSA-N methyl formate Chemical compound COC=O TZIHFWKZFHZASV-UHFFFAOYSA-N 0.000 description 46
- 230000007306 turnover Effects 0.000 description 22
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 20
- 239000007789 gas Substances 0.000 description 19
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 18
- AVFZOVWCLRSYKC-UHFFFAOYSA-N 1-methylpyrrolidine Chemical compound CN1CCCC1 AVFZOVWCLRSYKC-UHFFFAOYSA-N 0.000 description 15
- AHVYPIQETPWLSZ-UHFFFAOYSA-N N-methyl-pyrrolidine Natural products CN1CC=CC1 AHVYPIQETPWLSZ-UHFFFAOYSA-N 0.000 description 15
- 238000000034 method Methods 0.000 description 14
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 12
- DNIAPMSPPWPWGF-GSVOUGTGSA-N (R)-(-)-Propylene glycol Chemical compound C[C@@H](O)CO DNIAPMSPPWPWGF-GSVOUGTGSA-N 0.000 description 9
- 239000007795 chemical reaction product Substances 0.000 description 9
- 235000011187 glycerol Nutrition 0.000 description 9
- DNIAPMSPPWPWGF-UHFFFAOYSA-N monopropylene glycol Natural products CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 9
- 229960004063 propylene glycol Drugs 0.000 description 9
- 235000013772 propylene glycol Nutrition 0.000 description 9
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 8
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 8
- 239000000047 product Substances 0.000 description 7
- ZUHZGEOKBKGPSW-UHFFFAOYSA-N tetraglyme Chemical compound COCCOCCOCCOCCOC ZUHZGEOKBKGPSW-UHFFFAOYSA-N 0.000 description 7
- 150000001298 alcohols Chemical class 0.000 description 6
- 238000004587 chromatography analysis Methods 0.000 description 6
- 150000003235 pyrrolidines Chemical class 0.000 description 6
- IQTWKCSNWONACC-UHFFFAOYSA-N 1-octylpyrrolidine Chemical compound CCCCCCCCN1CCCC1 IQTWKCSNWONACC-UHFFFAOYSA-N 0.000 description 5
- 239000003085 diluting agent Substances 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- LVGLLYVYRZMJIN-UHFFFAOYSA-N carbon monoxide;rhodium Chemical group [Rh].[Rh].[Rh].[Rh].[O+]#[C-].[O+]#[C-].[O+]#[C-].[O+]#[C-].[O+]#[C-].[O+]#[C-].[O+]#[C-].[O+]#[C-].[O+]#[C-].[O+]#[C-].[O+]#[C-].[O+]#[C-] LVGLLYVYRZMJIN-UHFFFAOYSA-N 0.000 description 4
- 238000004817 gas chromatography Methods 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- XBRDBODLCHKXHI-UHFFFAOYSA-N epolamine Chemical compound OCCN1CCCC1 XBRDBODLCHKXHI-UHFFFAOYSA-N 0.000 description 3
- 239000003446 ligand Substances 0.000 description 3
- 239000007791 liquid phase Substances 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- IGNTWNVBGLNYDV-UHFFFAOYSA-N triisopropylphosphine Chemical compound CC(C)P(C(C)C)C(C)C IGNTWNVBGLNYDV-UHFFFAOYSA-N 0.000 description 3
- MBVAQOHBPXKYMF-LNTINUHCSA-N (z)-4-hydroxypent-3-en-2-one;rhodium Chemical compound [Rh].C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O MBVAQOHBPXKYMF-LNTINUHCSA-N 0.000 description 2
- ZFPGARUNNKGOBB-UHFFFAOYSA-N 1-Ethyl-2-pyrrolidinone Chemical compound CCN1CCCC1=O ZFPGARUNNKGOBB-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 2
- WAIPAZQMEIHHTJ-UHFFFAOYSA-N [Cr].[Co] Chemical compound [Cr].[Co] WAIPAZQMEIHHTJ-UHFFFAOYSA-N 0.000 description 2
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical compound CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 description 2
- -1 alkali metal salts Chemical class 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 239000007798 antifreeze agent Substances 0.000 description 2
- 239000007810 chemical reaction solvent Substances 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- NNBZCPXTIHJBJL-UHFFFAOYSA-N decalin Chemical compound C1CCCC2CCCCC21 NNBZCPXTIHJBJL-UHFFFAOYSA-N 0.000 description 2
- 229910001873 dinitrogen Inorganic materials 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 150000002460 imidazoles Chemical class 0.000 description 2
- 230000006698 induction Effects 0.000 description 2
- 125000001477 organic nitrogen group Chemical group 0.000 description 2
- XYFCBTPGUUZFHI-UHFFFAOYSA-N phosphine group Chemical group P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 2
- 150000003284 rhodium compounds Chemical class 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- POILWHVDKZOXJZ-ARJAWSKDSA-M (z)-4-oxopent-2-en-2-olate Chemical compound C\C([O-])=C\C(C)=O POILWHVDKZOXJZ-ARJAWSKDSA-M 0.000 description 1
- CYSGHNMQYZDMIA-UHFFFAOYSA-N 1,3-Dimethyl-2-imidazolidinon Chemical compound CN1CCN(C)C1=O CYSGHNMQYZDMIA-UHFFFAOYSA-N 0.000 description 1
- VIESAWGOYVNHLV-UHFFFAOYSA-N 1,3-dihydropyrrol-2-one Chemical class O=C1CC=CN1 VIESAWGOYVNHLV-UHFFFAOYSA-N 0.000 description 1
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- KZEVSDGEBAJOTK-UHFFFAOYSA-N 1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-2-[5-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]-1,3,4-oxadiazol-2-yl]ethanone Chemical compound N1N=NC=2CN(CCC=21)C(CC=1OC(=NN=1)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)=O KZEVSDGEBAJOTK-UHFFFAOYSA-N 0.000 description 1
- DURPTKYDGMDSBL-UHFFFAOYSA-N 1-butoxybutane Chemical compound CCCCOCCCC DURPTKYDGMDSBL-UHFFFAOYSA-N 0.000 description 1
- MNZAKDODWSQONA-UHFFFAOYSA-N 1-dibutylphosphorylbutane Chemical compound CCCCP(=O)(CCCC)CCCC MNZAKDODWSQONA-UHFFFAOYSA-N 0.000 description 1
- JVCRHTKQAPRUKG-UHFFFAOYSA-N 1-dodecylpyrrolidine Chemical compound CCCCCCCCCCCCN1CCCC1 JVCRHTKQAPRUKG-UHFFFAOYSA-N 0.000 description 1
- FYVMBPXFPFAECB-UHFFFAOYSA-N 2-(1-methylpyrrolidin-2-yl)ethanol Chemical compound CN1CCCC1CCO FYVMBPXFPFAECB-UHFFFAOYSA-N 0.000 description 1
- LDXJRKWFNNFDSA-UHFFFAOYSA-N 2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-1-[4-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]piperazin-1-yl]ethanone Chemical compound C1CN(CC2=NNN=C21)CC(=O)N3CCN(CC3)C4=CN=C(N=C4)NCC5=CC(=CC=C5)OC(F)(F)F LDXJRKWFNNFDSA-UHFFFAOYSA-N 0.000 description 1
- 125000000954 2-hydroxyethyl group Chemical group [H]C([*])([H])C([H])([H])O[H] 0.000 description 1
- RAPTZNFAMIHBTG-UHFFFAOYSA-N 3-methyl-1-pyrrolidin-1-ylbutan-1-one Chemical compound CC(C)CC(=O)N1CCCC1 RAPTZNFAMIHBTG-UHFFFAOYSA-N 0.000 description 1
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 239000007983 Tris buffer Substances 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- GPMUMMNTAZMBEC-UHFFFAOYSA-N bis(oxomethylidene)rhodium Chemical compound [Rh].[O+]#[C-].[O+]#[C-] GPMUMMNTAZMBEC-UHFFFAOYSA-N 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 235000013877 carbamide Nutrition 0.000 description 1
- GGRQQHADVSXBQN-FGSKAQBVSA-N carbon monoxide;(z)-4-hydroxypent-3-en-2-one;rhodium Chemical compound [Rh].[O+]#[C-].[O+]#[C-].C\C(O)=C\C(C)=O GGRQQHADVSXBQN-FGSKAQBVSA-N 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000003245 coal Substances 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
- 150000003983 crown ethers Chemical class 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 239000000295 fuel oil Substances 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 150000007975 iminium salts Chemical class 0.000 description 1
- 229910001026 inconel Inorganic materials 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- AUONHKJOIZSQGR-UHFFFAOYSA-N oxophosphane Chemical compound P=O AUONHKJOIZSQGR-UHFFFAOYSA-N 0.000 description 1
- SJLOMQIUPFZJAN-UHFFFAOYSA-N oxorhodium Chemical compound [Rh]=O SJLOMQIUPFZJAN-UHFFFAOYSA-N 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- DLRJIFUOBPOJNS-UHFFFAOYSA-N phenetole Chemical compound CCOC1=CC=CC=C1 DLRJIFUOBPOJNS-UHFFFAOYSA-N 0.000 description 1
- 229910000073 phosphorus hydride Inorganic materials 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 229910003450 rhodium oxide Inorganic materials 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- PXXNTAGJWPJAGM-UHFFFAOYSA-N vertaline Natural products C1C2C=3C=C(OC)C(OC)=CC=3OC(C=C3)=CC=C3CCC(=O)OC1CC1N2CCCC1 PXXNTAGJWPJAGM-UHFFFAOYSA-N 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
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Description
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ãããDETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention relates to a method for efficiently producing alcohols such as ethylene glycol and ethanol from carbon monoxide and hydrogen by a liquid phase reaction.
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ãããå·¥æ¥çã«éèŠãªåºç€ååŠåã§ããã Ethylene glycol is a raw material for polyester,
Ethanol is used as an antifreeze agent, etc. Ethanol is used as a solvent, fuel, antifreeze agent, and various chemical raw materials, and may also be used as a raw material for ethylene, all of which are industrially important basic chemicals.
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Traditionally, these two-carbon alcohols ( C2 alcohols) have been produced primarily from petroleum, but in recent years, with the aim of diversifying chemical raw materials, they have been produced from carbon sources such as coal, natural gas, and heavy oil. This kind of gas is produced from easily obtained carbon monoxide and hydrogen.
The development of technology to produce C2 alcohol has become an important issue.
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ãŠããã A method for producing C2 alcohols such as ethylene glycol and ethanol from carbon monoxide and hydrogen through a liquid phase reaction is a method using a cobalt catalyst (US Pat. No. 2,534,018, US Pat. No. 2,636,046, etc.). ), method using ruthenium catalyst (U.S. Pat. No. 4,170,605, JP-A-Sho
55-115834, JP 57-109735, etc.)
Also, methods using rhodium catalysts have been proposed.
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ãã€ã³ã䜿çšããæ¹æ³ãèšèŒãããŠããã Many proposals have already been made regarding methods using rhodium catalysts, including quaternary ammonium salts (Japanese Unexamined Patent Publication No. 51-32506), alkali metal salts (Japanese Unexamined Patent Publication No. 51-36403), and bis-catalysts. (Tertiary phosphine) iminium salt (JP-A-51-63110
There is a method of adding such as Also,
A method of adding organic nitrogen ligands was published in 1972.
This method has been proposed in JP-A No. 42809, Japanese Patent Laid-Open No. 52-42810, etc. In this case, it has also been proposed to use imidazoles as organic nitrogen ligands (Japanese Unexamined Patent Publication No. 170022/1983). Furthermore, JP-A-55-9065
The publication describes a method of coexisting phosphine oxide. Further, JP-A-60-136524 and JP-A-60-149537 describe methods using trialkylphosphines.
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However, the above method has a problem in that the production activity of C 2 alcohol per catalyst metal [turnover number: number of moles of product/(g-atom catalyst metal/reaction time)] is low.
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ãå®å®æ§ã®ç¹ã§æªã æºè¶³ãåŸããã®ã§ã¯ãªãã In addition, in the direct synthesis of ethylene glycol, methanol, methyl formate, ethanol, etc. are produced as by-products in addition to ethylene glycol, but in the conventional method,
As shown in Japanese Unexamined Patent Publication No. 59-170022, etc., there is a problem that a large amount of methanol with low added value is produced. There is a practical need to improve the selectivity of two alcohols. In addition, when using a rhodium catalyst, it is important to use a ligand with good stability, and in the case of the imidazoles mentioned above, since they have unsaturated bonds in their molecules, they are still unstable in terms of stability. It's not something I can be satisfied with.
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As a result of extensive research to overcome the above problems, the present inventors discovered that by allowing pyrrolidines to exist in the reaction system when reacting carbon monoxide and hydrogen using a catalyst containing rhodium, The present inventors have discovered that specific high catalytic activity and selectivity that could not be expected from the results of conventional methods have been achieved.
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žåççŽ ãšæ°ŽçŽ ãåå¿ãããéã«åå¿ç³»ã«ãããª
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ãããã®ã§ããã That is, the present invention provides a method for producing ethylene glycol and ethanol, which is characterized by using a rhodium-containing catalyst and allowing pyrrolidines to be present in the reaction system when carbon monoxide and hydrogen are reacted.
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çºæã®æ矩ã¯å€§ããã According to the present invention, C 2 alcohols such as ethylene glycol and ethanol can be produced with high selectivity from synthesis gas by liquid phase reaction, so the present invention has great significance.
以äžã«æ¬çºæã詳现ã«èª¬æããã The present invention will be explained in detail below.
æ¬çºæã§äœ¿çšãããããªãžã³é¡ã¯åŒ(1)ã§ç€ºãã
ãã The pyrrolidines used in the present invention are represented by formula (1).
ããã§ïŒ²ã¯ã¡ãã«ããšãã«ãããã«ããªã¯ã
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ãããããã·ã¢ã«ãã«åºã§ããããŸãRâ²ã¯ïŒšã
ã¢ã«ãã«åºåã¯ããããã·ã¢ã«ãã«åºã§ããã Here, R is an alkyl group such as methyl, ethyl, butyl, octyl, dodecyl, 2-hydroxyethyl, or a hydroxyalkyl group in which a part of the alkyl group is substituted with an OH group. Also, Râ² is H,
It is an alkyl group or a hydroxyalkyl group.
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žåççŽ ãšæ°ŽçŽ ã®ã¢ã«æ¯
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ããã The molar ratio of carbon monoxide and hydrogen used in the present invention is usually CO: H2 = 1:10 to 5:1, preferably in the range of 1:4 to 2:1. The pressure of this mixed gas (synthesis gas) is 250Kg/cm 2 to 3000Kg/cm 2
Preferably it is in the range of 300Kg/cm 2 to 2000Kg/cm 2 .
The pyrrolidines of the present invention can be used as reaction solvents. It can also be used after being diluted with a suitable diluent. As the diluent, those commonly used in this type of reaction can be used, but preferred diluents include benzene, toluene, xylene,
Hydrocarbons such as decalin, hexane, heptane and N
- pyrrolidones such as methylpyrrolidone, N-ethylpyrrolidone, alkyl ureas such as NN'-dimethylimidazolidinone, or tetrahydrofuran, crown ether, dioxane,
Examples include ethers such as dibutyl ether, ethyl phenyl ether, and tetraglyme.
These diluents can be used alone or as a mixture.
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以äžã§ããã Although any ratio of the pyrrolidines to the diluent can be used, the ratio of the pyrrolidines in the total solvent is usually 1 wt% or more, preferably 3 wt% or more.
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žåããžãŠã çãæããããã In the present invention, any rhodium compound or rhodium metal can be used as a catalyst as long as it can produce soluble active species under the reaction conditions.
Examples of rhodium compounds include tetrarhodium dodecacarbonyl, tris(acetylacetone)
Examples include rhodium, acetylacetonatodicarbonyl rhodium, rhodium oxide, and the like.
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ãã枩床ç¯å²ã¯180ã300âã§ããã The catalyst concentration in the reaction solvent is usually 0.01Ã10 -3 g-atom to 5 g per reaction solution in terms of metallic rhodium.
âatom range, preferably 0.1Ã10 â3 gâ
It ranges from atom to 1 g-atom. The reaction temperature is carried out in the range of 150 to 350°C, but the more preferable temperature range is 180 to 300°C.
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¬ç¥ã®æ¹æ³ã«ãã容æã«è¡ãããã The method of the present invention can be carried out in either batch or continuous reaction mode, and separation of the product and catalyst from the reaction solution can be easily carried out by known methods such as distillation and extraction. sell.
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詳现ã«èª¬æããã Next, the present invention will be explained in more detail with reference to Examples and Comparative Examples.
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ã§ãã€ããExample 1 7 ml of N-methylpyrrolidine and tetrarhodium dodecacarbonyl were placed in a nitrogen-purged autoclave with an internal volume of 20 ml (made of Inconel steel).
After charging 0.00625 mmol and replacing the inside of the reactor with a mixed gas of CO:H 2 = 1:1, a mixed gas of the same composition was pressurized and the reaction was carried out at 270°C for 1 hour under a constant pressure of 1800 kg/cm 2 . . After the reaction, the autoclave was cooled and the products were analyzed by gas chromatography, which revealed that 22.05 mmol of ethylene glycol, 10.02 mmol of ethanol, 1.13 mmol of methanol,
0.18 mmol of methyl formate was obtained. The turnover numbers of ethylene glycol and ethanol are 882 mol/(g-atomRh)h and 400 mol/h, respectively.
(g-atomRh)h. In addition, the selectivity for C 2 alcohol, which is a combination of ethylene glycol and ethanol, was 98%.
ããã§éžæçã¯æ¬¡åŒã®ãããªççŽ å¹çã§ç€ºã
ãã Here, the selectivity is expressed as carbon efficiency as shown in the following formula.
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ïŒïŒÃEGÃ100ïŒMeOHïŒMFïŒïŒÃEtOHïŒ2EG
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ã¿ããŒã«0.14ãåŸãããã«ãããªããEthylene glycol selectivity = 2 x EG x 100 / MeOH + MF + 2 x EtOH + 2EG Ethanol selectivity = 2 x EtOH x 100 / MeOH + MF + 2 x EtOH + 2EG MeOH: number of moles of ethanol produced, MF: number of moles of methyl formate produced, EtOH: number of moles of ethanol produced Number of moles produced, EG: Number of moles produced of ethylene glycol Comparative Example 1 When the reaction was carried out under the same conditions as in Example 1 except that 1-(3-methylbutyryl)pyrrolidine was used instead of N-methylpyrrolidine, ethylene glycol was 0.45%. Only 0.20 mmol of ethanol and 0.14 mmol of methanol were obtained.
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ããããªãã€ããComparative Example 2 A reaction was carried out under the same conditions as in Example 1 except that pyrrolidine was used instead of N-methylpyrrolidine, but no production of ethylene glycol and ethanol was observed.
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atomRhïŒïœãš10.8molïŒïŒïœâatomRhïŒïœã§ã
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ã§ãã€ããExample 2 A reaction was carried out under the same conditions as in Example 1 except that the reaction temperature was 230°C.
4.96 mmol of ethanol, 0.27 mmol of ethanol, 2.12 mmol of methanol and 0.09 mmol of methyl formate were obtained. The turnover numbers of ethylene glycol and ethanol are each 198 mol/(g-
atomRh)h and 10.8 mol/(g-atomRh)h. The selectivity for C2 alcohol was 82.6%.
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27.6molïŒïŒïœâatomRhïŒïœã§ãã€ããComparative Example 3 A reaction was carried out under the same conditions as in Example 2 except that 7 ml of N-methylpyrrolidone was used instead of 7 ml of N-methylpyrrolidine.
0.69 mmol and 0.14 mmol of methanol were obtained. The turnover number of ethylene glycol is
It was 27.6 mol/(g-atomRh)h.
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atomRhïŒïœã§ãã€ããExample 3 2 ml of 1-(2-hydroxyethyl)pyrrolidine,
5ml of toluene and tetrarhodium dodecacarbonyl
The reaction was carried out under the same conditions as in Example 1 except that 0.025 mmol was used and the reaction temperature was 230°C.
Ethylene glycol 5.80 mmol, ethanol
0.43 mmol, methanol 11.46 mmol and methyl formate 1.51 mmol were obtained. The turnover number of ethylene glycol is 58.0mol/(g-
atomRh)h.
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âatomRhïŒïœã§ãã€ããComparative example 4 1-(2-hydroxyethyl)pyrrolidine 2 ml
The same conditions as in Example 3 were used except that 7 ml of toluene was used instead of 5 ml of toluene. Ethylene glycol 0.14 mmol, methanol 7.55
3.15 mmol of methyl formate were obtained.
No production of ethanol was observed. The turnover number of ethylene glycol is 1.4mol/(g
-atomRh)h.
å®æœäŸ ïŒ
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žã¡ãã«0.24ããªã¢ã«ãåŸããããExample 4 A reaction was carried out under the same conditions as in Example 1 except that the reaction temperature was 250°C. In this case, the amount of ethylene glycol produced was 12.25 mmol, and the amount of ethanol produced was 2.06 mmol. The turnover number of ethylene glycol is 490mol/(g-
atomRh)h. Additionally, 1.47 mmol of methanol and 0.24 mmol of methyl formate were obtained.
å®æœäŸ ïŒ
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æéã¯8.69ããªã¢ã«ã§ããããšã¿ããŒã«ã®çæé
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ã€ããExample 5 A reaction was carried out under the same conditions as in Example 4, except that 7 ml of 1-methyl-2-pyrrolidine ethanol was used as the solvent. In this case, the amount of ethylene glycol produced was 8.69 mmol, and the amount of ethanol produced was 1.78 mmol. Additionally, 2.94 mmol of methanol and 0.14 mmol of methyl formate were obtained. The turnover number of ethylene glycol was 348.
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ïŒmlãçšããä»ã¯å®æœäŸïŒãšåæ§ã®æ¡ä»¶ã§åå¿ã
è¡ããšãã¬ã³ã°ãªã³ãŒã«0.30ããªã¢ã«ããšã¿ããŒ
ã«0.04ããªã¢ã«ãã¡ã¿ããŒã«0.36ããªã¢ã«ãåŸ
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12molïŒïŒïœâatomRhïŒïœã§ãã€ããComparative Example 5 A reaction was carried out under the same conditions as in Example 1, except that 2 ml of N-methylpyrrolidine and 5 ml of tributylphosphine oxide were used instead of 7 ml of N-methylpyrrolidine, and 0.30 mmol of ethylene glycol, 0.04 mmol of ethanol, and 0.36 mmol of methanol were used. Obtained. The turnover number of ethylene glycol is
It was 12 mol/(g-atomRh)h.
å®æœäŸ ïŒ
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ããExample 6 2 ml of 1-(2-hydroxyethyl)pyrrolidine
The reaction was carried out under the same conditions as in Comparative Example 5 except that 5 ml of N-ethylpyrrolidone and ethylene glycol were used.
6.00 mmol of ethanol, 3.8 mmol of ethanol, 1.71 mmol of methanol, and 0.11 mmol of methyl formate were obtained.
å®æœäŸ ïŒ
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ã«ä»èŸŒã¿ãå®æœäŸïŒãšåæ§ã®æ¹æ³ã§1800KgïŒcm2ã
230âã§ïŒæéåå¿ãè¡ã€ããšããããšãã¬ã³ã°
ãªã³ãŒã«6.69ãããªã¢ã«ããšã¿ããŒã«0.46ããªã¢
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ããŒæ°ã¯66.9molïŒïŒïœâatomRhïŒïœã§ãã€ããExample 7 7 ml of N-methylpyrrolidine and 0.025 mmol of tetrarhodium dodecacarbonyl were charged into an autoclave, and 1800 kg/cm 2 was prepared in the same manner as in Example 1.
When the reaction was carried out at 230°C for 1 hour, 6.69 mmol of ethylene glycol, 0.46 mmol of ethanol, 6.06 mmol of methanol, and 0.35 mmol of methyl formate were obtained. The turnover number of ethylene glycol was 66.9 mol/(g-atomRh)h.
å®æœäŸ ïŒ
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žã¡ãã«0.57ããªã¢ã«ãåŸãããšãã¬ã³ã°ãªã³
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ïŒãšæ¯ã¹C2ã¢ã«ã³ãŒã«ã®çæéãå¢å ãããExample 8 The reaction was carried out in the same manner as in Example 7 except that 6 ml of N-methylpyrrolidine was coexisting with 1 ml of N-methylpyrrolidone. 9.27 mmol of ethylene glycol, 1.23 mmol of ethanol, 10.53 mmol of methanol,
0.57 mmol of methyl formate was obtained. The turnover number of ethylene glycol was 92.7. Compared to Example 7, the amount of C 2 alcohol produced increased.
å®æœäŸ ïŒ
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ãšåæ§ã«åå¿ãè¡ããšãã¬ã³ã°ãªã³ãŒã«9.69ããª
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12.45ããªã¢ã«ãã®é
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ããExample 9 1 ml of N,N'-dimethylimidazolidinone was coexisted with 6 ml of N-methylpyrrolidine, and the rest was Example 7.
Carry out the reaction in the same manner as ethylene glycol 9.69 mmol, ethanol 2.10 mmol, methanol
12.45 mmol and 0.69 mmol of methyl formate were obtained.
Compared to Example 7, the amount of C 2 alcohol produced increased.
å®æœäŸ 10
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ã«ããšã¿ããŒã«0.92ããªã¢ã«ãã¡ã¿ããŒã«15.07
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žã¡ãã«0.95ããªã¢ã«ãåŸãããã
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99.0molïŒïŒïœâatomRhïŒïœã§ãã€ããExample 10 A reaction was carried out under the same conditions as in Example 3 except that 2 ml of N-methylpyrrolidine and 5 ml of tetrahydrofuran were used, resulting in 9.90 mmol of ethylene glycol, 0.92 mmol of ethanol, and 15.07 mmol of methanol.
0.95 mmol of methyl formate was obtained.
The turnover number of ethylene glycol is
It was 99.0 mol/(g-atomRh)h.
æ¯èŒäŸ ïŒ
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žã¡ãã«2.36ããªã¢ã«ãåŸ
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ã¯15.4molïŒïŒïœâatomRhïŒïœã§ãã€ããComparative Example 6 A reaction was carried out under the same conditions as in Example 10 except that 2 ml of N-methylpyrrolidine and 7 ml of tetrahydrofuran were used instead of 5 ml of tetrahydrofuran. 1.54 mmol of ethylene glycol, 10.33 mmol of methanol, and 2.36 mmol of methyl formate were obtained. Ta. The turnover number of ethylene glycol was 15.4 mol/(g-atomRh)h.
å®æœäŸ 11
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ãã®æé«å§åã¯çŽ500KgïŒcm2ã§ãã€ããExample 11 An autoclave (manufactured by Hastelloy C) equipped with a magnetic induction stirring device with an internal volume of 40 ml was purged with nitrogen gas, and 0.1 mmol of rhodium acetylacetonate (biscarbonyl), 0.5 mmol of triisopropylphosphine, and 2 ml of N-methylpyrrolidine were added. , 3 ml of tetraglyme was charged, and the gas was replaced with a mixed gas of CO:H 2 =1:1. Next, the autoclave was filled with a mixed gas of the same composition at 360 kg/cm 2 at room temperature, and the reaction was carried out for 1 hour from the time when the temperature of the reaction system reached 230°C. The maximum pressure when the reaction temperature was reached was about 500 Kg/cm 2 .
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ã«0.16ããªã¢ã«ãã¡ã¿ããŒã«4.62ããªã¢ã«ãã®é
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埮éã®ã¡ã¿ã³ãCO2ãæ€åºãããã At the end of the reaction, cool the autoclave to room temperature,
Analysis of the reaction products by gas chromatography revealed 3.46 mmol of ethylene glycol, 0.16 mmol of ethanol, 4.62 mmol of methanol, 0.14 mmol of methyl formate, trace amounts of 1,2-propanediol, glycerin, and trace amounts of methane and CO as gas products. 2 were detected.
ãšãã¬ã³ã°ãªã³ãŒã«ã®ã¿ãŒã³ãªãŒããŒæ°ã¯
34.5molïŒïŒïœâatomRhïŒïœã§ãã€ãã The turnover number of ethylene glycol is
It was 34.5 mol/(g-atomRh)h.
å®æœäŸ 12
å®æœäŸ11ã®æ¡ä»¶ã§æ··åã¬ã¹ã®å§åã宀枩ã§490
KgïŒcm2ã«å€æŽãã以å€ã¯åäžã®æ¡ä»¶ã§åå¿ãå®æœ
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çŽ685KgïŒcm2ã§ãã€ããExample 12 Under the conditions of Example 11, the pressure of the mixed gas was set to 490 at room temperature.
The reaction was carried out under the same conditions except that the amount was changed to Kg/cm 2 . The maximum pressure when the reaction temperature was reached was approximately 685 Kg/cm 2 .
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çæããã Gas chromatographic analysis of the reaction products revealed that 5.1 mmol of ethylene glycol, 0.20 mmol of ethanol, 3.88 mmol of methanol, 0.15 mmol of methyl formate, and trace amounts of 1,2-propanediol, glycerin, methane, and CO 2 were produced.
ãšãã¬ã³ã°ãªã³ãŒã«ã®ã¿ãŒã³ãªãŒããŒæ°ã¯
51.0molïŒïŒïœâatomRhïŒïœã§ãã€ãã The turnover number of ethylene glycol is
It was 51.0 mol/(g-atomRh)h.
å®æœäŸ 13
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ïŒæéåå¿ãè¡ã€ããExample 13 A reaction was carried out for 2 hours under the conditions of Example 11, except that N-n-octylpyrrolidine was used instead of N-methylpyrrolidine.
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ã«ã®ã¿ãŒã³ãªãŒããŒæ°28.3molïŒïŒïœâatomRhïŒ
ïœãåŸãããã Gas chromatographic analysis of the reaction products revealed 5.67 mmol of ethylene glycol, 0.13 mmol of ethanol, 4.31 mmol of methanol, 0.25 mmol of methyl formate, and trace amounts of 1,2-propanediol, glycerin, methane,
CO 2 etc. were detected. In addition, the turnover number of ethylene glycol is 28.3 mol/(g-atomRh)
h was obtained.
å®æœäŸ 14
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ã€ããExample 14 N-n-octylpyrrolidine under the conditions of Example 13
The reaction was carried out using 0.5 ml of tetraglyme and 4.5 ml of tetraglyme.
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ã³ãCO2ãªã©ãæ€åºãããã Gas chromatographic analysis of the reaction products revealed 4.75 mmol of ethylene glycol, 0.05 mmol of ethanol, 4.12 mmol of methanol, 0.34 mmol of methyl formate, and trace amounts of other products such as 1,2-propanediol, glycerin, methane, and CO2 . was detected.
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2.37molïŒïŒïœâatomRhïŒïœã§ãã€ãã The turnover number of ethylene glycol is
It was 2.37 mol/(g-atomRh)h.
å®æœäŸ 15
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枩床220âã§ïŒæéåå¿ãè¡ã€ããExample 15 In Example 13, 2 ml of N-n-dodecylpyrrolidine was used instead of N-n-octylpyrrolidine, and the reaction was carried out at a reaction temperature of 220°C for 2 hours.
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åãçæããã Gas chromatographic analysis of the reaction products revealed that 3.12 mmol of ethylene glycol, 0.03 mmol of ethanol, 2.70 mmol of methanol, 0.33 mmol of methyl formate, and trace amounts of other components such as 1,2 propanediol, glycerin, methane, and CO 2 were produced. .
ãšãã¬ã³ã°ãªã³ãŒã«ã®ã¿ãŒã³ãªãŒããŒæ°ã¯
23.7molïŒïŒïœâatomRhïŒïœã§ãã€ãã The turnover number of ethylene glycol is
It was 23.7 mol/(g-atomRh)h.
å®æœäŸ 16
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ã 1.0ããªã¢ã«ãããªã€ãœãããã«ãã¹ãã€ã³2.0
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220âã§15åéåå¿ãè¡ã€ããExample 16 Using the same autoclave as Example 11,
Acetylacetonate (biscarbonyl) rhodium 1.0 mmol, triisopropylphosphine 2.0
mmol, N-methylpyrrolidine 0.5ml, N,
Add 5 ml of N'-dimethylimidazolidinone,
The reaction was carried out at 220°C for 15 minutes.
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ãã€ãã Gas chromatographic analysis of the reaction products revealed that 7.08 mmol of ethylene glycol, 0.09 mmol of ethanol, 3.48 mmol of methanol, 0.21 mmol of methyl formate, and trace amounts of 1,2-propanediol, glycerin, methane, and CO 2 were produced. At this time, the turnover number of ethylene glycol was 28.3 mol/(g-atomRh)h.
å®æœäŸ 17
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å®å§åäžã240âã§ïŒæéãåå¿ããããExample 17 The inside of a 200 ml autoclave (manufactured by Hastelloy C) equipped with a magnetic induction stirring device was thoroughly replaced with nitrogen gas, and 1.4 mmol of rhodium acetylacetonate (biscarbonyl), 7.0 mmol of triisopropylphosphine, and N- After charging 15 ml of methylpyrrolidine and 45 ml of tetraglyme and replacing the inside of the autoclave with a mixed gas of CO:H 2 = 1:1, a mixed gas of the same composition was introduced under pressure and the mixture was heated at 240°C under a constant pressure of 520 kg/cm 2 . time to react.
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žã¡ãã«0.78ããªã¢ã«ããã®ä»ã«åŸ®éã®ïŒïŒïŒ
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ã¿ãŒã³ãªãŒããŒæ°ã¯38.92molïŒïŒïœâatomRhïŒ
ïœã§ãã€ãã After the reaction was completed, the autoclave was cooled, and the reaction products were taken out and analyzed by gas chromatography. As a result, ethylene glycol 54.50 mmol, ethanol 4.55 mmol, methanol 64.30 mmol, methanol 64.30 mmol,
Methyl formate 0.78 mmol, plus trace amounts of 1,2
Propanediol, glycerin, methane, CO2 , etc. were obtained. At this time, the turnover number of ethylene glycol is 38.92 mol/(g-atomRh)
It was h.
å®æœäŸ 18
å®æœäŸ13ã®æ¡ä»¶ã§ïŒ®âïœâãªã¯ãã«ãããªãžã³
0.048mlãããã©ã°ã©ã€ã 5.0mlã䜿çšããŠåå¿ã
è¡ã€ããExample 18 N-n-octylpyrrolidine under the conditions of Example 13
The reaction was carried out using 0.048 ml and 5.0 ml of tetraglyme.
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ã³ãCO2ãªã©ãæ€åºãããã Gas chromatographic analysis of the reaction products revealed 2.41 mmol of ethylene glycol, 0.01 mmol of ethanol, 6.21 mmol of methanol, 0.45 mmol of methyl formate, and trace amounts of other products such as 1,2-propanediol, glycerin, methane, and CO2 . was detected.
ãšãã¬ã³ã°ãªã³ãŒã«ã®ã¿ãŒã³ãªãŒããŒæ°ã¯
12.1molïŒïŒïœâatomRhïŒïœã§ãã€ãã The turnover number of ethylene glycol is
It was 12.1 mol/(g-atomRh)h.
å®æœäŸ 19
å®æœäŸ13ã®æ¡ä»¶ã§ïŒ®âïœâãªã¯ãã«ãããªãžã³
0.12mlãããã©ã°ã©ã€ã 5.0mlã䜿çšããŠåå¿ã
è¡ã€ããExample 19 N-n-octylpyrrolidine under the conditions of Example 13
The reaction was carried out using 0.12 ml and 5.0 ml of tetraglyme.
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æããšãã¬ã³ã°ãªã³ãŒã«3.13ããªã¢ã«ããšã¿ããŒ
ã«0.01ããªã¢ã«ãã¡ã¿ããŒã«5.82ããªã¢ã«ãã®é
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ã¡ãã«0.39ããªã¢ã«ããã®ä»ã«åŸ®éã®çæç©ãšã
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ã³ãCO2ãªã©ãæ€åºãããã Gas chromatography analysis of the reaction products revealed 3.13 mmol of ethylene glycol, 0.01 mmol of ethanol, 5.82 mmol of methanol, 0.39 mmol of methyl formate, and trace amounts of other products such as 1,2-propanediol, glycerin, methane, and CO2 . was detected.
ãšãã¬ã³ã°ãªã³ãŒã«ã®ã¿ãŒã³ãªãŒããŒæ°ã¯
15.7molïŒïŒïœâatomRhïŒïœã§ãã€ãã The turnover number of ethylene glycol is
It was 15.7 mol/(g-atomRh)h.
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ã³ã°ãªã³ãŒã«ããšã¿ããŒã«ã®ãããªC2ã¢ã«ã³ãŒ
ã«ã補é ããããšãå¯èœã§ããã
According to the method of the present invention, it is possible to produce C2 alcohols such as ethylene glycol and ethanol in high yields that were not possible with conventional catalyst systems.
Claims (1)
çŽ ãšæ°ŽçŽ ãåå¿ãããéã«åå¿ç³»ã«äžèšã®åŒ(1)
ïŒåŒäžãã¯ã¢ã«ãã«åºåã¯ã¢ã«ãã«åºã®äžéšã
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ã䜵çšããå Žåãé€ãïŒãç¹åŸŽãšãããšãã¬ã³ã°
ãªã³ãŒã«ããã³ãšã¿ããŒã«ã®è£œé æ¹æ³ã [Claims] 1. When carbon monoxide and hydrogen are reacted using a rhodium-containing catalyst, the following formula (1) is added to the reaction system:
(In the formula, R is an alkyl group or a part of the alkyl group is
The presence of a pyrrolidine represented by a hydroxyalkyl group substituted with an OH group, where R' is H, an alkyl group, or a hydroxyalkyl group (unless trialkylphosphine oxide is used in combination) A method for producing ethylene glycol and ethanol, characterized by:
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP61149253A JPS635043A (en) | 1986-06-25 | 1986-06-25 | Production of 2c alcohol |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP61149253A JPS635043A (en) | 1986-06-25 | 1986-06-25 | Production of 2c alcohol |
Publications (2)
Publication Number | Publication Date |
---|---|
JPS635043A JPS635043A (en) | 1988-01-11 |
JPS641452B2 true JPS641452B2 (en) | 1989-01-11 |
Family
ID=15471217
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP61149253A Granted JPS635043A (en) | 1986-06-25 | 1986-06-25 | Production of 2c alcohol |
Country Status (1)
Country | Link |
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JP (1) | JPS635043A (en) |
Families Citing this family (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH02135050A (en) * | 1988-11-12 | 1990-05-23 | Urashima Shokuhin Kogyo Kk | Preparation of sheet food composed mainly of cheese |
CN103537282B (en) * | 2013-10-11 | 2016-04-06 | æµæ±å€§åŠ | For the synthesis of gas synthesizing alcohol methanogenic rhodium base catalyst in parallel and preparation method thereof |
-
1986
- 1986-06-25 JP JP61149253A patent/JPS635043A/en active Granted
Also Published As
Publication number | Publication date |
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JPS635043A (en) | 1988-01-11 |
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