JPS6353166B2 - - Google Patents
Info
- Publication number
- JPS6353166B2 JPS6353166B2 JP61235501A JP23550186A JPS6353166B2 JP S6353166 B2 JPS6353166 B2 JP S6353166B2 JP 61235501 A JP61235501 A JP 61235501A JP 23550186 A JP23550186 A JP 23550186A JP S6353166 B2 JPS6353166 B2 JP S6353166B2
- Authority
- JP
- Japan
- Prior art keywords
- ruthenium
- acetic acid
- ethanol
- gas
- cobalt
- 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
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 123
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical group CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 103
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims description 63
- 229910052707 ruthenium Inorganic materials 0.000 claims description 63
- 239000007789 gas Substances 0.000 claims description 61
- 239000007788 liquid Substances 0.000 claims description 46
- 238000000034 method Methods 0.000 claims description 42
- 230000015572 biosynthetic process Effects 0.000 claims description 25
- 238000003786 synthesis reaction Methods 0.000 claims description 25
- 238000006243 chemical reaction Methods 0.000 claims description 22
- 150000003304 ruthenium compounds Chemical class 0.000 claims description 17
- 150000002366 halogen compounds Chemical class 0.000 claims description 11
- 239000007791 liquid phase Substances 0.000 claims description 10
- 150000001869 cobalt compounds Chemical class 0.000 claims description 8
- 150000001875 compounds Chemical class 0.000 claims description 7
- 238000004519 manufacturing process Methods 0.000 claims description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 4
- 229910052760 oxygen Inorganic materials 0.000 claims description 4
- 239000001301 oxygen Substances 0.000 claims description 4
- 239000007795 chemical reaction product Substances 0.000 claims description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 36
- -1 organic acid salts Chemical class 0.000 description 16
- 239000002904 solvent Substances 0.000 description 14
- 229910017052 cobalt Inorganic materials 0.000 description 11
- 239000010941 cobalt Substances 0.000 description 11
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 9
- 125000004429 atom Chemical group 0.000 description 9
- 229910002091 carbon monoxide Inorganic materials 0.000 description 9
- NQZFAUXPNWSLBI-UHFFFAOYSA-N carbon monoxide;ruthenium Chemical group [Ru].[Ru].[Ru].[O+]#[C-].[O+]#[C-].[O+]#[C-].[O+]#[C-].[O+]#[C-].[O+]#[C-].[O+]#[C-].[O+]#[C-].[O+]#[C-].[O+]#[C-].[O+]#[C-].[O+]#[C-] NQZFAUXPNWSLBI-UHFFFAOYSA-N 0.000 description 8
- 239000001257 hydrogen Substances 0.000 description 8
- 229910052739 hydrogen Inorganic materials 0.000 description 8
- 150000003839 salts Chemical class 0.000 description 8
- 238000010521 absorption reaction Methods 0.000 description 7
- 239000003054 catalyst Substances 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 6
- 239000003446 ligand Substances 0.000 description 6
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 6
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 5
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 4
- 239000002253 acid Substances 0.000 description 4
- 230000007423 decrease Effects 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 239000012071 phase Substances 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 238000004064 recycling Methods 0.000 description 4
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- SJRJJKPEHAURKC-UHFFFAOYSA-N N-Methylmorpholine Chemical compound CN1CCOCC1 SJRJJKPEHAURKC-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 150000001242 acetic acid derivatives Chemical class 0.000 description 3
- 238000009835 boiling Methods 0.000 description 3
- 239000006227 byproduct Substances 0.000 description 3
- 238000006555 catalytic reaction Methods 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 150000002148 esters Chemical class 0.000 description 3
- 229910052736 halogen Inorganic materials 0.000 description 3
- 150000007975 iminium salts Chemical group 0.000 description 3
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 239000002244 precipitate Substances 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- WOCIAKWEIIZHES-UHFFFAOYSA-N ruthenium(iv) oxide Chemical compound O=[Ru]=O WOCIAKWEIIZHES-UHFFFAOYSA-N 0.000 description 3
- CXWXQJXEFPUFDZ-UHFFFAOYSA-N tetralin Chemical compound C1=CC=C2CCCCC2=C1 CXWXQJXEFPUFDZ-UHFFFAOYSA-N 0.000 description 3
- RFFLAFLAYFXFSW-UHFFFAOYSA-N 1,2-dichlorobenzene Chemical compound ClC1=CC=CC=C1Cl RFFLAFLAYFXFSW-UHFFFAOYSA-N 0.000 description 2
- MNZAKDODWSQONA-UHFFFAOYSA-N 1-dibutylphosphorylbutane Chemical compound CCCCP(=O)(CCCC)CCCC MNZAKDODWSQONA-UHFFFAOYSA-N 0.000 description 2
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 description 2
- IKHGUXGNUITLKF-UHFFFAOYSA-N Acetaldehyde Chemical compound CC=O IKHGUXGNUITLKF-UHFFFAOYSA-N 0.000 description 2
- KWOLFJPFCHCOCG-UHFFFAOYSA-N Acetophenone Chemical compound CC(=O)C1=CC=CC=C1 KWOLFJPFCHCOCG-UHFFFAOYSA-N 0.000 description 2
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- CPELXLSAUQHCOX-UHFFFAOYSA-N Hydrogen bromide Chemical compound Br CPELXLSAUQHCOX-UHFFFAOYSA-N 0.000 description 2
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- SMWDFEZZVXVKRB-UHFFFAOYSA-N Quinoline Chemical compound N1=CC=CC2=CC=CC=C21 SMWDFEZZVXVKRB-UHFFFAOYSA-N 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- KXKVLQRXCPHEJC-UHFFFAOYSA-N acetic acid trimethyl ester Natural products COC(C)=O KXKVLQRXCPHEJC-UHFFFAOYSA-N 0.000 description 2
- 230000002411 adverse Effects 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- 150000001350 alkyl halides Chemical class 0.000 description 2
- 150000003863 ammonium salts Chemical class 0.000 description 2
- RDOXTESZEPMUJZ-UHFFFAOYSA-N anisole Chemical compound COC1=CC=CC=C1 RDOXTESZEPMUJZ-UHFFFAOYSA-N 0.000 description 2
- 229910052787 antimony Inorganic materials 0.000 description 2
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 2
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 2
- 229910052785 arsenic Inorganic materials 0.000 description 2
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 description 2
- 229910052797 bismuth Inorganic materials 0.000 description 2
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 2
- 239000001569 carbon dioxide Substances 0.000 description 2
- 229910002092 carbon dioxide Inorganic materials 0.000 description 2
- 150000001868 cobalt Chemical class 0.000 description 2
- 229910000428 cobalt oxide Inorganic materials 0.000 description 2
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical compound [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 description 2
- NNBZCPXTIHJBJL-UHFFFAOYSA-N decalin Chemical compound C1CCCC2CCCCC21 NNBZCPXTIHJBJL-UHFFFAOYSA-N 0.000 description 2
- MQIKJSYMMJWAMP-UHFFFAOYSA-N dicobalt octacarbonyl Chemical group [Co+2].[Co+2].[O+]#[C-].[O+]#[C-].[O+]#[C-].[O+]#[C-].[O+]#[C-].[O+]#[C-].[O+]#[C-].[O+]#[C-] MQIKJSYMMJWAMP-UHFFFAOYSA-N 0.000 description 2
- GGSUCNLOZRCGPQ-UHFFFAOYSA-N diethylaniline Chemical compound CCN(CC)C1=CC=CC=C1 GGSUCNLOZRCGPQ-UHFFFAOYSA-N 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 150000002170 ethers Chemical class 0.000 description 2
- 150000004820 halides Chemical class 0.000 description 2
- 150000008282 halocarbons Chemical class 0.000 description 2
- 150000002367 halogens Chemical class 0.000 description 2
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 description 2
- 229910052500 inorganic mineral Inorganic materials 0.000 description 2
- AMXOYNBUYSYVKV-UHFFFAOYSA-M lithium bromide Chemical compound [Li+].[Br-] AMXOYNBUYSYVKV-UHFFFAOYSA-M 0.000 description 2
- HSZCZNFXUDYRKD-UHFFFAOYSA-M lithium iodide Chemical compound [Li+].[I-] HSZCZNFXUDYRKD-UHFFFAOYSA-M 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- QPJVMBTYPHYUOC-UHFFFAOYSA-N methyl benzoate Chemical compound COC(=O)C1=CC=CC=C1 QPJVMBTYPHYUOC-UHFFFAOYSA-N 0.000 description 2
- 239000011707 mineral Substances 0.000 description 2
- 150000002903 organophosphorus compounds Chemical class 0.000 description 2
- 150000004714 phosphonium salts Chemical group 0.000 description 2
- IOLCXVTUBQKXJR-UHFFFAOYSA-M potassium bromide Chemical compound [K+].[Br-] IOLCXVTUBQKXJR-UHFFFAOYSA-M 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 150000003303 ruthenium Chemical class 0.000 description 2
- 229910001925 ruthenium oxide Inorganic materials 0.000 description 2
- YBCAZPLXEGKKFM-UHFFFAOYSA-K ruthenium(iii) chloride Chemical compound [Cl-].[Cl-].[Cl-].[Ru+3] YBCAZPLXEGKKFM-UHFFFAOYSA-K 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- 239000011593 sulfur Substances 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 2
- 239000010409 thin film Substances 0.000 description 2
- 229910052723 transition metal Inorganic materials 0.000 description 2
- 150000003624 transition metals Chemical class 0.000 description 2
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 description 2
- KYLUAQBYONVMCP-UHFFFAOYSA-N (2-methylphenyl)phosphane Chemical compound CC1=CC=CC=C1P KYLUAQBYONVMCP-UHFFFAOYSA-N 0.000 description 1
- 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
- CYSGHNMQYZDMIA-UHFFFAOYSA-N 1,3-Dimethyl-2-imidazolidinon Chemical compound CN1CCN(C)C1=O CYSGHNMQYZDMIA-UHFFFAOYSA-N 0.000 description 1
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- ZFPGARUNNKGOBB-UHFFFAOYSA-N 1-Ethyl-2-pyrrolidinone Chemical compound CCN1CCCC1=O ZFPGARUNNKGOBB-UHFFFAOYSA-N 0.000 description 1
- HNAGHMKIPMKKBB-UHFFFAOYSA-N 1-benzylpyrrolidine-3-carboxamide Chemical compound C1C(C(=O)N)CCN1CC1=CC=CC=C1 HNAGHMKIPMKKBB-UHFFFAOYSA-N 0.000 description 1
- SQCZQTSHSZLZIQ-UHFFFAOYSA-N 1-chloropentane Chemical compound CCCCCCl SQCZQTSHSZLZIQ-UHFFFAOYSA-N 0.000 description 1
- ZSSWXNPRLJLCDU-UHFFFAOYSA-N 1-diethylphosphorylethane Chemical compound CCP(=O)(CC)CC ZSSWXNPRLJLCDU-UHFFFAOYSA-N 0.000 description 1
- KNFWHHCXXKWASF-UHFFFAOYSA-N 1-diheptylphosphorylheptane Chemical compound CCCCCCCP(=O)(CCCCCCC)CCCCCCC KNFWHHCXXKWASF-UHFFFAOYSA-N 0.000 description 1
- SNZSAFILJOCMFM-UHFFFAOYSA-N 1-dipropylphosphorylpropane Chemical compound CCCP(=O)(CCC)CCC SNZSAFILJOCMFM-UHFFFAOYSA-N 0.000 description 1
- GGYVTHJIUNGKFZ-UHFFFAOYSA-N 1-methylpiperidin-2-one Chemical compound CN1CCCCC1=O GGYVTHJIUNGKFZ-UHFFFAOYSA-N 0.000 description 1
- XEZNGIUYQVAUSS-UHFFFAOYSA-N 18-crown-6 Chemical compound C1COCCOCCOCCOCCOCCO1 XEZNGIUYQVAUSS-UHFFFAOYSA-N 0.000 description 1
- MPNXSZJPSVBLHP-UHFFFAOYSA-N 2-chloro-n-phenylpyridine-3-carboxamide Chemical compound ClC1=NC=CC=C1C(=O)NC1=CC=CC=C1 MPNXSZJPSVBLHP-UHFFFAOYSA-N 0.000 description 1
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- NPDACUSDTOMAMK-UHFFFAOYSA-N 4-Chlorotoluene Chemical compound CC1=CC=C(Cl)C=C1 NPDACUSDTOMAMK-UHFFFAOYSA-N 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- KZBUYRJDOAKODT-UHFFFAOYSA-N Chlorine Chemical compound ClCl KZBUYRJDOAKODT-UHFFFAOYSA-N 0.000 description 1
- 229910021503 Cobalt(II) hydroxide Inorganic materials 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- 229910016859 Lanthanum iodide Inorganic materials 0.000 description 1
- 241001676573 Minium Species 0.000 description 1
- OKIZCWYLBDKLSU-UHFFFAOYSA-M N,N,N-Trimethylmethanaminium chloride Chemical compound [Cl-].C[N+](C)(C)C OKIZCWYLBDKLSU-UHFFFAOYSA-M 0.000 description 1
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-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
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 239000012327 Ruthenium complex Substances 0.000 description 1
- 229910021603 Ruthenium iodide Inorganic materials 0.000 description 1
- ROZSPJBPUVWBHW-UHFFFAOYSA-N [Ru]=O Chemical class [Ru]=O ROZSPJBPUVWBHW-UHFFFAOYSA-N 0.000 description 1
- FXXACINHVKSMDR-UHFFFAOYSA-N acetyl bromide Chemical compound CC(Br)=O FXXACINHVKSMDR-UHFFFAOYSA-N 0.000 description 1
- WETWJCDKMRHUPV-UHFFFAOYSA-N acetyl chloride Chemical compound CC(Cl)=O WETWJCDKMRHUPV-UHFFFAOYSA-N 0.000 description 1
- 239000012346 acetyl chloride Substances 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 150000001502 aryl halides Chemical class 0.000 description 1
- 238000001479 atomic absorption spectroscopy Methods 0.000 description 1
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 description 1
- 239000012965 benzophenone Substances 0.000 description 1
- KCXMKQUNVWSEMD-UHFFFAOYSA-N benzyl chloride Chemical compound ClCC1=CC=CC=C1 KCXMKQUNVWSEMD-UHFFFAOYSA-N 0.000 description 1
- 229940073608 benzyl chloride Drugs 0.000 description 1
- LVRCYPYRKNAAMX-UHFFFAOYSA-M bis(triphenylphosphine)iminium chloride Chemical compound [Cl-].C1=CC=CC=C1[P+](C=1C=CC=CC=1)(C=1C=CC=CC=1)N=P(C=1C=CC=CC=1)(C=1C=CC=CC=1)C1=CC=CC=C1 LVRCYPYRKNAAMX-UHFFFAOYSA-M 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- OBNCKNCVKJNDBV-UHFFFAOYSA-N butanoic acid ethyl ester Natural products CCCC(=O)OCC OBNCKNCVKJNDBV-UHFFFAOYSA-N 0.000 description 1
- XQPRBTXUXXVTKB-UHFFFAOYSA-M caesium iodide Chemical compound [I-].[Cs+] XQPRBTXUXXVTKB-UHFFFAOYSA-M 0.000 description 1
- YMFAWOSEDSLYSZ-UHFFFAOYSA-N carbon monoxide;cobalt Chemical group [Co].[Co].[Co].[Co].[O+]#[C-].[O+]#[C-].[O+]#[C-].[O+]#[C-].[O+]#[C-].[O+]#[C-].[O+]#[C-].[O+]#[C-].[O+]#[C-].[O+]#[C-].[O+]#[C-].[O+]#[C-] YMFAWOSEDSLYSZ-UHFFFAOYSA-N 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- NEHMKBQYUWJMIP-NJFSPNSNSA-N chloro(114C)methane Chemical compound [14CH3]Cl NEHMKBQYUWJMIP-NJFSPNSNSA-N 0.000 description 1
- 239000003426 co-catalyst Substances 0.000 description 1
- 229940011182 cobalt acetate Drugs 0.000 description 1
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 description 1
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 1
- 229910001981 cobalt nitrate Inorganic materials 0.000 description 1
- GAYAMOAYBXKUII-UHFFFAOYSA-L cobalt(2+);dibenzoate Chemical compound [Co+2].[O-]C(=O)C1=CC=CC=C1.[O-]C(=O)C1=CC=CC=C1 GAYAMOAYBXKUII-UHFFFAOYSA-L 0.000 description 1
- AVWLPUQJODERGA-UHFFFAOYSA-L cobalt(2+);diiodide Chemical compound [Co+2].[I-].[I-] AVWLPUQJODERGA-UHFFFAOYSA-L 0.000 description 1
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical compound [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 description 1
- ASKVAEGIVYSGNY-UHFFFAOYSA-L cobalt(ii) hydroxide Chemical compound [OH-].[OH-].[Co+2] ASKVAEGIVYSGNY-UHFFFAOYSA-L 0.000 description 1
- FJDJVBXSSLDNJB-LNTINUHCSA-N cobalt;(z)-4-hydroxypent-3-en-2-one Chemical compound [Co].C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O FJDJVBXSSLDNJB-LNTINUHCSA-N 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- GBRBMTNGQBKBQE-UHFFFAOYSA-L copper;diiodide Chemical compound I[Cu]I GBRBMTNGQBKBQE-UHFFFAOYSA-L 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- JHPVVOXKINUOSC-UHFFFAOYSA-N diethyl(methyl)azanium;iodide Chemical compound [I-].CC[NH+](C)CC JHPVVOXKINUOSC-UHFFFAOYSA-N 0.000 description 1
- SBZXBUIDTXKZTM-UHFFFAOYSA-N diglyme Chemical compound COCCOCCOC SBZXBUIDTXKZTM-UHFFFAOYSA-N 0.000 description 1
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Chemical compound C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- YUWFEBAXEOLKSG-UHFFFAOYSA-N hexamethylbenzene Chemical compound CC1=C(C)C(C)=C(C)C(C)=C1C YUWFEBAXEOLKSG-UHFFFAOYSA-N 0.000 description 1
- GNOIPBMMFNIUFM-UHFFFAOYSA-N hexamethylphosphoric triamide Chemical compound CN(C)P(=O)(N(C)C)N(C)C GNOIPBMMFNIUFM-UHFFFAOYSA-N 0.000 description 1
- 239000012456 homogeneous solution Substances 0.000 description 1
- 150000004677 hydrates Chemical class 0.000 description 1
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical compound [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 229910000042 hydrogen bromide Inorganic materials 0.000 description 1
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 1
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 1
- 229910000043 hydrogen iodide Inorganic materials 0.000 description 1
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical compound II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- HVTICUPFWKNHNG-UHFFFAOYSA-N iodoethane Chemical compound CCI HVTICUPFWKNHNG-UHFFFAOYSA-N 0.000 description 1
- INQOMBQAUSQDDS-UHFFFAOYSA-N iodomethane Chemical compound IC INQOMBQAUSQDDS-UHFFFAOYSA-N 0.000 description 1
- XJTQJERLRPWUGL-UHFFFAOYSA-N iodomethylbenzene Chemical compound ICC1=CC=CC=C1 XJTQJERLRPWUGL-UHFFFAOYSA-N 0.000 description 1
- 239000003350 kerosene Substances 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- KYKBXWMMXCGRBA-UHFFFAOYSA-K lanthanum(3+);triiodide Chemical compound I[La](I)I KYKBXWMMXCGRBA-UHFFFAOYSA-K 0.000 description 1
- 229910001629 magnesium chloride Inorganic materials 0.000 description 1
- UZKWTJUDCOPSNM-UHFFFAOYSA-N methoxybenzene Substances CCCCOC=C UZKWTJUDCOPSNM-UHFFFAOYSA-N 0.000 description 1
- 229940095102 methyl benzoate Drugs 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- PYLWMHQQBFSUBP-UHFFFAOYSA-N monofluorobenzene Chemical compound FC1=CC=CC=C1 PYLWMHQQBFSUBP-UHFFFAOYSA-N 0.000 description 1
- GEMHFKXPOCTAIP-UHFFFAOYSA-N n,n-dimethyl-n'-phenylcarbamimidoyl chloride Chemical compound CN(C)C(Cl)=NC1=CC=CC=C1 GEMHFKXPOCTAIP-UHFFFAOYSA-N 0.000 description 1
- KSKTVNNRMXUMIY-UHFFFAOYSA-N n,n-dimethylethanamine;hydrochloride Chemical compound Cl.CCN(C)C KSKTVNNRMXUMIY-UHFFFAOYSA-N 0.000 description 1
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 1
- LEIZJJNFNQIIKH-UHFFFAOYSA-K propanoate;ruthenium(3+) Chemical compound [Ru+3].CCC([O-])=O.CCC([O-])=O.CCC([O-])=O LEIZJJNFNQIIKH-UHFFFAOYSA-K 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 229910001927 ruthenium tetroxide Inorganic materials 0.000 description 1
- OJLCQGGSMYKWEK-UHFFFAOYSA-K ruthenium(3+);triacetate Chemical compound [Ru+3].CC([O-])=O.CC([O-])=O.CC([O-])=O OJLCQGGSMYKWEK-UHFFFAOYSA-K 0.000 description 1
- LJZVDOUZSMHXJH-UHFFFAOYSA-K ruthenium(3+);triiodide Chemical compound [Ru+3].[I-].[I-].[I-] LJZVDOUZSMHXJH-UHFFFAOYSA-K 0.000 description 1
- GTCKPGDAPXUISX-UHFFFAOYSA-N ruthenium(3+);trinitrate Chemical compound [Ru+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O GTCKPGDAPXUISX-UHFFFAOYSA-N 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 229930195734 saturated hydrocarbon Natural products 0.000 description 1
- 229920002545 silicone oil Polymers 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 description 1
- 150000003457 sulfones Chemical class 0.000 description 1
- 150000003462 sulfoxides Chemical class 0.000 description 1
- MDDUHVRJJAFRAU-YZNNVMRBSA-N tert-butyl-[(1r,3s,5z)-3-[tert-butyl(dimethyl)silyl]oxy-5-(2-diphenylphosphorylethylidene)-4-methylidenecyclohexyl]oxy-dimethylsilane Chemical compound C1[C@@H](O[Si](C)(C)C(C)(C)C)C[C@H](O[Si](C)(C)C(C)(C)C)C(=C)\C1=C/CP(=O)(C=1C=CC=CC=1)C1=CC=CC=C1 MDDUHVRJJAFRAU-YZNNVMRBSA-N 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- RKHXQBLJXBGEKF-UHFFFAOYSA-M tetrabutylphosphanium;bromide Chemical compound [Br-].CCCC[P+](CCCC)(CCCC)CCCC RKHXQBLJXBGEKF-UHFFFAOYSA-M 0.000 description 1
- ZUHZGEOKBKGPSW-UHFFFAOYSA-N tetraglyme Chemical compound COCCOCCOCCOCCOC ZUHZGEOKBKGPSW-UHFFFAOYSA-N 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- RXMRGBVLCSYIBO-UHFFFAOYSA-M tetramethylazanium;iodide Chemical compound [I-].C[N+](C)(C)C RXMRGBVLCSYIBO-UHFFFAOYSA-M 0.000 description 1
- BALCYVFFDOBQPW-UHFFFAOYSA-M tetraphenylazanium;chloride Chemical compound [Cl-].C1=CC=CC=C1[N+](C=1C=CC=CC=1)(C=1C=CC=CC=1)C1=CC=CC=C1 BALCYVFFDOBQPW-UHFFFAOYSA-M 0.000 description 1
- WAGFXJQAIZNSEQ-UHFFFAOYSA-M tetraphenylphosphonium chloride Chemical compound [Cl-].C1=CC=CC=C1[P+](C=1C=CC=CC=1)(C=1C=CC=CC=1)C1=CC=CC=C1 WAGFXJQAIZNSEQ-UHFFFAOYSA-M 0.000 description 1
- HNJXPTMEWIVQQM-UHFFFAOYSA-M triethyl(hexadecyl)azanium;bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](CC)(CC)CC HNJXPTMEWIVQQM-UHFFFAOYSA-M 0.000 description 1
- AISMNBXOJRHCIA-UHFFFAOYSA-N trimethylazanium;bromide Chemical compound Br.CN(C)C AISMNBXOJRHCIA-UHFFFAOYSA-N 0.000 description 1
- CURCMGVZNYCRNY-UHFFFAOYSA-N trimethylazanium;iodide Chemical compound I.CN(C)C CURCMGVZNYCRNY-UHFFFAOYSA-N 0.000 description 1
- ZMBHCYHQLYEYDV-UHFFFAOYSA-N trioctylphosphine oxide Chemical compound CCCCCCCCP(=O)(CCCCCCCC)CCCCCCCC ZMBHCYHQLYEYDV-UHFFFAOYSA-N 0.000 description 1
- FIQMHBFVRAXMOP-UHFFFAOYSA-N triphenylphosphane oxide Chemical compound C=1C=CC=CC=1P(C=1C=CC=CC=1)(=O)C1=CC=CC=C1 FIQMHBFVRAXMOP-UHFFFAOYSA-N 0.000 description 1
- CPBWCZUONDSUDD-UHFFFAOYSA-N triphenylphosphane;hydroiodide Chemical compound I.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 CPBWCZUONDSUDD-UHFFFAOYSA-N 0.000 description 1
- 150000003672 ureas Chemical class 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
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-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
- Y02P20/584—Recycling of catalysts
Description
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æããæ¹æ³ã®æ¹è¯ã«é¢ãããDETAILED DESCRIPTION OF THE INVENTION Field of the Invention The present invention relates to a method for synthesizing ethanol directly from synthesis gas, ie carbon monoxide and hydrogen. More particularly, the present invention relates to an improved method for directly synthesizing ethanol from synthesis gas by a liquid phase homogeneous catalytic reaction using ruthenium and cobalt compounds as catalysts and halogen compounds as cocatalysts.
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åªãšããŠåºç¯å²ãªçšéãæããååç©ã§ããã Ethanol is a compound that has a wide range of uses as an intermediate raw material or solvent for various chemicals.
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ã¿ããŒã«ã補é ããããšãã§ããã(Problems to be Solved by the Prior Art and the Invention) Synthesis gas containing carbon monoxide and hydrogen is continuously fed into a catalyst-containing liquid medium containing a ruthenium compound and a halogen compound held in a reactor. The present inventors have already filed an application for a method of producing ethanol by supplying ethanol to produce ethanol and taking out the produced ethanol along with unreacted synthesis gas (Japanese Patent Application Laid-open No. 218540/1983). According to this method, a catalyst-containing liquid medium is held in a reactor, and ethanol is synthesized with this liquid medium. According to this method, alcohols or esters are entrained in unreacted synthesis gas, making it possible to produce highly concentrated ethanol.
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èŠãšãããã However, among the catalyst components, a part of the ruthenium compound evaporates out of the reaction system along with unreacted synthesis gas or gaseous reaction products, and the amount of ruthenium in the reaction system decreases with time. As a result, the ethanol production activity decreases as the amount of ruthenium in the reactor decreases, resulting in a drawback that ethanol cannot be produced stably. Therefore, a technique is needed to recover the volatilized ruthenium and recycle it to the reactor.
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ã«ã«ããã«ïŒRu3ïŒCOïŒ12ïŒã«å€åããã As a result of studies conducted by the present inventors, ruthenium evaporates along with unreacted synthesis gas in the form of ruthenium pentacarbonyl (Ru(CO) 5 ), which is a low boiling point. This compound transforms into triruthenium dodecacarbonyl (Ru 3 (CO) 12 ), which is sparingly soluble in various solvents, when exposed to heat or light at temperatures of several tens of degrees.
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ããå®æãããæ¢ã«åºé¡ãããŠããã When the unreacted synthesis gas is condensed, most of the volatile ruthenium is removed as a component of the condensate along with the product. A method for recovering ruthenium from this condensate and recycling it in a reactor has been completed by the present inventors and has already been applied for.
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ã«äœäžãããã On the other hand, ruthenium also accompanies non-condensable gases. Usually, a part of this non-condensable gas is exhausted to the outside of the system, and the rest is recycled to the reactor again by a gas compressor together with the raw material synthesis gas. As a result, ruthenium precipitates or adheres in the gas compressor, which not only adversely affects the gas compressor but also causes loss of expensive ruthenium and significantly reduces economic efficiency.
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ããšã¯ãããªãã A method for recovering volatilized ruthenium with methanol or ethanol in a homogeneous catalytic reaction using a ruthenium compound has already been disclosed (US-412033). According to this method, ruthenium compounds are recovered with a large amount of methanol or ethanol. However, methanol or ethanol has a low solubility of ruthenium (the solubility of ruthenium in methanol and ethanol is 1000ppm at 50â
(below), ruthenium will precipitate if it is concentrated to the extent that it does not affect the reaction in order to be recycled to the reactor. Additionally, methanol and ethanol have low boiling points and are easily entrained in gases, resulting in loss of their absorption solvents. Furthermore, when unreacted synthesis gas is recycled to the reactor, methanol or ethanol is entrained to the gas compressor.
Adversely affects gas compressor. Ruthenium must be recovered at low temperatures to prevent entrainment into this gas. This increases the cost of cooling equipment and energy costs. Therefore, methanol or ethanol is not preferred as an absorption solvent.
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åšããªãµã€ã¯ã«ããæè¡ãèŠè«ãããã Thus, in order to stably produce ethanol, a technology is required to recover and homogenize the volatilized ruthenium, and to recycle it to the reactor without affecting the reaction or equipment.
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ãããã®ã§ããã An object of the present invention is to provide a method for continuously and stably producing ethanol from synthesis gas by solving problems associated with recovering volatilized ruthenium, such as the solubility of ruthenium or loss of absorption solvent. It is something.
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ãå®æãããã«è³ã€ãã(Means for solving the problem) In order to solve the problem, the present inventors
We conducted intensive studies on the solubility of ruthenium and the influence of absorption solvents on the reaction. As a result, in a liquid-phase homogeneous catalytic reaction using a ruthenium compound, a cobalt compound as a catalyst, and a halogen compound as a co-catalyst, a non-condensable gas accompanied by volatile ruthenium is recovered by contacting with a liquid phase containing acetic acid, They discovered that even if the acetic acid solution was concentrated to an amount that could be recycled to the reactor, it remained a homogeneous solution, leading to the completion of the present invention.
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ãã Acetic acid is the main product in the ruthenium and cobalt catalyst system used in the process of the present invention, but when acetic acid is recycled to the reactor, the amount of acetic acid recovered minus the recycled amount, i.e., the net amount of acetic acid produced. It has already been found that the selectivity of ethanol is greatly improved by reducing the
- Publication No. 63536). Therefore, acetic acid can be recycled in large quantities to the reactor, and is also preferable in terms of reaction results.
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æ倱ãå°ãªãã Furthermore, the solubility of ruthenium in acetic acid is more than twice that of methanol and ethanol, and because the boiling point of acetic acid is higher than these alcohols, less amount is entrained in the gas, and therefore less acetic acid is lost. few.
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ãŒã«ã®è£œé æ¹æ³ã§ããã That is, the present invention continuously supplies synthesis gas to a liquid medium containing a ruthenium compound, a cobalt compound, and a halogen compound held in a reactor under high temperature and high pressure to produce an oxygen-containing compound mainly composed of ethanol. In this method, the unreacted synthesis gas is condensed below the reaction temperature, and the separated non-reacted This is a method for producing ethanol in which a condensable gas is brought into contact with a liquid phase containing acetic acid and volatile ruthenium is recovered.
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žå¡©ãªã©ãããã As the ruthenium compound used in the method of the present invention, any ruthenium compound that forms a complex having carbon monoxide coordination under the reaction conditions can be used. Examples of these include, in addition to metal ruthenium, ruthenium oxides such as ruthenium dioxide and ruthenium tetroxide, their hydrates, mineral acid salts of ruthenium such as ruthenium chloride, ruthenium iodide, and ruthenium nitrate, ruthenium acetate, Examples include organic acid salts of ruthenium such as ruthenium propionate.
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ãŠã é¯äœãªã©ã奜ãŸããã Ruthenium compounds can also be used directly in the form of coordination compounds, examples of which include ruthenium carbonyl, such as triruthenium dodecacarbonyl, and ruthenium combined with oxygen, sulfur, halogens, nitrogen, phosphorous, arsenic, etc. , antimony,
Examples include ruthenium complexes coordinated with ligands such as bismuth, and their salts. Among these ruthenium compounds, ruthenium oxide, ruthenium halide, ruthenium carbonyl, ruthenium acetylacetonate, or ruthenium in which at least some of the carbon monoxide ligands of ruthenium carbonyl are replaced with other ligands. Complexes and the like are preferred.
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éééšã®ç¯å²ã§ããã The amount of the ruthenium compound used in the method of the present invention in the liquid medium is 0.1 to 300 parts by weight of the liquid medium in terms of ruthenium metal.
Parts by weight range.
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ãããããã³ãã«ãé¯äœãªã©ã奜ãŸããã In addition to metal cobalt, cobalt compounds include cobalt oxide, cobalt hydroxide, cobalt chloride, cobalt iodide, cobalt mineral salts such as cobalt nitrate, cobalt acetate, cobalt benzoate, and cobalt naphthenate. These include organic acid salts of cobalt. In addition, coordination compounds can also be used, such as cobalt carbonyl, such as dicobalt octacarbonyl, tetracobalt dodecacarbonyl, cyclopentanedienyl cobalt dicarbonyl, and cobalt with oxygen. Examples include cobalt complexes coordinated with ligands containing sulfur, halogen, nitrogen, phosphorus, arsenic, antimony, bismuth, etc., and their salts. Among these cobalt compounds, at least some of the carbon monoxide ligands of cobalt oxide, cobalt halide, cobalt carbonyl, cobalt organic acid salt, cobalt acetylacetonate, or cobalt carbonyl are replaced with other ligands. Cobalt complexes and the like are preferred.
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éééšã®ç¯å²ã§ããã The amount of the ruthenium compound used in the method of the present invention in the liquid medium is 0.1 to 300 parts by weight of the liquid medium in terms of ruthenium metal.
Parts by weight range.
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åã奜ãŸããã¯ïŒã10ã°ã©ã ååã®ç¯å²ã§ããã The amount of cobalt compound used in the method of the invention in the liquid medium is also in the range of 0.1 to 100 gram atoms, preferably 1 to 10 gram atoms of cobalt per gram atom of ruthenium.
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ããã³éžææ§ã¯èããå°ããã Further, in the method of the present invention, it is necessary to use a halogen compound as a promoter for the ruthenium compound and the cobalt compound. In the absence of these halogen compounds, ethanol activity and selectivity are significantly lower.
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ããšãã§ããã These halogen compounds include metal salts such as alkali metal salts and alkaline earth metal salts having halogen ions such as chloride ions, bromide ions, and iodine ions as anions constituting the salts;
Examples include salts such as ammonium salts, quaternary phosphonium salts, and iminium salts, and hydrocarbon halides such as alkyl halides and aryl halides. Further, hydrogen halides, acid halides, transition metal halides, and the like can also be used. More specifically, (1) examples of metal salts include lithium chloride, lithium bromide, lithium iodide, sodium chloride, potassium bromide, cesium iodide, magnesium chloride, lanthanum iodide, etc.; (2) ammonium salts; Examples include trimethylammonium chloride, trimethylammonium bromide, trimethylammonium iodide, dimethylethylammonium chloride, methyldiethylammonium iodide, tetramethylammonium chloride, tetramethylammonium iodide, tetraphenylammonium chloride, cetyltriethylammonium bromide, etc. , (3) Examples of quaternary phosphonium salts include tetraphenylphosphonium chloride, tetra n-butylphosphonium bromide,
Examples of (4) iminium salts include bis(triphenylphosphine) iminium chloride, bis(triphenylphosphine) iodide, etc. (5) Examples of alkyl halides, such as minium bromide, bis(triphenylphosphine) iminium iodide, and iminium salts in which at least a portion of the phenyl group of these iminium compounds is substituted with a methyl group, ethyl group, etc. as methyl chloride, methylene chloride,
Chloroform, carbon tetrachloride, methyl iodide, ethyl iodide, benzyl chloride, benzyl iodide, etc.
(6) Examples of hydrogen halides include hydrogen chloride, hydrogen bromide, and hydrogen iodide; (7) Examples of acid halides include acetyl chloride and acetyl bromide; and (8) transition metal halides. Examples include nickel chloride, ruthenium chloride, and copper iodide.
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ãšãã§ããã Moreover, iodine, chlorine gas, and bromine gas can also be used.
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以äžãæ··åããŠçšããããšãã§ããã These halogen compounds can be used alone or in combination of two or more.
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The halogen atoms range from 0.1 to 200 gram atoms, more preferably from 1 to 50 gram atoms.
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奜ãŸããã The method of the invention is carried out in a liquid medium. The liquid medium used is preferably an aprotic liquid solvent.
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Halogenated hydrocarbons such as chloropentane, o-dichlorobenzene, p-chlorotoluene, fluorobenzene, dioxane, tetrahydrofuran,
Ethers such as ethyl ether, anisole, phenyl ether, diglyme, tetraglyme, and 18-crown-6, esters such as methyl acetate, ethyl butyrate, methyl benzoate, and γ-butyrolactone, and ketones such as acetone, acetophenone, and benzophenone. N-methylpyrrolidin-2-one, N-ethylpyrrolidin-2-one,
N-substituted amides such as N,N-dimethylacetamide, N-methylpiperidone, hexamethylphosphoric triamide, tertiary amines such as N,N-diethylaniline, N-methylmorpholine, pyridine, quinoline, sulfolane, etc. sulfones, sulfoxides such as dimethyl sulfoxide, urea derivatives such as 1,3-dimethyl-2-imidazolidinone, and triethylphosphine oxide, tri-n-propylphosphine oxide, tri-n-butyl. phosphine oxide, tri-n-heptylphosphine oxide, tri-n-octylphosphine oxide,
Triphenylphosphine oxide, tri-p-
Examples include oxides of trivalent organic phosphorus compounds such as tolylphosphine oxide, tri-p-chlorophenylphosphine oxide, and tributylphosphine oxide, and silicone oil.
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ãµã€ãé¡ããããããã Among these, particularly preferred liquid solvents include saturated hydrocarbons, aromatic hydrocarbons, halogenated hydrocarbons, ethers, and oxides of trivalent organic phosphorus compounds.
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é¡ä»¥äžãæ··åããŠã䜿çšã§ããã These liquid solvents can be used alone or in combination of two or more.
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ãã Further, if the liquid solvent used in the method of the present invention is liquid at least under the reaction conditions,
It can be used even if it is solid at room temperature and pressure.
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çã¯äœããªãã In the method of the present invention, the reaction temperature is in the range of 160 to 300°C, preferably in the range of 180 to 260°C. At reaction temperatures below 160°C, the reaction between carbon monoxide and hydrogen is extremely slow. Also, if the reaction temperature exceeds 300â,
Methane by-product increases significantly and ethanol selectivity decreases.
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ãŸããã Further, the reaction pressure is in the range of 150 to 800 kg/cm 2 G, preferably in the range of 300 to 500 kg/cm 2 G. The higher the reaction pressure, the better for the reaction of carbon monoxide and hydrogen, but the practical pressure is preferably 800 kg/cm 2 G or less.
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çŽ ãªã©ãååšããŠããŠãå·®ãæ¯ããªãã The molar ratio of carbon monoxide and hydrogen used as raw materials is preferably in the range of 1:10 to 10:1. However, extreme examples include the use of pure carbon monoxide in the presence of water,
By selecting the reaction conditions, it is possible to carry out the method of the invention even when using pure hydrogen in the presence of carbon dioxide. Further, other components inert to the present invention, such as methane, nitrogen, etc., may be present in the raw material synthesis gas.
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âã®ç¯å²ã奜ãŸããã¯30ã100âã§ããã In the method of the present invention, the method of condensing the unreacted synthesis gas below the reaction temperature and separating the non-condensable gases is carried out by methods known to those skilled in the art. For example, a method is usually used in which unreacted synthesis gas is passed through a cooling pipe and separated into a condensate and non-condensable gas in a gas-liquid separator. The cooling temperature at this time is -5 to 100
â range, preferably 30-100â.
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çãããã Furthermore, in the method of the present invention, the method of contacting the non-condensable gas with the liquid phase containing acetic acid is carried out in a manner known to those skilled in the art. For example, there is a method in which an acetic acid solution containing acetic acid is introduced from the upper part of the scrubber, and a non-condensable gas is introduced from the lower part. In this case, the scrubber is equipped with a filler, baffle plate, etc. in order to improve the contact efficiency between the two.
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ãæ¹æ³ã§ãæ¬çºæãå®æœããããšãã§ããã The present invention can also be carried out by simply blowing a non-condensable gas into the acetic acid solution.
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ããŠãæ¬çºæã®æ¹æ³ãéå®ãããã®ã§ã¯ãªãã However, the method of the present invention is not limited even if the two are brought into contact by other methods.
æ¬çºæã®æ¹æ³ãå³é¢ã«ããå ·äœçã«èª¬æããã The method of the present invention will be specifically explained with reference to the drawings.
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åªãšæ¥è§ŠããŠãšã¿ããŒã«ãçæããã In FIG. 1, a reactor 1 holds a liquid medium containing a ruthenium compound and a halogen compound. Synthesis gas passes through conduit 2 to reactor 1
supplied to The typical reaction temperature in reactor 1 is
180~260â, typical reaction pressure is 300~500
Kg/cm 2 G range. Such synthesis gas continuously supplied to the reactor 1 contacts a catalyst in a liquid medium to produce ethanol.
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äžå®ã«ä¿ãããã The produced ethanol, the by-products produced at the same time, and the easily volatile ruthenium complex (Ru(CO) 5 ) produced in the reactor are entrained in the synthesis gas flowing unreacted in the liquid medium and passed through conduit 3 to the cooler. Guided by 4. Here, the ethanol, by-products and volatile ruthenium are cooled and separated into non-condensable gas and condensate in a high-pressure gas-liquid separator 5. The liquid level in this high-pressure gas-liquid separator 5 is kept constant by a liquid level control valve 10.
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ïŒãéãäœå§æ°æ¶²åé¢åšïŒïŒã«å°ãããã The gas phase introduced into the conduit 6 is depressurized through the pressure reducing valve 8 to usually 10 to 30 kg/cm 2 G. Further, it passes through a cooler 9 and is guided to a low pressure gas-liquid separator 11.
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é¢èª¿ç¯åŒïŒïŒã«ãã€ãŠäžå®ã«ä¿ãããã On the other hand, the liquid phase led to the conduit 7 is
and is led to the low-pressure gas-liquid separator 11. This low-pressure gas-liquid separator 11 separates the gas into non-condensable gas and condensed liquid again. The liquid level of this low pressure gas-liquid separator 11 is kept constant by a liquid level control valve 13.
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ãã The liquid phase introduced into the conduit 12 is taken out via the liquid level control valve 13. This liquid phase contains a ruthenium compound in addition to reaction products such as ethanol.
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䌎ããã On the other hand, the gas phase passes through conduit 14 and is led to ruthenium scrubber 15 . This gas phase is accompanied by volatile ruthenium, unreacted synthesis gas, small amounts of carbon dioxide and products such as methane and small amounts of methanol.
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ïŒãšã»ãŒåã10ã30KgïŒcm2ã§æäœãããã This gas phase, ie non-condensable gas, is contacted in the ruthenium scrubber 15 with acetic acid conducted through conduit 16 and the volatile ruthenium is absorbed into the acetic acid solution. Ruthenium scrubber 15 is usually 20-50
Operated at °C. In addition, usually a low pressure gas-liquid separator 1
It is operated at 10 to 30 kg/cm 2 G, which is almost the same as 1.
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ããã Further, the non-condensable gas that does not contain volatile ruthenium passes through the cooler 17 and is taken out via the pressure reducing valve 18.
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ããå°ç®¡ïŒïŒã«å°ãããã On the other hand, acetic acid taken out from the lower part of the ruthenium scrubber 15 is taken out by the pump 19 so that the liquid level in the ruthenium scrubber becomes constant, and is led to the conduit 20.
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žæº¶æ¶²ã«åé¢ãããã A portion of this acetic acid solution containing volatile ruthenium is reduced to normal pressure through a pressure reducing valve 21, and then guided to a thin film evaporator 22, where it is converted into ruthenium-free acetic acid and contains ruthenium concentrated to an amount that can be recycled. Separated into acetic acid solution.
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ãŠåå¿åšããªãµã€ã¯ã«ãããã This ruthenium-containing concentrated acetic acid solution is pressurized through pump 23 and recycled through conduit 24 to the reactor.
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ã®ã§ããã(Operation) The method of the present invention involves bringing a non-condensable gas into contact with a liquid phase containing acetic acid to recover volatile ruthenium.
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ä»çããªããªãã According to this method, the volatilized ruthenium compound can be efficiently recovered and recycled to the reactor as a homogeneous liquid, and the loss of ruthenium is extremely reduced. Additionally, ruthenium precipitation or adhesion to the gas compressor due to recycling of unreacted synthesis gas is eliminated.
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žã®æ倱ãæžå°ããã Additionally, the amount of acetic acid entrained in the gas is suppressed by the ruthenium scrubber, reducing acetic acid loss.
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ãã®ã§ããã In other words, the method of the present invention is more effective than the conventional method.
This will improve C1 chemistry technology to an industrial level.
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éšããäŸçµŠãããExample 1 12 g (56 mg atoms as Ru) of triruthenium dodecacarbonyl (Ru 3 (CO) 12 ), 28.8 g (168 mg atoms as Co) of dicobalt octacarbonyl (Co 2 (CO) 8 ), 47.6 g (Cl as 2240mg atom) of lithium chloride (LiCl) and as solvent
560 g of tributylphosphine oxide (Bu 3 P0) was placed in a tubular reactor with a capacity of 1.5, and after the reactor was closed, synthesis gas was fed little by little from the bottom of the reactor. When the pressure in the reactor reached 360 Kg/cm 2 G, temperature increase was started. When the temperature of the reactor reached 320â, feed the synthesis gas and increase the reaction pressure to 450Kg/cm 2
While maintaining the pressure at G, gas was supplied at a space velocity of 2500/hour. At the same time, 150 g of acetic acid was supplied from the bottom of the reactor.
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ãã€ãŒã§åæããããã®çµæã第ïŒè¡šã«ç€ºãã The gas at the outlet of the reactor is condensed and passed through the liquid level control valve 13 of the low-pressure gas-liquid separator 11.
226 g of liquid was collected and analyzed by gas chromatography. The results are shown in Table 1.
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ããããã«å ç®ãããTable 1 Methanol 25.2g Ethanol 53.1g Propanol 13.2g Butanol 4.7g Formic acid 1.3g Acetic acid 153.9g (3.9g) Acetaldehyde 5.3g Others 7.5g * Esters such as methyl acetate and ethyl acetate are treated as the corresponding alcohol and acid, respectively. added to.
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ããæ£å³ã®çæéãè¡šããã The value in parentheses represents the net production amount excluding the supplied acetic acid from the recovered acetic acid.
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It was hot. The condensable gas at the outlet of the pressure reducing valve 18 was further blown into the acetic acid absorption liquid, and the ruthenium concentration in this acetic acid solution was analyzed by atomic absorption spectroscopy, but the ruthenium was below the detection limit.
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ïŒRu3ïŒCOïŒ12ïŒã®åœ¢æ
ã§ååšãããã®éã¯4.37ïœ
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šã芳å¯ãããªãã€ãã On the other hand, Ruthenium scrubber 11 (10 cm in diameter,
130cm high pipe type scrubber) at 30â, 10Kg/cm 2
G and fed acetic acid through conduit 16 at 20 kg/hour. After 50 hours, acetic acid was recovered through the pressure reducing valve 21, and the ruthenium was analyzed, and it was found that ruthenium existed in the form of triruthenium dodecacarbonyl (Ru 3 (CO) 12 ), and the amount was 4.37 g.
It was hot. This corresponds to ruthenium volatilization of 0.09g per hour. The recovered acetic acid was concentrated so that 0.09 g of ruthenium was present per 150 g of acetic acid recycled per hour, but the acetic acid solution was homogeneous and no precipitation of ruthenium was observed.
ïŒæ¯èŒäŸïŒ
ããªã«ãããŠã ããã«ã«ã«ããã«ïŒRu3
ïŒCOïŒ12ïŒ0.09ïœãïŒæéãããã®ã¡ã¿ããŒã«ã®ç
æéãããªãã¡ã25.2ïœã®ã¡ã¿ããŒã«ã«æº¶è§£ãã
ããšãããã50âã§ãåäžæ¶²ã¯åŸãããªãã€ãã(Comparative example) Triruthenium dodecacarbonyl (Ru 3
An attempt was made to dissolve 0.09 g of (CO) 12 ) in the amount of methanol produced per hour, that is, 25.2 g of methanol, but a homogeneous liquid could not be obtained even at 50°C.
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åžå溶åªãšããŠé
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ã«å䌎ããã«ãããŠã ãã»ãšãã©ååããããšã
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ã§ããã(Effect of the invention) If acetic acid is used as an absorption solvent, most of the ruthenium accompanying the non-condensable gas can be recovered. Furthermore, even if this acetic acid solution containing ruthenium is concentrated to a recyclable amount, ruthenium does not precipitate and can be recycled to the reactor as a homogeneous liquid.
ãã®ããã«ãæ¬çºæã®æ¹æ³ãçšããã°ãã«ãã
ãŠã ãååããåå¿åšãžãªãµã€ã¯ã«ããããã»ã¹
ãåäžæ¶²ãšããŠåãæ±ãããšãã§ããé«äŸ¡ãªã«ã
ããŠã ã®ååæ倱ã極ããŠå°ãªãããããšãã§ã
ãã As described above, by using the method of the present invention, the process of recovering ruthenium and recycling it to the reactor can be handled as a homogeneous liquid, and the recovery loss of expensive ruthenium can be extremely reduced.
第ïŒå³ã¯ãæ¬çºæã®æ¹æ³ãå®æœãã補é ãããŒ
ã·ãŒãã®ïŒäŸã瀺ããã®ã§ãããå³äžãå笊å·ã¯
次ã®éãã§ããã
ïŒâŠåå¿åšãïŒïŒïŒïŒïŒïŒâŠå·åŽåšãïŒâŠé«å§
æ°æ¶²åé¢åšãïŒïŒïŒïŒïŒïŒïŒâŠæžå§åŒãïŒïŒïŒïŒ
ïŒâŠæ¶²é¢èª¿ç¯åŒãïŒïŒâŠäœå§æ°æ¶²åé¢åšãïŒïŒâŠ
ã«ãããŠã ã¹ã¯ã©ããŒãïŒïŒïŒïŒïŒâŠãã³ããïŒ
ïŒâŠèèèžçºåšãïŒïŒïŒïŒïŒïŒïŒïŒïŒïŒïŒïŒïŒïŒ
ïŒïŒïŒïŒïŒïŒïŒïŒâŠå°ç®¡ã
FIG. 1 shows an example of a manufacturing flow sheet for carrying out the method of the present invention. In the figure, each symbol is as follows. 1...Reactor, 4,9,17...Cooler, 5...High pressure gas-liquid separator, 8,18,21...Pressure reducing valve, 10,1
3...Liquid level control valve, 11...Low pressure gas-liquid separator, 15...
Ruthenium scrubber, 19, 23...pump, 2
2... Thin film evaporator, 2, 3, 6, 7, 12, 14,
16, 20, 26... Conduit.
Claims (1)
ãããŠã ååç©ãã³ãã«ãååç©ããã³ããã²ã³
ååç©ãå«æãã液äœåªäœã«åæã¬ã¹ãé£ç¶çã«
äŸçµŠããŠããšã¿ããŒã«ãäž»æåãšããå«é žçŽ åå
ç©ãããªãåå¿çæç©ãåæããåå¿çæç©ãæª
åå¿ã®åæã¬ã¹ã«å䌎ãããŠåå¿åšããåãåºã
ãŠãšã¿ããŒã«ã補é ããæ¹æ³ã«ãããŠãæªåå¿ã®
åæã¬ã¹ãåå¿æž©åºŠä»¥äžã§åçž®ããåé¢ããéå
çž®æ§ã¬ã¹ãé ¢é žãå«æãã液çžã«æ¥è§Šãããæ®æ£
ã«ãããŠã ãååããããšãç¹åŸŽãšãããšã¿ããŒ
ã«ã®è£œé æ¹æ³ã1. Synthesis gas is continuously supplied to a liquid medium containing a ruthenium compound, a cobalt compound, and a halogen compound held in a reactor under high temperature and high pressure to produce a reaction product consisting of an oxygen-containing compound whose main component is ethanol. In this method, the unreacted synthesis gas is condensed below the reaction temperature, and the separated non-condensable gas is converted into acetic acid. A method for producing ethanol, the method comprising recovering volatilized ruthenium by bringing it into contact with a liquid phase containing ethanol.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP61235501A JPS6391337A (en) | 1986-10-04 | 1986-10-04 | Production of ethanol |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP61235501A JPS6391337A (en) | 1986-10-04 | 1986-10-04 | Production of ethanol |
Publications (2)
Publication Number | Publication Date |
---|---|
JPS6391337A JPS6391337A (en) | 1988-04-22 |
JPS6353166B2 true JPS6353166B2 (en) | 1988-10-21 |
Family
ID=16986957
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP61235501A Granted JPS6391337A (en) | 1986-10-04 | 1986-10-04 | Production of ethanol |
Country Status (1)
Country | Link |
---|---|
JP (1) | JPS6391337A (en) |
Families Citing this family (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB9503385D0 (en) * | 1995-02-21 | 1995-04-12 | Bp Chem Int Ltd | Process |
JP4945374B2 (en) * | 2007-08-29 | 2012-06-06 | æ¬ç°æç å·¥æ¥æ ªåŒäŒç€Ÿ | Subpallet reversing device and workpiece machining / assembling method with subpallet reversal |
-
1986
- 1986-10-04 JP JP61235501A patent/JPS6391337A/en active Granted
Also Published As
Publication number | Publication date |
---|---|
JPS6391337A (en) | 1988-04-22 |
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