WO2012018007A1 - Procédé pour la séparation de méthanol - Google Patents
Procédé pour la séparation de méthanol Download PDFInfo
- Publication number
- WO2012018007A1 WO2012018007A1 PCT/JP2011/067666 JP2011067666W WO2012018007A1 WO 2012018007 A1 WO2012018007 A1 WO 2012018007A1 JP 2011067666 W JP2011067666 W JP 2011067666W WO 2012018007 A1 WO2012018007 A1 WO 2012018007A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- methanol
- zeolite membrane
- carbon atoms
- methyl
- mass
- Prior art date
Links
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 title claims abstract description 411
- 238000000034 method Methods 0.000 title claims abstract description 39
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims abstract description 126
- 239000012528 membrane Substances 0.000 claims abstract description 121
- 229910021536 Zeolite Inorganic materials 0.000 claims abstract description 107
- 239000010457 zeolite Substances 0.000 claims abstract description 107
- 239000000203 mixture Substances 0.000 claims abstract description 81
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 73
- 125000004432 carbon atom Chemical group C* 0.000 claims abstract description 55
- 150000004702 methyl esters Chemical class 0.000 claims abstract description 31
- 239000013078 crystal Substances 0.000 claims abstract description 20
- 238000005809 transesterification reaction Methods 0.000 claims abstract description 19
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims abstract description 18
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 59
- 238000000926 separation method Methods 0.000 claims description 39
- 239000012466 permeate Substances 0.000 claims description 37
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 36
- 238000004519 manufacturing process Methods 0.000 claims description 30
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 19
- 229910000323 aluminium silicate Inorganic materials 0.000 claims description 19
- 239000000377 silicon dioxide Substances 0.000 claims description 18
- 238000006243 chemical reaction Methods 0.000 claims description 15
- 230000004907 flux Effects 0.000 claims description 13
- 150000002148 esters Chemical class 0.000 claims description 12
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims description 11
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 11
- 229910052710 silicon Inorganic materials 0.000 claims description 9
- 239000010703 silicon Substances 0.000 claims description 9
- 229910052782 aluminium Inorganic materials 0.000 claims description 8
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 8
- 239000000047 product Substances 0.000 claims description 6
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 claims description 4
- RJUFJBKOKNCXHH-UHFFFAOYSA-N Methyl propionate Chemical compound CCC(=O)OC RJUFJBKOKNCXHH-UHFFFAOYSA-N 0.000 claims description 3
- 229940017219 methyl propionate Drugs 0.000 claims description 3
- 230000003204 osmotic effect Effects 0.000 claims 1
- 238000009834 vaporization Methods 0.000 claims 1
- 239000012295 chemical reaction liquid Substances 0.000 abstract 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 29
- 239000007788 liquid Substances 0.000 description 20
- 238000005373 pervaporation Methods 0.000 description 17
- KKCBUQHMOMHUOY-UHFFFAOYSA-N sodium oxide Chemical compound [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 description 16
- 229910001948 sodium oxide Inorganic materials 0.000 description 16
- BTANRVKWQNVYAZ-UHFFFAOYSA-N butan-2-ol Chemical compound CCC(C)O BTANRVKWQNVYAZ-UHFFFAOYSA-N 0.000 description 15
- 238000005259 measurement Methods 0.000 description 14
- KFZMGEQAYNKOFK-UHFFFAOYSA-N 2-propanol Substances CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 13
- 238000002474 experimental method Methods 0.000 description 13
- 239000002994 raw material Substances 0.000 description 12
- 239000012527 feed solution Substances 0.000 description 11
- 238000004821 distillation Methods 0.000 description 10
- 239000000243 solution Substances 0.000 description 10
- 239000000843 powder Substances 0.000 description 9
- MSXVEPNJUHWQHW-UHFFFAOYSA-N 2-methylbutan-2-ol Chemical compound CCC(C)(C)O MSXVEPNJUHWQHW-UHFFFAOYSA-N 0.000 description 8
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 8
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 8
- -1 isovaleric acid ester Chemical class 0.000 description 8
- 239000011259 mixed solution Substances 0.000 description 8
- 239000002904 solvent Substances 0.000 description 7
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 6
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 description 6
- 239000003054 catalyst Substances 0.000 description 6
- KZHJGOXRZJKJNY-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Si]=O.O=[Al]O[Al]=O.O=[Al]O[Al]=O.O=[Al]O[Al]=O KZHJGOXRZJKJNY-UHFFFAOYSA-N 0.000 description 6
- 238000010438 heat treatment Methods 0.000 description 6
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 description 6
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 6
- 229910052863 mullite Inorganic materials 0.000 description 6
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 6
- 150000001298 alcohols Chemical class 0.000 description 5
- 238000009835 boiling Methods 0.000 description 5
- 230000008859 change Effects 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- VHVMXWZXFBOANQ-UHFFFAOYSA-N 1-Penten-3-ol Chemical compound CCC(O)C=C VHVMXWZXFBOANQ-UHFFFAOYSA-N 0.000 description 4
- HNVRRHSXBLFLIG-UHFFFAOYSA-N 3-hydroxy-3-methylbut-1-ene Chemical compound CC(C)(O)C=C HNVRRHSXBLFLIG-UHFFFAOYSA-N 0.000 description 4
- MXLMTQWGSQIYOW-UHFFFAOYSA-N 3-methyl-2-butanol Chemical compound CC(C)C(C)O MXLMTQWGSQIYOW-UHFFFAOYSA-N 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 230000032683 aging Effects 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- WOZVHXUHUFLZGK-UHFFFAOYSA-N dimethyl terephthalate Chemical compound COC(=O)C1=CC=C(C(=O)OC)C=C1 WOZVHXUHUFLZGK-UHFFFAOYSA-N 0.000 description 4
- 239000011521 glass Substances 0.000 description 4
- PHTQWCKDNZKARW-UHFFFAOYSA-N isoamylol Chemical compound CC(C)CCO PHTQWCKDNZKARW-UHFFFAOYSA-N 0.000 description 4
- MKUWVMRNQOOSAT-UHFFFAOYSA-N methylvinylmethanol Natural products CC(O)C=C MKUWVMRNQOOSAT-UHFFFAOYSA-N 0.000 description 4
- 239000012454 non-polar solvent Substances 0.000 description 4
- AQIXEPGDORPWBJ-UHFFFAOYSA-N pentan-3-ol Chemical compound CCC(O)CC AQIXEPGDORPWBJ-UHFFFAOYSA-N 0.000 description 4
- QPRQEDXDYOZYLA-UHFFFAOYSA-N 2-methylbutan-1-ol Chemical compound CCC(C)CO QPRQEDXDYOZYLA-UHFFFAOYSA-N 0.000 description 3
- RZVAJINKPMORJF-UHFFFAOYSA-N Acetaminophen Chemical compound CC(=O)NC1=CC=C(O)C=C1 RZVAJINKPMORJF-UHFFFAOYSA-N 0.000 description 3
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- KXKVLQRXCPHEJC-UHFFFAOYSA-N acetic acid trimethyl ester Natural products COC(C)=O KXKVLQRXCPHEJC-UHFFFAOYSA-N 0.000 description 3
- 230000005540 biological transmission Effects 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 238000006116 polymerization reaction Methods 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 239000005297 pyrex Substances 0.000 description 3
- KBPLFHHGFOOTCA-UHFFFAOYSA-N 1-Octanol Chemical compound CCCCCCCCO KBPLFHHGFOOTCA-UHFFFAOYSA-N 0.000 description 2
- XFRVVPUIAFSTFO-UHFFFAOYSA-N 1-Tridecanol Chemical compound CCCCCCCCCCCCCO XFRVVPUIAFSTFO-UHFFFAOYSA-N 0.000 description 2
- BZAZNULYLRVMSW-UHFFFAOYSA-N 2-Methyl-2-buten-3-ol Natural products CC(C)=C(C)O BZAZNULYLRVMSW-UHFFFAOYSA-N 0.000 description 2
- YIWUKEYIRIRTPP-UHFFFAOYSA-N 2-ethylhexan-1-ol Chemical compound CCCCC(CC)CO YIWUKEYIRIRTPP-UHFFFAOYSA-N 0.000 description 2
- BYDRTKVGBRTTIT-UHFFFAOYSA-N 2-methylprop-2-en-1-ol Chemical compound CC(=C)CO BYDRTKVGBRTTIT-UHFFFAOYSA-N 0.000 description 2
- ZSPTYLOMNJNZNG-UHFFFAOYSA-N 3-Buten-1-ol Chemical compound OCCC=C ZSPTYLOMNJNZNG-UHFFFAOYSA-N 0.000 description 2
- HFYAEUXHCMTPOL-UHFFFAOYSA-N 3-Methyl-1-penten-3-ol Chemical compound CCC(C)(O)C=C HFYAEUXHCMTPOL-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 2
- OQAGVSWESNCJJT-UHFFFAOYSA-N Methyl 3-methylbutanoate Chemical compound COC(=O)CC(C)C OQAGVSWESNCJJT-UHFFFAOYSA-N 0.000 description 2
- CRZQGDNQQAALAY-UHFFFAOYSA-N Methyl benzeneacetate Chemical compound COC(=O)CC1=CC=CC=C1 CRZQGDNQQAALAY-UHFFFAOYSA-N 0.000 description 2
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 2
- 239000004642 Polyimide Substances 0.000 description 2
- 229920000297 Rayon Polymers 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- XXROGKLTLUQVRX-UHFFFAOYSA-N allyl alcohol Chemical compound OCC=C XXROGKLTLUQVRX-UHFFFAOYSA-N 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 150000001735 carboxylic acids Chemical class 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 230000006837 decompression Effects 0.000 description 2
- 238000000151 deposition Methods 0.000 description 2
- LQZZUXJYWNFBMV-UHFFFAOYSA-N dodecan-1-ol Chemical compound CCCCCCCCCCCCO LQZZUXJYWNFBMV-UHFFFAOYSA-N 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 230000008020 evaporation Effects 0.000 description 2
- ZSIAUFGUXNUGDI-UHFFFAOYSA-N hexan-1-ol Chemical compound CCCCCCO ZSIAUFGUXNUGDI-UHFFFAOYSA-N 0.000 description 2
- 239000003112 inhibitor Substances 0.000 description 2
- 150000002484 inorganic compounds Chemical class 0.000 description 2
- 229910010272 inorganic material Inorganic materials 0.000 description 2
- CPJRRXSHAYUTGL-UHFFFAOYSA-N isopentenyl alcohol Chemical compound CC(=C)CCO CPJRRXSHAYUTGL-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
- TZIHFWKZFHZASV-UHFFFAOYSA-N methyl formate Chemical compound COC=O TZIHFWKZFHZASV-UHFFFAOYSA-N 0.000 description 2
- NUKZAGXMHTUAFE-UHFFFAOYSA-N methyl hexanoate Chemical compound CCCCCC(=O)OC NUKZAGXMHTUAFE-UHFFFAOYSA-N 0.000 description 2
- BHIWKHZACMWKOJ-UHFFFAOYSA-N methyl isobutyrate Chemical compound COC(=O)C(C)C BHIWKHZACMWKOJ-UHFFFAOYSA-N 0.000 description 2
- JGHZJRVDZXSNKQ-UHFFFAOYSA-N methyl octanoate Chemical compound CCCCCCCC(=O)OC JGHZJRVDZXSNKQ-UHFFFAOYSA-N 0.000 description 2
- OSWPMRLSEDHDFF-UHFFFAOYSA-N methyl salicylate Chemical compound COC(=O)C1=CC=CC=C1O OSWPMRLSEDHDFF-UHFFFAOYSA-N 0.000 description 2
- KPSSIOMAKSHJJG-UHFFFAOYSA-N neopentyl alcohol Chemical compound CC(C)(C)CO KPSSIOMAKSHJJG-UHFFFAOYSA-N 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- GLDOVTGHNKAZLK-UHFFFAOYSA-N octadecan-1-ol Chemical compound CCCCCCCCCCCCCCCCCCO GLDOVTGHNKAZLK-UHFFFAOYSA-N 0.000 description 2
- NWVVVBRKAWDGAB-UHFFFAOYSA-N p-methoxyphenol Chemical compound COC1=CC=C(O)C=C1 NWVVVBRKAWDGAB-UHFFFAOYSA-N 0.000 description 2
- ZHZCYWWNFQUZOR-UHFFFAOYSA-N pent-4-en-2-ol Chemical compound CC(O)CC=C ZHZCYWWNFQUZOR-UHFFFAOYSA-N 0.000 description 2
- JYVLIDXNZAXMDK-UHFFFAOYSA-N pentan-2-ol Chemical compound CCCC(C)O JYVLIDXNZAXMDK-UHFFFAOYSA-N 0.000 description 2
- 229920001721 polyimide Polymers 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 229920001296 polysiloxane Polymers 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- ASUAYTHWZCLXAN-UHFFFAOYSA-N prenol Chemical compound CC(C)=CCO ASUAYTHWZCLXAN-UHFFFAOYSA-N 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 229910001220 stainless steel Inorganic materials 0.000 description 2
- 239000010935 stainless steel Substances 0.000 description 2
- BTSIZIIPFNVMHF-ONEGZZNKSA-N (E)-2-penten-1-ol Chemical compound CC\C=C\CO BTSIZIIPFNVMHF-ONEGZZNKSA-N 0.000 description 1
- 239000001586 (Z)-pent-2-en-1-ol Substances 0.000 description 1
- WBYWAXJHAXSJNI-VOTSOKGWSA-M .beta-Phenylacrylic acid Natural products [O-]C(=O)\C=C\C1=CC=CC=C1 WBYWAXJHAXSJNI-VOTSOKGWSA-M 0.000 description 1
- WJFKNYWRSNBZNX-UHFFFAOYSA-N 10H-phenothiazine Chemical compound C1=CC=C2NC3=CC=CC=C3SC2=C1 WJFKNYWRSNBZNX-UHFFFAOYSA-N 0.000 description 1
- NVGOATMUHKIQQG-UHFFFAOYSA-N 2-Methyl-3-buten-1-ol Chemical compound OCC(C)C=C NVGOATMUHKIQQG-UHFFFAOYSA-N 0.000 description 1
- BFSVOASYOCHEOV-UHFFFAOYSA-N 2-diethylaminoethanol Chemical compound CCN(CC)CCO BFSVOASYOCHEOV-UHFFFAOYSA-N 0.000 description 1
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 description 1
- 229940093475 2-ethoxyethanol Drugs 0.000 description 1
- GWYFCOCPABKNJV-UHFFFAOYSA-M 3-Methylbutanoic acid Natural products CC(C)CC([O-])=O GWYFCOCPABKNJV-UHFFFAOYSA-M 0.000 description 1
- NSPPRYXGGYQMPY-UHFFFAOYSA-N 3-Methylbuten-2-ol-1 Natural products CC(C)C(O)=C NSPPRYXGGYQMPY-UHFFFAOYSA-N 0.000 description 1
- UZFMOKQJFYMBGY-UHFFFAOYSA-N 4-hydroxy-TEMPO Chemical group CC1(C)CC(O)CC(C)(C)N1[O] UZFMOKQJFYMBGY-UHFFFAOYSA-N 0.000 description 1
- 239000005711 Benzoic acid Substances 0.000 description 1
- WPYMKLBDIGXBTP-UHFFFAOYSA-N Benzoic acid Natural products OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 1
- WWZKQHOCKIZLMA-UHFFFAOYSA-N Caprylic acid Natural products CCCCCCCC(O)=O WWZKQHOCKIZLMA-UHFFFAOYSA-N 0.000 description 1
- 239000005635 Caprylic acid (CAS 124-07-2) Substances 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- JGFBQFKZKSSODQ-UHFFFAOYSA-N Isothiocyanatocyclopropane Chemical compound S=C=NC1CC1 JGFBQFKZKSSODQ-UHFFFAOYSA-N 0.000 description 1
- BZLVMXJERCGZMT-UHFFFAOYSA-N Methyl tert-butyl ether Chemical compound COC(C)(C)C BZLVMXJERCGZMT-UHFFFAOYSA-N 0.000 description 1
- UEEJHVSXFDXPFK-UHFFFAOYSA-N N-dimethylaminoethanol Chemical compound CN(C)CCO UEEJHVSXFDXPFK-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- IAXXETNIOYFMLW-GYSYKLTISA-N [(1r,3r,4r)-4,7,7-trimethyl-3-bicyclo[2.2.1]heptanyl] 2-methylprop-2-enoate Chemical compound C1C[C@@]2(C)[C@H](OC(=O)C(=C)C)C[C@@H]1C2(C)C IAXXETNIOYFMLW-GYSYKLTISA-N 0.000 description 1
- 239000001089 [(2R)-oxolan-2-yl]methanol Substances 0.000 description 1
- 238000010306 acid treatment Methods 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 125000005396 acrylic acid ester group Chemical group 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 239000003570 air Substances 0.000 description 1
- ANBBXQWFNXMHLD-UHFFFAOYSA-N aluminum;sodium;oxygen(2-) Chemical compound [O-2].[O-2].[Na+].[Al+3] ANBBXQWFNXMHLD-UHFFFAOYSA-N 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 235000010233 benzoic acid Nutrition 0.000 description 1
- WLJVXDMOQOGPHL-UHFFFAOYSA-N benzyl-alpha-carboxylic acid Natural products OC(=O)CC1=CC=CC=C1 WLJVXDMOQOGPHL-UHFFFAOYSA-N 0.000 description 1
- GWYFCOCPABKNJV-UHFFFAOYSA-N beta-methyl-butyric acid Natural products CC(C)CC(O)=O GWYFCOCPABKNJV-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 description 1
- 150000001656 butanoic acid esters Chemical class 0.000 description 1
- PWLNAUNEAKQYLH-UHFFFAOYSA-N butyric acid octyl ester Natural products CCCCCCCCOC(=O)CCC PWLNAUNEAKQYLH-UHFFFAOYSA-N 0.000 description 1
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 1
- 239000000292 calcium oxide Substances 0.000 description 1
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 1
- 150000001244 carboxylic acid anhydrides Chemical class 0.000 description 1
- 229930016911 cinnamic acid Natural products 0.000 description 1
- 235000013985 cinnamic acid Nutrition 0.000 description 1
- CCRCUPLGCSFEDV-UHFFFAOYSA-N cinnamic acid methyl ester Natural products COC(=O)C=CC1=CC=CC=C1 CCRCUPLGCSFEDV-UHFFFAOYSA-N 0.000 description 1
- 150000004696 coordination complex Chemical class 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- HPXRVTGHNJAIIH-UHFFFAOYSA-N cyclohexanol Chemical compound OC1CCCCC1 HPXRVTGHNJAIIH-UHFFFAOYSA-N 0.000 description 1
- XCIXKGXIYUWCLL-UHFFFAOYSA-N cyclopentanol Chemical compound OC1CCCC1 XCIXKGXIYUWCLL-UHFFFAOYSA-N 0.000 description 1
- 229960002887 deanol Drugs 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000003205 fragrance Substances 0.000 description 1
- 150000002400 hexanoic acid esters Chemical class 0.000 description 1
- 239000012510 hollow fiber Substances 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 229940035429 isobutyl alcohol Drugs 0.000 description 1
- WDAXFOBOLVPGLV-UHFFFAOYSA-N isobutyric acid ethyl ester Natural products CCOC(=O)C(C)C WDAXFOBOLVPGLV-UHFFFAOYSA-N 0.000 description 1
- 125000005397 methacrylic acid ester group Chemical group 0.000 description 1
- 229940095102 methyl benzoate Drugs 0.000 description 1
- WBYWAXJHAXSJNI-UHFFFAOYSA-N methyl p-hydroxycinnamate Natural products OC(=O)C=CC1=CC=CC=C1 WBYWAXJHAXSJNI-UHFFFAOYSA-N 0.000 description 1
- 229960001047 methyl salicylate Drugs 0.000 description 1
- CCRCUPLGCSFEDV-BQYQJAHWSA-N methyl trans-cinnamate Chemical compound COC(=O)\C=C\C1=CC=CC=C1 CCRCUPLGCSFEDV-BQYQJAHWSA-N 0.000 description 1
- 239000012778 molding material Substances 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- UUIQMZJEGPQKFD-UHFFFAOYSA-N n-butyric acid methyl ester Natural products CCCC(=O)OC UUIQMZJEGPQKFD-UHFFFAOYSA-N 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- BTSIZIIPFNVMHF-UHFFFAOYSA-N nor-leaf alcohol Natural products CCC=CCO BTSIZIIPFNVMHF-UHFFFAOYSA-N 0.000 description 1
- 229960002446 octanoic acid Drugs 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- LQAVWYMTUMSFBE-UHFFFAOYSA-N pent-4-en-1-ol Chemical compound OCCCC=C LQAVWYMTUMSFBE-UHFFFAOYSA-N 0.000 description 1
- CPKRTCXZUIFKME-UHFFFAOYSA-N pentan-1-ol;pentan-2-ol Chemical compound CCCCCO.CCCC(C)O CPKRTCXZUIFKME-UHFFFAOYSA-N 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 229950000688 phenothiazine Drugs 0.000 description 1
- WVDDGKGOMKODPV-ZQBYOMGUSA-N phenyl(114C)methanol Chemical compound O[14CH2]C1=CC=CC=C1 WVDDGKGOMKODPV-ZQBYOMGUSA-N 0.000 description 1
- 229960003424 phenylacetic acid Drugs 0.000 description 1
- 239000003279 phenylacetic acid Substances 0.000 description 1
- 150000003021 phthalic acid derivatives Chemical class 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 235000019353 potassium silicate Nutrition 0.000 description 1
- 150000003151 propanoic acid esters Chemical class 0.000 description 1
- 150000004053 quinones Chemical class 0.000 description 1
- 150000003902 salicylic acid esters Chemical class 0.000 description 1
- 238000001577 simple distillation Methods 0.000 description 1
- 229910001388 sodium aluminate Inorganic materials 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 1
- BSYVTEYKTMYBMK-UHFFFAOYSA-N tetrahydrofurfuryl alcohol Chemical compound OCC1CCCO1 BSYVTEYKTMYBMK-UHFFFAOYSA-N 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/74—Separation; Purification; Use of additives, e.g. for stabilisation
- C07C29/76—Separation; Purification; Use of additives, e.g. for stabilisation by physical treatment
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D61/00—Processes of separation using semi-permeable membranes, e.g. dialysis, osmosis or ultrafiltration; Apparatus, accessories or auxiliary operations specially adapted therefor
- B01D61/36—Pervaporation; Membrane distillation; Liquid permeation
- B01D61/362—Pervaporation
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/02—Inorganic material
- B01D71/028—Molecular sieves
- B01D71/0281—Zeolites
Definitions
- the present invention relates to a method for efficiently separating methanol.
- esters are used for many purposes.
- phthalic acid esters are used as plasticizers
- acrylic acid esters or methacrylic acid esters are used as monomers for producing polymers, and the resulting polymers are used as molding materials, paints, adhesives, and the like.
- dimethyl terephthalate is used as a raw material for producing polyester.
- propionic acid ester, butyric acid ester, isovaleric acid ester, caproic acid ester, caprylic acid ester, benzoic acid ester, phenylacetic acid ester, cinnamic acid ester, and salicylic acid ester are used as synthetic fragrances.
- methyl acrylate and methyl methacrylate are sometimes collectively referred to as methyl (meth) acrylate.
- monohydric alcohol esters having 4 or more carbon atoms are produced by transesterification with methyl esters.
- an alcohol having 2 or more carbon atoms may be referred to as a higher alcohol
- an ester of an alcohol having 2 or more carbon atoms may be referred to as a higher ester.
- the advantages of the transesterification reaction using methyl ester as a raw material include methyl ester and higher alcohol as raw materials. It is easy to obtain a high-concentration product and is easy to handle, and the only by-product is methanol.
- the transesterification reaction is an equilibrium reaction, and methyl ester or higher alcohol is usually used in an excess molar amount in order to obtain a higher ester efficiently.
- Methyl ester may be used in excess moles relative to the higher alcohol, but if the boiling point of the methyl ester is higher than that of the higher alcohol or if the methyl ester is more valuable than the higher alcohol, the higher alcohol is in excess of the methyl ester. Mole is often used. Therefore, the reaction solution at the end of the reaction is a mixture of methanol as a reaction by-product, higher unreacted alcohol and higher ester as a reaction product. Among these, the higher ester which is a reaction product has a large boiling point difference from methanol and higher alcohol, so that separation by distillation is relatively easy, and a mixture of methanol and higher alcohol excluding the higher ester can be obtained. .
- the reaction solution is heated to a temperature equal to or higher than the boiling point of methanol of 64.7 ° C. (under atmospheric pressure).
- the methanol produced may be removed from the reaction solution by evaporation.
- the higher alcohol is used in an excess molar amount relative to the methyl ester, the composition of the reaction solution at the initial stage of the reaction is low in methanol and high in high alcohol. Steam is obtained.
- Non-Patent Document 1 when methyl ester that forms an azeotrope with methanol is a raw material, a vapor of a mixture of methanol, a higher alcohol, and methyl ester can be obtained by heating the reaction solution.
- the methyl esters that form such an azeotrope are shown in Table 1 (Non-Patent Document 1).
- a higher alcohol can be separated and recovered at a high concentration from a mixture of methanol and a higher alcohol or a mixture of methanol, a higher alcohol and a methyl ester, it can be reused as a raw material for transesterification.
- methanol can be recovered at a high concentration, methanol can be used for other purposes. In this case, it is desirable that the concentration of other components contained in the recovered component is as low as possible.
- Distillation is usually used to separate methanol and higher alcohols.
- distillation is a process that consumes a great deal of heat energy.
- the boiling point of the higher alcohol is close to that of methanol, if high concentrations of methanol and higher alcohol are to be obtained, precise separation by a multistage distillation column is required, and more heat energy is consumed. become.
- extraction by addition of a solvent may be used to separate methanol and higher alcohol.
- water is used as the solvent, only methanol can be dissolved in water, and if a nonpolar solvent such as hexane is used, only higher alcohols can be dissolved in the nonpolar solvent.
- a high-purity higher alcohol is to be obtained when a nonpolar solvent is used, the nonpolar solvent and the higher alcohol must be separated by some method, which complicates the process. Further, when water is used, it is difficult to separate higher alcohol and methanol, which have a high solubility in water.
- a separation method using a membrane for separating a mixture has been proposed. Separation using a membrane is superior in terms of consumption of heat energy compared to separation by distillation alone.
- membranes used for separation include organic polyvinyl alcohol membranes, polyimide membranes, and inorganic zeolite membranes.
- Organic membranes are superior in terms of productivity compared to inorganic membranes, and inorganic membranes are superior in terms of separability, heat resistance, and chemical resistance.
- Patent Document 1 As a separation method using a membrane for separation of the mixture, for example, vapor of a mixture obtained by transesterification using ethanol and methyl methacrylate as raw materials using a special polyimide hollow fiber membrane having chemical resistance, or 1 -A method for selectively separating methanol from the vapor of a mixture obtained by transesterification using butanol and methyl (meth) acrylate as raw materials has been proposed (Patent Document 1).
- methanol having a higher concentration than the azeotropic composition of methanol and methyl (meth) acrylate can be obtained.
- the composition of the raw material does not describe a composition in which methyl (meth) acrylate is excessive, higher alcohol is excessive, and vapor of a mixture composed of methanol and a monohydric alcohol having 4 or more carbon atoms is generated.
- water, methanol, or ethanol can be efficiently separated at a relatively high concentration from the exemplified azeotropic mixture.
- a mixture to be separated is a mixture of water / alcohol solvent, alcohol solvent / hydrocarbon solvent, alcohol solvent / ether solvent, which has methanol and 4 or more carbon atoms. Mixtures consisting of monohydric alcohols are not described.
- Patent Document 4 a method for separating methanol and methyl acetate, which are azeotropic mixtures, using a Y-type zeolite membrane has been proposed.
- methanol and methyl acetate having a higher concentration than the azeotropic composition can be obtained with less heat energy than the multistage distillation column.
- what is exemplified as a mixture to be separated does not describe a mixture of methanol and a monohydric alcohol having 4 or more carbon atoms.
- JP 2007-63171 A Japanese Patent Laid-Open No. 10-212117 JP-A-8-257301 JP 2006-306762 A
- An object of the present invention is to efficiently separate high-concentration methanol from a mixture containing methanol and a monohydric alcohol having 4 or more carbon atoms.
- the present invention is a method for separating methanol from a mixture containing methanol and a monohydric alcohol having 4 or more carbon atoms using a zeolite membrane having a FAU type crystal structure.
- the present invention performs a transesterification reaction between a monohydric alcohol having 4 or more carbon atoms and a methyl ester derived from a carboxylic acid having 3 or more carbon atoms. From the obtained reaction solution, a FAU type crystal structure is obtained. This is a method for separating methanol using a zeolite membrane having
- the present invention performs a transesterification reaction between a monohydric alcohol having 4 or more carbon atoms and a methyl ester derived from a carboxylic acid having 3 or more carbon atoms. From the resultant reaction solution, a FAU type crystal structure is obtained.
- This is a method for producing a transesterification product in which methanol is separated using a zeolite membrane having the following.
- high-concentration methanol can be efficiently separated from a mixture containing methanol and a monohydric alcohol having 4 or more carbon atoms.
- a zeolite membrane having a FAU type crystal structure that is, an X-type zeolite membrane or a Y-type zeolite membrane is used from the viewpoint of separability, heat resistance, and chemical resistance.
- a Y-type zeolite membrane is preferable.
- X-type zeolite membrane and Y-type zeolite membrane can be formed by depositing NaX-type zeolite crystals and NaY-type zeolite crystals on the surface of a porous tubular support containing an inorganic compound as a component.
- an inorganic compound that is a component of the porous tubular support ⁇ -alumina, mullite, and stainless steel are preferable in view of membrane separation performance.
- a heating method a method using hot water of high temperature and high pressure, a so-called hydrothermal synthesis method is preferable.
- heating can be performed with a heat medium such as oil, hot air, microwaves, or the like.
- a heat medium such as oil, hot air, microwaves, or the like.
- the temperature is preferably 100 to 140 ° C.
- the heating time is preferably 3 to 27 hours for the X-type zeolite membrane, and preferably 2 to 6 hours for the Y-type zeolite membrane. .
- the temperature is set to 120 to 140 ° C. for 1 to 2 hours, and then the temperature is set to 100 ° C. or more and less than 120 ° C. Heating for ⁇ 4 hours is preferred.
- 2450 MHz which can be utilized with a household microwave oven is preferable as a frequency.
- the silica / alumina molar ratio of the aluminosilicate gel is 2 to 10 in the case of the X-type zeolite membrane. Is preferred.
- components other than silica and alumina constituting the alumina silicate gel include sodium oxide and water.
- the molar ratio of the sodium oxide / silica is preferably 1 to 3, and the molar ratio of water / sodium oxide is preferably 20 to 50.
- the silica / alumina molar ratio of the aluminosilicate gel is preferably 20 or more, and more preferably 25 or more.
- the upper limit of the silica / alumina molar ratio is preferably 50 or less.
- components other than silica and alumina constituting the alumina silicate gel include sodium oxide and water.
- the molar ratio of sodium oxide / silica is preferably 0.6 to 1.2, and the molar ratio of water / sodium oxide is preferably 40 to 100.
- the aging of the aluminosilicate gel is preferably 15 to 21 hours at 20 to 40 ° C.
- the thus obtained Y-type zeolite membrane has a silicon / aluminum molar ratio of the zeolite constituting the membrane of 2.5 or more, and a membrane having high separation performance and high permeation flux can be obtained. It is preferable that the molar ratio of silicon / aluminum of the zeolite constituting the Y-type zeolite membrane is 2.7 or more. When the silicon / aluminum molar ratio of the zeolite constituting the Y-type zeolite membrane is 4.0 or less, an increase in silicon content lost in the aluminosilicate gel can be suppressed and defects such as pinholes are generated. It is preferable that a Y-type zeolite membrane can be produced without any problems.
- a mixture having a methanol concentration of 10% by mass and a 1-butanol concentration of 90% by mass is used as a feed liquid, and the temperature is 60 ° C.
- the monohydric alcohol having 4 or more carbon atoms which is a component of the mixture with methanol to be separated in the present invention, is not particularly limited.
- 1-butanol, 2-butanol (sec-butyl alcohol), 2-methyl-1-propanol (isobutyl alcohol), 2-methyl are relatively close in boiling point to methanol and difficult to separate by simple distillation.
- -2-propanol (t-butyl alcohol), 3-buten-1-ol, 3-buten-2-ol, methallyl alcohol, 2-pentanol, 3-pentanol, 2-methyl-2-butanol (t -Amyl alcohol), 3-methyl-2-butanol, 2,2-dimethyl-1-propanol, 4-penten-2-ol, 1-penten-3-ol, 3-methyl-1-penten-3-ol Or 2-methyl-3-buten-2-ol is preferred.
- ethanol which is an alcohol with 2 carbon atoms
- composition of the mixture of methanol and monohydric alcohol having 4 or more carbon atoms used in the present invention is not particularly limited, but in order to obtain a high-concentration methanol of 90% by mass or higher at a temperature of 40 ° C. or higher,
- the methanol concentration is preferably 5% by mass or more.
- Membrane separation can be performed even if the mixture of methanol and a monohydric alcohol having 4 or more carbon atoms contains a methyl ester derived from a carboxylic acid having 3 or more carbon atoms.
- the methyl ester derived from a carboxylic acid having 3 or more carbon atoms is not particularly limited.
- methyl ester derived from a carboxylic acid having 3 or more carbon atoms methyl propionate or methyl (meth) acrylate is difficult to separate by distillation by forming an azeotrope with methanol, In particular, it is preferable from the viewpoint that membrane separation is effective.
- Methyl esters derived from carboxylic acids having 2 or less carbon atoms such as methyl formate and methyl acetate, are more selective for separation by zeolite membranes than methyl esters derived from carboxylic acids having 3 or more carbon atoms. There is a low tendency.
- a mixture of methanol, a monohydric alcohol having 4 or more carbon atoms, and a methyl ester derived from a carboxylic acid having 3 or more carbon atoms is further composed of a carboxylic acid having 3 or more carbon atoms and a monohydric alcohol having 4 or more carbon atoms.
- Membrane separation can be carried out even if it contains an induced ester.
- Such a mixture containing methanol and a monohydric alcohol having 4 or more carbon atoms can be obtained by a transesterification reaction.
- a catalyst By adding a catalyst to a monohydric alcohol having 4 or more carbon atoms and a methyl ester derived from a carboxylic acid having 3 or more carbon atoms to cause a transesterification reaction, a monohydric alcohol having 4 or more carbon atoms as a raw material, In addition to a methyl ester derived from a carboxylic acid having 3 or more carbon atoms, a catalyst, a mixture containing methanol as a product, and an ester derived from a carboxylic acid having 3 or more carbon atoms and a monohydric alcohol having 4 or more carbon atoms A reaction solution is obtained.
- the catalyst that can be used in the transesterification reaction is not particularly limited, but a metal complex catalyst such as titanium tetraalkoxide and dialkyltin oxide and a basic catalyst such as calcium oxide are preferable. Acidic catalysts such as sulfuric acid and paratoluene sulfonic acid may dissolve the membrane when contacted with the zeolite membrane.
- polymerization inhibitors include N-oxy radical compounds such as 4-hydroxy-2,2,6,6-tetramethylpiperidine-N-oxyl, phenol compounds such as p-methoxyphenol, and quinone compounds such as hydroquinone. And amine compounds such as phenothiazine. These can be used alone or in admixture of two or more.
- methanol is selectively permeated and monovalent alcohol having 4 or more carbon atoms is hardly permeated.
- the high-concentration methanol when permeated in the vapor state is preferably cooled to a liquid state.
- a method of separating a mixture containing methanol and a monohydric alcohol having 4 or more carbon atoms in the present invention by a zeolite membrane having a FAU type crystal structure a liquid state (pervaporation method) or a vapor state (vapor) And a method of separation by a permeation method).
- the pervaporation method is preferable in that the apparatus can be made compact, and the vapor permeation method is preferable in that the consumption of heat energy can be reduced without causing a phase change.
- use in combination with distillation is preferable from the viewpoint of reducing the selectivity of separation and the consumption of heat energy.
- a difference in methanol concentration between the permeation side and the supply side with respect to the membrane.
- Specific means for providing the concentration difference include applying a large differential pressure between the permeate side and the supply side, or flowing a gas other than methanol so that methanol does not stay on the permeate side.
- the supply side In order to apply a large differential pressure, the supply side must be pressurized or the permeate side must be depressurized.
- the pressure on the supply side is preferably 50 to 470 kPa
- the pressure on the transmission side is preferably 0.5 kPa or less
- the pressure on the supply side is atmospheric pressure
- the pressure side on the transmission side is 0.1 kPa or less. More preferred.
- gas other than methanol flowing so that methanol does not stay on the permeate side air, nitrogen, and argon are preferable in consideration of inertness that does not react with methanol and availability.
- the temperature of the mixture on the supply side in the separation is preferably 0 to 200 ° C. in view of ease of realization, and preferably 30 to 180 ° C. in consideration of the permeation amount of methanol, and the selectivity of membrane separation and the heat consumed. Considering energy, 50 to 150 ° C. is more preferable.
- the mixture is supplied in a vapor state by the vapor permeation method, the vapor can be superheated before the membrane separation in order to increase the permeation amount of methanol.
- methanol can be efficiently separated from a mixture containing methanol and a monohydric alcohol having 4 or more carbon atoms.
- methanol can be efficiently separated from the obtained reaction solution, and thus the transesterified product can be efficiently obtained.
- Porous mullite support made by Nikkato Corporation, trade name: PM tube, outer diameter
- NaY-type zeolite powder (trade name: HSZ-320NAA, manufactured by Tosoh Corporation) 12 mm, an inner diameter of 9 mm, an average pore diameter of 1.3 ⁇ m, a porosity of 45%, and a total length of 100 mm) were applied with fingers until the zeolite powder precipitated.
- Aluminosilicate gel was charged into an autoclave having a capacity of 0.5 L, and the support coated with the above-mentioned zeolite powder was immersed therein.
- the autoclave was sealed and hydrothermal synthesis was performed at 100 ° C. for 6 hours.
- the produced Y-type zeolite membrane (Y-type-1) is washed with water, dried, and using an X-ray analyzer (XRD-6100, manufactured by Shimadzu Corporation), the light source: Cu-K ⁇ , An X-ray diffraction spectrum was measured at a measurement point interval of 0.1 degree and a measurement range of 5 to 45 degree, and it was confirmed that a peak of NaY type zeolite crystal appeared.
- a zeolite membrane was formed under the same conditions, and the zeolite membrane was accelerated using SEM / EDS (with a scanning electron microscope JSM6060A manufactured by JEOL Ltd./minicup type EDS detector manufactured by JEOL Ltd.): As a result of measurement at 20 kV, spot size (filament current): 60 mA, measurement time: 300 seconds, working distance: 10 mm, the silicon / aluminum molar ratio was 2.5.
- Aluminosilicate gel is charged into an autoclave, the support coated with zeolite powder is immersed, the autoclave is sealed, and hydrothermal synthesis is performed at 100 ° C. for 6 hours. Then, the aluminosilicate gel is charged into a Pyrex (registered trademark) container. Then, a support coated with zeolite powder is immersed, and microwaves are continuously applied to a Pyrex (registered trademark) container using a microwave reactor (manufactured by Shikoku Keiki Kogyo Co., Ltd., microwave frequency 2450 ⁇ 50 MHz, output 1 kW).
- a microwave reactor manufactured by Shikoku Keiki Kogyo Co., Ltd., microwave frequency 2450 ⁇ 50 MHz, output 1 kW.
- the Y-type zeolite membrane (Y) was prepared in the same manner as in Production Example 1 except that the temperature in the container was changed to 100 ° C. by irradiation and the microwave was intermittently irradiated to change the treatment to 100 ° C. for 4 hours.
- a mold-2) was produced.
- a zeolite membrane was formed under the same conditions, and the zeolite membrane was manufactured using SEM / EDS (with scanning electron microscope JSM6060A manufactured by JEOL Ltd./minicup type EDS detector manufactured by JEOL Ltd.). As a result of measurement under the same conditions as in Example 1, the molar ratio of silicon / aluminum was 2.7.
- a zeolite membrane was formed under the same conditions, and the zeolite membrane was manufactured using SEM / EDS (with scanning electron microscope JSM6060A manufactured by JEOL Ltd./minicup type EDS detector manufactured by JEOL Ltd.). As a result of measurement under the same conditions as in Example 1, the silicon / aluminum molar ratio was 2.3.
- a Y-type zeolite membrane As an aluminosilicate gel, a Y-type zeolite membrane (Y-type -8) was produced in the same manner as in Production Example 1 except that the process of aging at 30 ° C. for 17 hours was changed to the process of aging at 30 ° C. for 12 hours. .
- a Y-type zeolite membrane (Y-type-9) was prepared in the same manner as in Production Example 1, except that the treatment was aged at 30 ° C. for 17 hours and the treatment was aged at 30 ° C. for 24 hours. .
- NaX-type zeolite powder (Sigma Aldrich Japan Co., Ltd., Molecular Sieves 13X powder) was added to the surface of the porous mullite support with a finger until the zeolite powder was precipitated. .
- Silica / alumina / sodium oxide / water 3.6 / 1 / 5.04 / 252 (molar ratio) was prepared, and the mixture was stirred at room temperature for 4 hours to obtain an aluminosilicate gel. Obtained.
- Aluminosilicate gel was charged into an autoclave having a capacity of 0.5 L, and the support coated with the above-mentioned zeolite powder was immersed therein.
- the autoclave was sealed and hydrothermal synthesis was performed at 100 ° C. for 24 hours.
- the produced X-type zeolite membrane (X-type-1) is washed with water, dried, and using an X-ray analyzer (XRD-6100 manufactured by Shimadzu Corporation), the light source: Cu-K ⁇ , An X-ray diffraction spectrum was measured at a measurement point interval of 0.1 degree and a measurement range of 5 to 45 degree, and it was confirmed that a peak of NaX type zeolite crystal appeared.
- a zeolite membrane was formed under the same conditions, and the zeolite membrane was manufactured using SEM / EDS (with scanning electron microscope JSM6060A manufactured by JEOL Ltd./minicup type EDS detector manufactured by JEOL Ltd.). As a result of measurement under the same conditions as in Example 1, the silicon / aluminum molar ratio was 2.5.
- Example 1 Among the zeolite membranes produced as described above, the separation performance by pervaporation of those prepared on the porous support was measured.
- a Y-type zeolite membrane was attached to the apparatus shown in FIG. More specifically, a supply liquid container (2) having a capacity of 0.3 L is installed inside the constant temperature water tank (1), and the temperature of the supply liquid in the supply liquid container (2) is kept constant. did.
- the feed solution was filled with 0.25 L of a mixture of methanol and 1-butanol.
- a Dimroth condenser was attached to the supply liquid container (2) to suppress volatilization of the supply liquid.
- the Y-type zeolite membrane (3) was immersed in the supply liquid, one end was sealed, and the other end was connected to the glass vacuum line (5) via the silicone tube (4).
- the glass decompression line (5) was branched by a switching cock (6), and each line was connected to a vacuum pump (9) via a trap pipe (7).
- the components of the feed liquid permeate the Y-type zeolite membrane (3) in the form of steam, and the permeated steam is cooled by liquid nitrogen filled in the Dewar bottle (8). It collected with the trap pipe
- the mass and composition of the liquid (permeate) collected in the trap tube (7) were measured by operating the cock (6) for switching every 0.5 hour.
- the permeate was added to the feed solution so that the mass and composition of the feed solution did not change.
- the measurement was terminated when the mass and composition of the permeate were stable and almost no change was observed three times in succession, and the average was determined as the amount of permeate (kg) and methanol concentration (% by mass). Normally, the mass and composition of the permeate became stable after 1 to 1.5 hours had passed from the start of permeation, and the measurement was completed when 2.5 to 3 hours had elapsed.
- the effective membrane area of the Y-type zeolite membrane (3) formed on the porous support was 18.84 cm from the fact that the 50 mm long portion of the 100 mm long porous mullite support was exposed. It was 2.
- the pressure reduction degree of the apparatus under measurement was kept at 0.1 kPa or less.
- the composition of the permeate was measured with a gas chromatograph.
- a feed solution which is a methanol / 1-butanol mixture with a methanol concentration of 9.80% by mass is prepared from methanol (special grade manufactured by Kanto Chemical Co., Ltd.) and 1-butanol (special grade manufactured by Kanto Chemical Co., Ltd.).
- the obtained zeolite membrane (Y-type-1) was immersed, and pervaporation experiment was conducted at a temperature of 60 ° C. When the mass and composition of the permeate were stabilized, the permeate methanol concentration was 95.70% by mass, the separation factor ⁇ was 210, and the permeation flux Q was 0.60 kg / (m 2 ⁇ h). The results are shown in Table 2. Note that the effective membrane area of the zeolite membrane in the pervaporation experiment was 18.84 cm 2 .
- Examples 2 to 19 The pervaporation experiment of methanol / 1-butanol mixture using a zeolite membrane was performed in the same manner as in Example 1 except that the methanol concentration of the feed solution and the zeolite membrane were changed as shown in Tables 2 and 3. The results of the examples are shown in Tables 2 and 3.
- the effective membrane area of the zeolite membrane in the pervaporation separation experiment was 18.84 cm 2
- the effective membrane area of only the zeolite membrane (Y-type-6) prepared in Production Example 6 was 15.70 cm 2 .
- Example 20 The feed solution was changed from a methanol / 1.-butanol mixture with a methanol concentration of 9.80% by mass to a methanol / 2-butanol (sec-butyl alcohol, manufactured by Kanto Chemical Co., Inc.) mixture with a methanol concentration of 9.32% by mass. Except for the above, the pervaporation experiment was conducted at a temperature of 60 ° C. in the same manner as in Example 1. When the mass and composition of the permeate were stabilized, the permeate methanol concentration was 93.00% by mass, the separation factor ⁇ was 130, and the permeation flux Q was 0.80 kg / (m 2 ⁇ h).
- Example 21 The feed solution was changed from a methanol / 1-butanol mixture having a methanol concentration of 9.80% by mass to a methanol / 2-methyl-1-propanol (isobutyl alcohol, special grade manufactured by Kanto Chemical Co., Ltd.) having a methanol concentration of 9.83% by mass.
- the pervaporation experiment was performed at a temperature of 60 ° C. in the same manner as in Example 1 except that the change was made.
- the permeate methanol concentration was 93.29% by mass
- the separation factor ⁇ was 130
- the permeation flux Q was 0.74 kg / (m 2 ⁇ h).
- Example 22 The feed solution was changed from a methanol / 1-butanol mixture having a methanol concentration of 9.80% by mass to methanol / 2-methyl-2-propanol having a methanol concentration of 9.04% by mass (t-butyl alcohol, manufactured by Kanto Chemical Co., Ltd. ) Pervaporation experiment was conducted at a temperature of 60 ° C. in the same manner as in Example 1 except that the mixture was changed.
- the permeate methanol concentration was 97.40% by mass
- the separation factor ⁇ was 380
- the permeation flux Q was 0.76 kg / (m 2 ⁇ h).
- the pervaporation experiment was carried out at a temperature of 60 ° C. in the same manner as in Example 1 except that the mixture was changed to a mixture of 50.66.
- the pervaporation experiment was conducted at a temperature of 60 ° C. in the same manner as in Example 1 except that the mixture was changed to a mixture of /20.09/29.83/40.05.
- Example 25 The supply liquid container (2) in FIG. 1 is replaced with a container having a volume of 0.1 L, and 0.0371 kg of 1-butanol, 0.0501 kg of methyl methacrylate, titanium tetra-n-butoxide ( 0.00085 kg (manufactured by Kanto Chemical Co., Inc.) and 0.00007 kg of p-methoxyphenol (special grade manufactured by Kanto Chemical Co., Ltd.) were charged and stirred until uniform. A zeolite membrane (Y-type-1) was immersed in this solution and connected to a glass vacuum line (5). The temperature of the supply liquid was kept constant at 80 ° C. by the constant temperature water bath (1), and pressure reduction in the apparatus was started when the temperature reached 80 ° C.
- Example 2 Example except that the Y-type zeolite membrane was replaced with a commercially available T-type zeolite membrane (Mitsui Engineering & Shipbuilding Co., Ltd., outer diameter 12 mm, total length 100 mm, exposed portion length 50 mm, effective membrane area 18.84 cm 2 )
- T-type zeolite membrane Mitsubishi Chemical Company LLC.
- pervaporation separation experiments were conducted at a temperature of 60 ° C. However, the permeate did not distill after 3 hours from the start of permeation.
- a mixture of methanol and a monohydric alcohol having 4 or more carbon atoms can be efficiently separated.
- a raw material can be recovered and reused at a high concentration in a transesterification reaction. Can do.
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Abstract
L'invention porte sur un procédé pour la séparation efficace de méthanol d'un mélange qui contient du méthanol et un monoalcool ayant 4 ou plus de 4 atomes de carbone. L'invention porte sur un procédé pour la séparation de méthanol d'un mélange qui contient du méthanol et un monoalcool ayant 4 ou plus de 4 atomes de carbone utilisant une membrane zéolitique qui a une structure cristalline FAU. L'invention porte sur un procédé pour la séparation de méthanol d'un liquide réactionnel, qui a été obtenu par la mise en œuvre d'une transestérification entre un monoalcool ayant 4 ou plus de 4 atomes de carbone et un ester méthylique issu d'un acide carboxylique ayant 3 ou plus de 3 atomes de carbone, utilisant une membrane zéolitique qui a une structure cristalline FAU.
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Cited By (7)
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CN109851502A (zh) * | 2018-12-06 | 2019-06-07 | 沈阳化工大学 | 一种通过酯醇交换制备丙酸酯的方法 |
JP2020040003A (ja) * | 2018-09-07 | 2020-03-19 | 学校法人 関西大学 | ろ過膜 |
WO2020175247A1 (fr) * | 2019-02-28 | 2020-09-03 | 日本ゼオン株式会社 | Procédé de fabrication d'une membrane de séparation |
JP2020143050A (ja) * | 2019-02-28 | 2020-09-10 | 三菱ケミカル株式会社 | メタノールの分離方法 |
KR20200130244A (ko) * | 2019-05-09 | 2020-11-18 | 가부시키가이샤 미쯔이 이앤에스 머시너리 | 제올라이트 막에 제공하는 피처리 유체의 처리방법 |
JP7389295B1 (ja) * | 2023-04-28 | 2023-11-29 | 住友化学株式会社 | 組成物、重合体、硬化物、成形体及びポリメタクリル酸メチルの製造方法 |
WO2024095957A1 (fr) * | 2022-10-31 | 2024-05-10 | 三菱ケミカル株式会社 | Composition à teneur en composé ester ainsi que procédé de fabrication de celle-ci, composition polymérisable, polymère (méth)acrylique ainsi que procédé de fabrication de celui-ci |
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JP2020040003A (ja) * | 2018-09-07 | 2020-03-19 | 学校法人 関西大学 | ろ過膜 |
JP7219440B2 (ja) | 2018-09-07 | 2023-02-08 | 学校法人 関西大学 | ろ過膜 |
CN109851502A (zh) * | 2018-12-06 | 2019-06-07 | 沈阳化工大学 | 一种通过酯醇交换制备丙酸酯的方法 |
JP7464037B2 (ja) | 2019-02-28 | 2024-04-09 | 日本ゼオン株式会社 | 分離膜製造方法 |
WO2020175247A1 (fr) * | 2019-02-28 | 2020-09-03 | 日本ゼオン株式会社 | Procédé de fabrication d'une membrane de séparation |
JPWO2020175247A1 (fr) * | 2019-02-28 | 2020-09-03 | ||
JP2020143050A (ja) * | 2019-02-28 | 2020-09-10 | 三菱ケミカル株式会社 | メタノールの分離方法 |
US11969692B2 (en) | 2019-02-28 | 2024-04-30 | Zeon Corporation | Method of producing separation membrane |
JP7463761B2 (ja) | 2019-02-28 | 2024-04-09 | 三菱ケミカル株式会社 | メタノールの分離方法 |
KR102267831B1 (ko) * | 2019-05-09 | 2021-06-21 | 가부시키가이샤 미쯔이 이앤에스 머시너리 | 제올라이트 막에 제공하는 피처리 유체의 처리방법 |
US11090618B1 (en) | 2019-05-09 | 2021-08-17 | Mitsui E&S Machinery Co., Ltd. | Treatment method of fluid to be treated by zeolite membrane |
KR20200130244A (ko) * | 2019-05-09 | 2020-11-18 | 가부시키가이샤 미쯔이 이앤에스 머시너리 | 제올라이트 막에 제공하는 피처리 유체의 처리방법 |
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