JP2014503493A - 酢酸と無水酢酸の同時製造 - Google Patents
酢酸と無水酢酸の同時製造 Download PDFInfo
- Publication number
- JP2014503493A JP2014503493A JP2013538843A JP2013538843A JP2014503493A JP 2014503493 A JP2014503493 A JP 2014503493A JP 2013538843 A JP2013538843 A JP 2013538843A JP 2013538843 A JP2013538843 A JP 2013538843A JP 2014503493 A JP2014503493 A JP 2014503493A
- Authority
- JP
- Japan
- Prior art keywords
- reaction composition
- carbonylation
- acetic anhydride
- liquid reaction
- carbonylation reactor
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- WFDIJRYMOXRFFG-UHFFFAOYSA-N acetic acid anhydride Natural products CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 title claims abstract description 222
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 title claims abstract description 126
- 238000004519 manufacturing process Methods 0.000 title claims description 7
- 238000005810 carbonylation reaction Methods 0.000 claims abstract description 131
- 230000006315 carbonylation Effects 0.000 claims abstract description 129
- 239000000203 mixture Substances 0.000 claims abstract description 128
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 123
- 238000006243 chemical reaction Methods 0.000 claims abstract description 115
- 238000000034 method Methods 0.000 claims abstract description 52
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 claims abstract description 24
- KXKVLQRXCPHEJC-UHFFFAOYSA-N acetic acid trimethyl ester Natural products COC(C)=O KXKVLQRXCPHEJC-UHFFFAOYSA-N 0.000 claims abstract description 24
- 239000007788 liquid Substances 0.000 claims description 71
- 150000001875 compounds Chemical class 0.000 claims description 46
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims description 44
- 229910002091 carbon monoxide Inorganic materials 0.000 claims description 44
- 238000005886 esterification reaction Methods 0.000 claims description 42
- 230000032050 esterification Effects 0.000 claims description 36
- 239000003054 catalyst Substances 0.000 claims description 33
- 230000008569 process Effects 0.000 claims description 31
- INQOMBQAUSQDDS-UHFFFAOYSA-N iodomethane Chemical compound IC INQOMBQAUSQDDS-UHFFFAOYSA-N 0.000 claims description 22
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 claims description 19
- 229910052740 iodine Inorganic materials 0.000 claims description 19
- 239000011630 iodine Substances 0.000 claims description 18
- 239000002994 raw material Substances 0.000 claims description 14
- 239000007791 liquid phase Substances 0.000 claims description 13
- 239000007858 starting material Substances 0.000 claims description 11
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 claims description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 9
- 239000010948 rhodium Substances 0.000 claims description 8
- 229910052703 rhodium Inorganic materials 0.000 claims description 6
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 claims description 6
- 239000007787 solid Substances 0.000 claims description 3
- 150000003284 rhodium compounds Chemical class 0.000 claims description 2
- 229940125898 compound 5 Drugs 0.000 claims 1
- 229910052751 metal Inorganic materials 0.000 description 21
- 239000002184 metal Substances 0.000 description 21
- 239000007789 gas Substances 0.000 description 12
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 11
- 229910052739 hydrogen Inorganic materials 0.000 description 11
- 239000001257 hydrogen Substances 0.000 description 11
- 239000000463 material Substances 0.000 description 10
- 239000000047 product Substances 0.000 description 10
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 8
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 6
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 description 6
- 150000004694 iodide salts Chemical class 0.000 description 6
- GOKCJCODOLGYQD-UHFFFAOYSA-N 4,6-dichloro-2-imidazol-1-ylpyrimidine Chemical compound ClC1=CC(Cl)=NC(N2C=NC=C2)=N1 GOKCJCODOLGYQD-UHFFFAOYSA-N 0.000 description 4
- 239000002826 coolant Substances 0.000 description 4
- 238000013461 design Methods 0.000 description 4
- 238000004821 distillation Methods 0.000 description 4
- HSZCZNFXUDYRKD-UHFFFAOYSA-M lithium iodide Chemical compound [Li+].[I-] HSZCZNFXUDYRKD-UHFFFAOYSA-M 0.000 description 4
- 150000002739 metals Chemical class 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 229910052698 phosphorus Inorganic materials 0.000 description 4
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 3
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 3
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 3
- 239000006227 byproduct Substances 0.000 description 3
- 239000007795 chemical reaction product Substances 0.000 description 3
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 3
- 229910052744 lithium Inorganic materials 0.000 description 3
- 150000002736 metal compounds Chemical class 0.000 description 3
- 229910052759 nickel Inorganic materials 0.000 description 3
- LSMAIBOZUPTNBR-UHFFFAOYSA-N phosphanium;iodide Chemical compound [PH4+].[I-] LSMAIBOZUPTNBR-UHFFFAOYSA-N 0.000 description 3
- 239000011574 phosphorus Substances 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- 238000011084 recovery Methods 0.000 description 3
- XZXYQEHISUMZAT-UHFFFAOYSA-N 2-[(2-hydroxy-5-methylphenyl)methyl]-4-methylphenol Chemical compound CC1=CC=C(O)C(CC=2C(=CC=C(C)C=2)O)=C1 XZXYQEHISUMZAT-UHFFFAOYSA-N 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 229940107816 ammonium iodide Drugs 0.000 description 2
- 125000006615 aromatic heterocyclic group Chemical group 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 125000001183 hydrocarbyl group Chemical group 0.000 description 2
- 238000011065 in-situ storage Methods 0.000 description 2
- 229910052741 iridium Inorganic materials 0.000 description 2
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 description 2
- AMXOYNBUYSYVKV-UHFFFAOYSA-M lithium bromide Chemical compound [Li+].[Br-] AMXOYNBUYSYVKV-UHFFFAOYSA-M 0.000 description 2
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 125000004433 nitrogen atom Chemical group N* 0.000 description 2
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 2
- -1 nitrogen-containing iodides Chemical class 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 239000011949 solid catalyst Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000011144 upstream manufacturing Methods 0.000 description 2
- YJTKZCDBKVTVBY-UHFFFAOYSA-N 1,3-Diphenylbenzene Chemical group C1=CC=CC=C1C1=CC=CC(C=2C=CC=CC=2)=C1 YJTKZCDBKVTVBY-UHFFFAOYSA-N 0.000 description 1
- ARSMIBSHEYKMJT-UHFFFAOYSA-M 1,3-dimethylimidazolium iodide Chemical compound [I-].CN1C=C[N+](C)=C1 ARSMIBSHEYKMJT-UHFFFAOYSA-M 0.000 description 1
- BVUPLMFUPRCOEH-UHFFFAOYSA-M 1,3-dimethylpyridin-1-ium;iodide Chemical compound [I-].CC1=CC=C[N+](C)=C1 BVUPLMFUPRCOEH-UHFFFAOYSA-M 0.000 description 1
- OSNIIMCBVLBNGS-UHFFFAOYSA-N 1-(1,3-benzodioxol-5-yl)-2-(dimethylamino)propan-1-one Chemical compound CN(C)C(C)C(=O)C1=CC=C2OCOC2=C1 OSNIIMCBVLBNGS-UHFFFAOYSA-N 0.000 description 1
- MCTWTZJPVLRJOU-UHFFFAOYSA-N 1-methyl-1H-imidazole Chemical compound CN1C=CN=C1 MCTWTZJPVLRJOU-UHFFFAOYSA-N 0.000 description 1
- KGIGUEBEKRSTEW-UHFFFAOYSA-N 2-vinylpyridine Chemical compound C=CC1=CC=CC=N1 KGIGUEBEKRSTEW-UHFFFAOYSA-N 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- LEKJTGQWLAUGQA-UHFFFAOYSA-N acetyl iodide Chemical compound CC(I)=O LEKJTGQWLAUGQA-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 150000001462 antimony Chemical class 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 239000000498 cooling water Substances 0.000 description 1
- 150000004696 coordination complex Chemical class 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 125000005842 heteroatom Chemical group 0.000 description 1
- 239000002638 heterogeneous catalyst Substances 0.000 description 1
- 229910000043 hydrogen iodide Inorganic materials 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 229910001505 inorganic iodide Inorganic materials 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- XMBWDFGMSWQBCA-UHFFFAOYSA-M iodide Chemical compound [I-] XMBWDFGMSWQBCA-UHFFFAOYSA-M 0.000 description 1
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical compound II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 description 1
- XIXADJRWDQXREU-UHFFFAOYSA-M lithium acetate Chemical compound [Li+].CC([O-])=O XIXADJRWDQXREU-UHFFFAOYSA-M 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- 229910001510 metal chloride Inorganic materials 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- JNMIXMFEVJHFNY-UHFFFAOYSA-M methyl(triphenyl)phosphanium;iodide Chemical compound [I-].C=1C=CC=CC=1[P+](C=1C=CC=CC=1)(C)C1=CC=CC=C1 JNMIXMFEVJHFNY-UHFFFAOYSA-M 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 150000002897 organic nitrogen compounds Chemical class 0.000 description 1
- 125000001477 organic nitrogen group Chemical group 0.000 description 1
- 150000002903 organophosphorus compounds Chemical class 0.000 description 1
- 229910052762 osmium Inorganic materials 0.000 description 1
- SYQBFIAQOQZEGI-UHFFFAOYSA-N osmium atom Chemical compound [Os] SYQBFIAQOQZEGI-UHFFFAOYSA-N 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 125000004437 phosphorous atom Chemical group 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 239000002952 polymeric resin Substances 0.000 description 1
- 238000004886 process control Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 239000012429 reaction media Substances 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 229910052707 ruthenium 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
- 238000003756 stirring Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 125000005497 tetraalkylphosphonium group Chemical group 0.000 description 1
- DPKBAXPHAYBPRL-UHFFFAOYSA-M tetrabutylazanium;iodide Chemical compound [I-].CCCC[N+](CCCC)(CCCC)CCCC DPKBAXPHAYBPRL-UHFFFAOYSA-M 0.000 description 1
- CCIYPTIBRAUPLQ-UHFFFAOYSA-M tetrabutylphosphanium;iodide Chemical compound [I-].CCCC[P+](CCCC)(CCCC)CCCC CCIYPTIBRAUPLQ-UHFFFAOYSA-M 0.000 description 1
- JTFPRVNRGNKAAV-UHFFFAOYSA-M tetraoctylphosphanium;iodide Chemical compound [I-].CCCCCCCC[P+](CCCCCCCC)(CCCCCCCC)CCCCCCCC JTFPRVNRGNKAAV-UHFFFAOYSA-M 0.000 description 1
- AEFPPQGZJFTXDR-UHFFFAOYSA-M tetraphenylphosphanium;iodide Chemical compound [I-].C1=CC=CC=C1[P+](C=1C=CC=CC=1)(C=1C=CC=CC=1)C1=CC=CC=C1 AEFPPQGZJFTXDR-UHFFFAOYSA-M 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- DXJLCRNXYNRGRA-UHFFFAOYSA-M tributyl(methyl)azanium;iodide Chemical compound [I-].CCCC[N+](C)(CCCC)CCCC DXJLCRNXYNRGRA-UHFFFAOYSA-M 0.000 description 1
- RLZMYANQLOCZOB-UHFFFAOYSA-M tributyl(methyl)phosphanium;iodide Chemical compound [I-].CCCC[P+](C)(CCCC)CCCC RLZMYANQLOCZOB-UHFFFAOYSA-M 0.000 description 1
- IMFACGCPASFAPR-UHFFFAOYSA-N tributylamine Chemical compound CCCCN(CCCC)CCCC IMFACGCPASFAPR-UHFFFAOYSA-N 0.000 description 1
- TUQOTMZNTHZOKS-UHFFFAOYSA-N tributylphosphine Chemical compound CCCCP(CCCC)CCCC TUQOTMZNTHZOKS-UHFFFAOYSA-N 0.000 description 1
- WRTMQOHKMFDUKX-UHFFFAOYSA-N triiodide Chemical compound I[I-]I WRTMQOHKMFDUKX-UHFFFAOYSA-N 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/10—Preparation of carboxylic acids or their salts, halides or anhydrides by reaction with carbon monoxide
- C07C51/12—Preparation of carboxylic acids or their salts, halides or anhydrides by reaction with carbon monoxide on an oxygen-containing group in organic compounds, e.g. alcohols
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/54—Preparation of carboxylic acid anhydrides
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/08—Preparation of carboxylic acid esters by reacting carboxylic acids or symmetrical anhydrides with the hydroxy or O-metal group of organic compounds
-
- 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
- Y02P20/582—Recycling of unreacted starting or intermediate materials
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
Description
本願発明は、酢酸と無水酢酸の同時製造方法に関係する。より詳しく述べると、本願発明は、第1のカルボニル化反応器内で無水酢酸を含む第1の反応生成組成物を生成すること、第1のカルボニル化反応器からの第1の反応生成組成物を取出すこと、エステル化ゾーン内で第1の反応生成組成物をメタノールと接触させて、反応させ、そして組成物中に含まれている無水酢酸の一部又は全部を酢酸及び酢酸メチルに変換すること、得られた反応組成物を第2のカルボニル化反応器に供給すること、そして反応組成物を一酸化炭素と接触させて、カルボニル化を引き起こすことによる酢酸と無水酢酸の製造に関係する。
液相中で、酢酸メチル及び/又はジメチルエーテル、並びに1若しくは複数のヨウ素含有化合物を含む組成物を、カルボニル化触媒の存在下、一酸化炭素と接触させることによる無水酢酸の製造が、特許文献において広く報告されている。例えば米国特許第3,927,078号;同第4,046,807号;同第4,115,444号;同第4,252,741号;同第4,374,070号;同第4,430,273号;同第4,559,183号;同第5,003,104号;及び同第5,292,948号、並びに欧州特許第8396号;同第87,869号;及び同第87,870号を参照のこと。
本発明は、液相中、実質的に無水条件下での無水酢酸と酢酸の同時製造方法を提供し、該方法は、以下のステップ:
(1)第1のカルボニル化反応器内で、(i)酢酸メチル、ジメチルエーテル又はその組合せ物から選択される少なくとも1の原料化合物;と(ii)第1の一酸化炭素流を含む成分を連続的に組合せて、液相中、第1の液体反応組成物を生成すること、ここでは:
該成分が、カルボニル化触媒の存在下で組合され、
該成分が、少なくとも一部の原料化合物を無水酢酸に変換するのに有効な条件下で組合され、且つ
該第1の液体反応組成物が:(i)少なくとも一部の未反応の原料化合物、(ii)溶存一酸化炭素、及び(iii)無水酢酸生成物を含む;
(2)第1のカルボニル化反応器から第1の液体反応組成物の少なくとも一部を連続的に取出し、そして液相中、第2の液体反応組成物中に酢酸メチル及び酢酸が生成されるように第1の反応組成物からの少なくとも一部の無水酢酸と少なくとも一部のメタノールとを反応させるのに有効な条件下で、エステル化ゾーン内で第1の液体反応組成物の少なくとも一部をメタノールと接触させて、第2の液体反応組成物を形成すること;
(3)液相中、一酸化炭素を追加しながら第2のカルボニル化反応器に第2の液体反応組成物を連続的に供給して、第3の液体反応組成物を生成すること、ここでは:
少なくとも一部の未反応の原料化合物、(2)からの酢酸メチル、又はその両方が無水酢酸に変換されるのに有効な条件下で、第2の液体反応組成物と第2の一酸化炭素流とが組合され、且つ、
第3の反応組成物が、(i)未反応の原料化合物、(2)からの酢酸メチル、又はその両方、(ii)酢酸、及び(iii)無水酢酸生成物を含む、そして、
(4)第2のカルボニル化反応器から第3の液体反応組成物を連続的に取出すこと、を含む。
詳細な説明
カルボニル化ステップ
第1のカルボニル化ステップ
エステル化
第2のカルボニル化ステップ
更なる処理
Claims (16)
- 液相中、実質的に無水条件下での無水酢酸と酢酸の同時製造方法であって、以下のステップ:
(1)第1のカルボニル化反応器内で、(i)酢酸メチル、ジメチルエーテル又はその組合せ物から選択される少なくとも1種類の原料化合物;と(ii)第1の一酸化炭素流、を含む成分を連続的に組合せて、液相中、第1の液体反応組成物を生成すること、ここでは:
該成分が、カルボニル化触媒の存在下で組合され、
該成分が、少なくとも一部の原料化合物を無水酢酸に変換するのに有効な条件下で組合され、且つ
該第1の液体反応組成物が:(i)少なくとも一部の未反応の原料化合物、(ii)溶存一酸化炭素、及び(iii)無水酢酸生成物を含む;
(2)第1のカルボニル化反応器から第1の液体反応組成物の少なくとも一部を連続的に取出し、そして液相中、第2の液体反応組成物中に酢酸メチル及び酢酸が生成されるように第1の反応組成物からの少なくとも一部の無水酢酸及び少なくとも一部のメタノールを反応させるのに有効な条件下、エステル化ゾーン内で第1の液体反応組成物の少なくとも一部をメタノールと接触させて第2の液体反応組成物を形成すること;
(3)液相中、一酸化炭素を追加しながら第2のカルボニル化反応器に第2の液体反応組成物を連続的に供給して、第3の液体反応組成物を生成すること、ここでは:
少なくとも一部の未反応の原料化合物、(2)からの酢酸メチル、又はその両方が無水酢酸に変換されるのに有効な条件下で、第2の液体反応組成物と第2の一酸化炭素流とが組合され、且つ
第3の反応組成物が、(i)未反応の原料化合物、(2)からの酢酸メチル、又はその両方、(ii)酢酸、及び(iii)無水酢酸生成物を含む;そして
(4)第2のカルボニル化反応器から第3の液体反応組成物を連続的に取出すこと、を含む方法。 - 前記エステル化ゾーンが、液体反応組成物、第2の液体反応組成物、又は両方から一部の熱を取出すように構成された少なくとも1つの熱交換器を備える、請求項1に記載の方法。
- 前記の少なくとも1つの熱交換器が、水を蒸気に変換する、請求項2に記載の方法。
- 前記カルボニル化反応器の少なくとも1つが100〜300℃の温度及び21.7〜276.7絶対bar(bara)の(総)圧力で操作され、且つ、カルボニル化反応器内での滞留時間が4分〜120分である、請求項1〜3のいずれか1項に記載の方法。
- 前記カルボニル化反応器が175〜220℃の温度及び35.5〜104.4baraの(総)圧力で操作され、且つ、カルボニル化反応器内での滞留時間が15〜40分であって、第1のカルボニル化反応器から取出され、そしてステップ(2)のエステル化ゾーンに供給される第1の反応組成物の組成が、8〜38重量パーセントの無水酢酸、15〜60重量パーセントの原料化合物、6〜25重量パーセントのヨウ化メチル、18〜40重量パーセントの酢酸である、請求項1〜4のいずれか1項に記載の方法。
- 前記エステル化ゾーンに供給されるメタノールの量が、第1の反応組成物としてエステル化ゾーンに供給される無水酢酸1moleあたり0.6〜0.85moleである、請求項1〜5のいずれか1項に記載の方法。
- 前記エステル化ゾーンに供給されるメタノールの量が、第1の反応組成物としてエステル化ゾーンに供給される無水酢酸1moleあたりゼロ超だが、1mole未満である、請求項1〜5のいずれか1項に記載の方法。
- 前記エステル化ゾーンに供給されるメタノールの量が、エステル化ゾーンに供給される無水酢酸のモル数に対して化学量論的過剰をもたらすのに十分なモル数のメタノールである、請求項1〜5のいずれか1項に記載の方法。
- 第1のカルボニル化反応器に酢酸を供給することをさらに含む、請求項1〜8のいずれか1項に記載の方法。
- 前記カルボニル化触媒に、ロジウム又はロジウム化合物が含まれる、請求項1〜9のいずれか1項に記載の方法。
- 前記の第1のカルボニル化反応器で組合される成分に、少なくとも1種類のヨウ素含有化合物がさらに含まれる、請求項1〜10のいずれか1項に記載の方法。
- 前記の少なくとも1種類のヨウ素含有化合物が、ヨウ化メチル又は第1の液体反応組成物中のヨウ化メチルを形成する化合物である、請求項11に記載の方法。
- 前記の少なくとも一部のカルボニル化触媒が、第1の液体反応組成物中に溶存している、請求項1〜12のいずれか1項に記載の方法。
- 前記の少なくとも一部のカルボニル化触媒が、第1の液体反応組成物の存在下で固体である、請求項1〜12のいずれか1項に記載の方法。
- 前記の第1の一酸化炭素流が、第1の液体反応組成物の中になる位置に供給される、請求項1〜14のいずれか1項に記載の方法。
- 前記の第2の一酸化炭素流が、第3の液体反応組成物の中になる位置に供給される、請求項1〜15のいずれか1項に記載の方法。
Applications Claiming Priority (5)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US41321410P | 2010-11-12 | 2010-11-12 | |
US61/413,214 | 2010-11-12 | ||
US13/289,518 US9012683B2 (en) | 2010-11-12 | 2011-11-04 | Coproduction of acetic acid and acetic anhydride |
US13/289,518 | 2011-11-04 | ||
PCT/US2011/059954 WO2012064830A1 (en) | 2010-11-12 | 2011-11-09 | Coproduction of acetic acid and acetic anhydride |
Publications (2)
Publication Number | Publication Date |
---|---|
JP2014503493A true JP2014503493A (ja) | 2014-02-13 |
JP5894178B2 JP5894178B2 (ja) | 2016-03-23 |
Family
ID=46048390
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP2013538843A Active JP5894178B2 (ja) | 2010-11-12 | 2011-11-09 | 酢酸と無水酢酸の同時製造 |
Country Status (7)
Country | Link |
---|---|
US (1) | US9012683B2 (ja) |
EP (1) | EP2637997B1 (ja) |
JP (1) | JP5894178B2 (ja) |
CN (1) | CN103180281B (ja) |
BR (1) | BR112013011436A2 (ja) |
TW (1) | TWI508943B (ja) |
WO (1) | WO2012064830A1 (ja) |
Families Citing this family (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US8530696B2 (en) * | 2010-09-24 | 2013-09-10 | Celanese International Corporation | Pump around reactor for production of acetic acid |
US9415366B2 (en) | 2012-12-31 | 2016-08-16 | Eastman Chemical Company | Systems and methods for processing variable acetyl streams |
EP2964602A2 (en) * | 2013-03-07 | 2016-01-13 | BP Chemicals Limited | Process |
CN109092359A (zh) * | 2018-09-25 | 2018-12-28 | 煜格(北京)科技有限公司 | 一种甲醇羰基合成醋酸及醋酸甲酯的催化剂体系及其应用 |
Citations (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS58164539A (ja) * | 1982-02-13 | 1983-09-29 | ビ−ピ−・ケミカルズ・リミテツド | カルボン酸および酸無水物の同時製造方法 |
EP0087870B1 (en) * | 1982-02-13 | 1985-04-17 | BP Chemicals Limited | Process for the production of acetic anhydride and acetic acid |
JPH02104551A (ja) * | 1988-07-13 | 1990-04-17 | Hoechst Ag | 酢酸及び無水酢酸の製造法 |
JPH04264049A (ja) * | 1990-11-02 | 1992-09-18 | Hoechst Ag | 酢酸及び無水酢酸を同時に連続的に製造する方法 |
JPH0625031A (ja) * | 1992-04-15 | 1994-02-01 | Air Prod And Chem Inc | 酸素化されたアセチル化合物の合成方法 |
JPH06336453A (ja) * | 1993-05-28 | 1994-12-06 | Daicel Chem Ind Ltd | 無水酢酸及び酢酸の製造方法 |
JPH09132546A (ja) * | 1995-08-22 | 1997-05-20 | Bp Chem Internatl Ltd | アルコールおよび/またはその反応性誘導体のカルボニル化方法 |
US5922911A (en) * | 1998-04-24 | 1999-07-13 | Eastman Chemical Company | Process for the manufacture of acetic anhydride |
Family Cites Families (49)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
SE364254B (ja) | 1967-04-05 | 1974-02-18 | Monsanto Co | |
US3772360A (en) | 1969-07-01 | 1973-11-13 | Smithkline Corp | Adamantyl substituted glycerophosphoryl(and phosphonyl)ethanolamines |
US3927078A (en) * | 1972-08-21 | 1975-12-16 | Chevron Res | Methylene and oxymethylene bis-ester production |
US4559183A (en) * | 1973-09-04 | 1985-12-17 | The Halcon Sd Group, Inc. | Preparation of carboxylic acid anhydrides |
DE2450965C2 (de) * | 1974-10-26 | 1983-06-09 | Hoechst Ag, 6230 Frankfurt | Verfahren zur Herstellung von Essigsäureanhydrid |
US4115444A (en) * | 1975-03-10 | 1978-09-19 | Halcon International, Inc. | Process for preparing carboxylic acid anhydrides |
US4039395A (en) | 1975-08-11 | 1977-08-02 | Monsanto Company | Purification of acetic acid |
DE2836084A1 (de) | 1978-08-17 | 1980-03-06 | Hoechst Ag | Verfahren zur herstellung von essigsaeureanhydrid |
JPS5538369A (en) | 1978-09-01 | 1980-03-17 | Texaco Development Corp | Manufacture of carboxylic acids and their esters |
US4252741A (en) * | 1978-10-06 | 1981-02-24 | Halcon Research & Development Corp. | Carbonylation with Group VIII noble metal catalysts |
US4358411A (en) | 1979-06-29 | 1982-11-09 | The Halcon Sd Group, Inc. | Preparation of carbonylation products |
DE2939839A1 (de) | 1979-10-02 | 1981-04-23 | Hoechst Ag, 6000 Frankfurt | Verfahren zur herstellung von essigsaeureanhydrid |
US4417077A (en) | 1980-10-01 | 1983-11-22 | University Of Illinois Foundation | Heterogeneous anionic transition metal catalysts |
US4374070A (en) * | 1980-11-21 | 1983-02-15 | Eastman Kodak Company | Preparation of acetic anhydride |
US4366259A (en) | 1981-10-29 | 1982-12-28 | Texaco, Inc. | Production of acetic acid and propionic acid and their esters |
DE3148006A1 (de) | 1981-12-04 | 1983-06-09 | Hoechst Ag, 6230 Frankfurt | Verfahren zur herstellung von essigsaeureanhydrid und/oder essigsaeure und/oder ethylidendiacetat |
NZ203225A (en) | 1982-02-13 | 1985-01-31 | Bp Chem Int Ltd | Coproduction of monocarboxylic acids and anhydrides |
ZA833528B (en) | 1982-05-22 | 1984-12-24 | Bp Chem Int Ltd | Process for the production of one or more carboxylic acid anhydrides |
EP0109212B1 (en) | 1982-11-04 | 1987-05-27 | BP Chemicals Limited | Process for the preparation of acids |
US4629809A (en) | 1983-07-21 | 1986-12-16 | Texaco Inc. | Process for selectively preparing acetic acid by carbonylation of methanol in the presence of a novel iodide-free catalyst system |
GB8404136D0 (en) | 1984-02-16 | 1984-03-21 | Bp Chem Int Ltd | Carbonylation process |
US5144068A (en) | 1984-05-03 | 1992-09-01 | Hoechst Celanese Corporation | Methanol carbonylation process |
US5155261A (en) | 1987-02-05 | 1992-10-13 | Reilly Industries, Inc. | Process for acetic acid preparation and heterogenous catalyst for same |
US5003104A (en) * | 1987-03-03 | 1991-03-26 | Bp Chemicals Limited | Carbonylation process and catalyst |
GB8807284D0 (en) | 1988-03-26 | 1988-04-27 | Bp Chem Int Ltd | Chemical process |
GB8809027D0 (en) | 1988-04-16 | 1988-05-18 | British Petroleum Co Plc | Carbonylation of allylic alcohols |
US5442107A (en) | 1989-04-06 | 1995-08-15 | Bp Chemicals Limited | Preparing carboxylic acids |
WO1990011991A1 (en) | 1989-04-06 | 1990-10-18 | Bp Chemicals Limited | Process for preparing carboxylic acids |
GB9021454D0 (en) | 1990-10-03 | 1990-11-14 | Bp Chem Int Ltd | Process |
DE69108567T2 (de) * | 1990-12-20 | 1995-08-03 | Eastman Chem Co | Kontinuierliches verfahren zur herstellung von essigsäureanhydrid oder einer mischung von essigsäureanhydrid und essigsäure. |
GB9211671D0 (en) | 1992-06-02 | 1992-07-15 | Bp Chem Int Ltd | Process |
US5488143A (en) | 1992-06-30 | 1996-01-30 | Korea Institute Of Science And Technology | Processes for the carbonylation of methanol to form acetic acid, methyl acetate and acetic anhydride |
GB9218346D0 (en) | 1992-08-28 | 1992-10-14 | Bp Chem Int Ltd | Process |
KR0168207B1 (ko) | 1993-08-18 | 1999-03-20 | 고지마 아키로 | 무수아세트산 또는 무수아세트산 및 아세트산의 제조방법 |
US5880311A (en) | 1994-07-22 | 1999-03-09 | Tonen Corporation | Method of contacting catalyst particles with gas and liquid |
US5510524A (en) | 1995-02-21 | 1996-04-23 | Bp Chemicals Limited | Process for the production of a carboxylic acid |
US5696284A (en) | 1995-06-21 | 1997-12-09 | Bp Chemicals Limited | Process for the carbonylation of alkyl alcohols and/or reactive derivatives thereof |
US5900505A (en) | 1997-02-04 | 1999-05-04 | Eastman Chemical Company | Heterogeneous vapor phase carbonylation process |
GB9802027D0 (en) | 1998-01-31 | 1998-03-25 | Bp Chem Int Ltd | Chemical process |
WO1999054273A1 (en) | 1998-04-17 | 1999-10-28 | Bp Chemicals Limited | Process for the production of acetic acid and/or acetic anhydride |
GB9816385D0 (en) | 1998-07-29 | 1998-09-23 | Bp Chem Int Ltd | Process |
US6211405B1 (en) | 1998-10-23 | 2001-04-03 | Celanese International Corporation | Addition of iridium to the rhodium/inorganic iodide catalyst system |
US6452043B1 (en) | 2000-04-05 | 2002-09-17 | Eastman Chemical Company | Carbonylation of lower alkyl alcohols and their derivatives using metals supported on carbonized polysulfonated divinylbenzene-styrene copolymers |
DE10138778A1 (de) | 2001-08-07 | 2003-02-20 | Basf Ag | Flexibles Verfahren zur gemeinsamen Herstellung von Ameisensäure sowie einer Carbonsäure mit mindestens zwei Kohlenstoffatomen und/oder deren Derivaten |
JP3660982B2 (ja) | 2001-11-08 | 2005-06-15 | 独立行政法人産業技術総合研究所 | カルボン酸塩の製造方法 |
US6667418B2 (en) | 2002-04-16 | 2003-12-23 | Celanese International Corporation | Oxidation treatment of a recycle stream in production of acetic acid by methanol carbonylation |
AU2003230306A1 (en) | 2002-05-06 | 2003-11-17 | Eastman Chemical Company | Continuous carbonylation process |
FR2839972B1 (fr) | 2002-05-23 | 2005-08-19 | Inst Francais Du Petrole | Procede de carbonylation des alcools utilisant un catalyseur a base de rhodium ou d'iridium dans un liquide ionique non-aqueux,avec un recyclage efficace du catalyseur |
US7737298B2 (en) * | 2006-06-09 | 2010-06-15 | Eastman Chemical Company | Production of acetic acid and mixtures of acetic acid and acetic anhydride |
-
2011
- 2011-11-04 US US13/289,518 patent/US9012683B2/en active Active
- 2011-11-09 JP JP2013538843A patent/JP5894178B2/ja active Active
- 2011-11-09 EP EP11791112.3A patent/EP2637997B1/en active Active
- 2011-11-09 BR BR112013011436A patent/BR112013011436A2/pt not_active IP Right Cessation
- 2011-11-09 WO PCT/US2011/059954 patent/WO2012064830A1/en active Application Filing
- 2011-11-09 CN CN201180054074.8A patent/CN103180281B/zh active Active
- 2011-11-11 TW TW100141379A patent/TWI508943B/zh active
Patent Citations (11)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS58164539A (ja) * | 1982-02-13 | 1983-09-29 | ビ−ピ−・ケミカルズ・リミテツド | カルボン酸および酸無水物の同時製造方法 |
EP0087870B1 (en) * | 1982-02-13 | 1985-04-17 | BP Chemicals Limited | Process for the production of acetic anhydride and acetic acid |
JPH02104551A (ja) * | 1988-07-13 | 1990-04-17 | Hoechst Ag | 酢酸及び無水酢酸の製造法 |
US5380929A (en) * | 1988-07-13 | 1995-01-10 | Hoechst Aktiengesellschaft | Process for the preparation of acetic acid and acetic anhydride |
JPH04264049A (ja) * | 1990-11-02 | 1992-09-18 | Hoechst Ag | 酢酸及び無水酢酸を同時に連続的に製造する方法 |
JPH0625031A (ja) * | 1992-04-15 | 1994-02-01 | Air Prod And Chem Inc | 酸素化されたアセチル化合物の合成方法 |
JPH06336453A (ja) * | 1993-05-28 | 1994-12-06 | Daicel Chem Ind Ltd | 無水酢酸及び酢酸の製造方法 |
JPH09132546A (ja) * | 1995-08-22 | 1997-05-20 | Bp Chem Internatl Ltd | アルコールおよび/またはその反応性誘導体のカルボニル化方法 |
US5917089A (en) * | 1995-08-22 | 1999-06-29 | Bp Chemicals Limited | Process for the carbonylation of an alcohol and/or a reactive derivative thereof |
US5922911A (en) * | 1998-04-24 | 1999-07-13 | Eastman Chemical Company | Process for the manufacture of acetic anhydride |
JP2002512995A (ja) * | 1998-04-24 | 2002-05-08 | イーストマン ケミカル カンパニー | 無水酢酸の製造方法 |
Also Published As
Publication number | Publication date |
---|---|
TWI508943B (zh) | 2015-11-21 |
CN103180281A (zh) | 2013-06-26 |
JP5894178B2 (ja) | 2016-03-23 |
US9012683B2 (en) | 2015-04-21 |
CN103180281B (zh) | 2015-03-25 |
US20120123156A1 (en) | 2012-05-17 |
EP2637997B1 (en) | 2016-09-07 |
WO2012064830A1 (en) | 2012-05-18 |
TW201226384A (en) | 2012-07-01 |
BR112013011436A2 (pt) | 2016-08-09 |
EP2637997A1 (en) | 2013-09-18 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
JP5507544B2 (ja) | 酢酸に富むフラッシュ流を与えるメタノールをカルボニル化するための方法及び装置 | |
RU2584422C2 (ru) | Циркуляционный реактор для получения уксусной кислоты | |
JP5281000B2 (ja) | 酢酸および酢酸と無水酢酸との混合物の製造 | |
JP5894178B2 (ja) | 酢酸と無水酢酸の同時製造 | |
JP4662624B2 (ja) | 無水酢酸の製造方法 | |
JP5873101B2 (ja) | 増加した製造速度での酢酸の製造 | |
KR102397805B1 (ko) | 아세트산 생산 방법 | |
US20110021816A1 (en) | Acetic anhydride production by way of carbonylation with enhanced reaction and flashing | |
CN105308016B (zh) | 用于联合生产乙酸和乙酸酐的方法 | |
EP1360165B1 (en) | Method for reducing eda in acetic anhydride production | |
KR20050019102A (ko) | 아세트산의 제조 방법 |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
A621 | Written request for application examination |
Free format text: JAPANESE INTERMEDIATE CODE: A621 Effective date: 20140821 |
|
A977 | Report on retrieval |
Free format text: JAPANESE INTERMEDIATE CODE: A971007 Effective date: 20150520 |
|
A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20150609 |
|
A601 | Written request for extension of time |
Free format text: JAPANESE INTERMEDIATE CODE: A601 Effective date: 20150908 |
|
A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20151209 |
|
TRDD | Decision of grant or rejection written | ||
A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 Effective date: 20160126 |
|
A61 | First payment of annual fees (during grant procedure) |
Free format text: JAPANESE INTERMEDIATE CODE: A61 Effective date: 20160225 |
|
R150 | Certificate of patent or registration of utility model |
Ref document number: 5894178 Country of ref document: JP Free format text: JAPANESE INTERMEDIATE CODE: R150 |
|
R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |