JP6671177B2 - プロセス - Google Patents
プロセス Download PDFInfo
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- JP6671177B2 JP6671177B2 JP2015560702A JP2015560702A JP6671177B2 JP 6671177 B2 JP6671177 B2 JP 6671177B2 JP 2015560702 A JP2015560702 A JP 2015560702A JP 2015560702 A JP2015560702 A JP 2015560702A JP 6671177 B2 JP6671177 B2 JP 6671177B2
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- acetic acid
- acetic anhydride
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- liquid reaction
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- 238000000034 method Methods 0.000 title claims description 39
- WFDIJRYMOXRFFG-UHFFFAOYSA-N acetic acid anhydride Natural products CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 claims description 405
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 328
- 238000006243 chemical reaction Methods 0.000 claims description 129
- 239000007788 liquid Substances 0.000 claims description 99
- 239000000203 mixture Substances 0.000 claims description 97
- 229910052751 metal Inorganic materials 0.000 claims description 72
- 239000002184 metal Substances 0.000 claims description 72
- 238000000926 separation method Methods 0.000 claims description 50
- 150000003839 salts Chemical class 0.000 claims description 48
- 239000003054 catalyst Substances 0.000 claims description 42
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 claims description 36
- KXKVLQRXCPHEJC-UHFFFAOYSA-N acetic acid trimethyl ester Natural products COC(C)=O KXKVLQRXCPHEJC-UHFFFAOYSA-N 0.000 claims description 36
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 claims description 32
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 21
- 238000004519 manufacturing process Methods 0.000 claims description 20
- 239000010948 rhodium Substances 0.000 claims description 20
- INQOMBQAUSQDDS-UHFFFAOYSA-N iodomethane Chemical compound IC INQOMBQAUSQDDS-UHFFFAOYSA-N 0.000 claims description 19
- 229910052703 rhodium Inorganic materials 0.000 claims description 17
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical group [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 claims description 17
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims description 12
- 229910002091 carbon monoxide Inorganic materials 0.000 claims description 12
- 229910003002 lithium salt Inorganic materials 0.000 claims description 11
- 159000000002 lithium salts Chemical group 0.000 claims description 11
- 230000032050 esterification Effects 0.000 claims description 8
- 238000005886 esterification reaction Methods 0.000 claims description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
- 238000010924 continuous production Methods 0.000 claims description 6
- 150000002739 metals Chemical class 0.000 claims description 3
- 238000002955 isolation Methods 0.000 claims description 2
- 238000000605 extraction Methods 0.000 claims 1
- 239000007789 gas Substances 0.000 description 19
- 238000005810 carbonylation reaction Methods 0.000 description 17
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 14
- HSZCZNFXUDYRKD-UHFFFAOYSA-M lithium iodide Chemical compound [Li+].[I-] HSZCZNFXUDYRKD-UHFFFAOYSA-M 0.000 description 14
- 239000000047 product Substances 0.000 description 12
- -1 alkaline earth metal acetates Chemical class 0.000 description 10
- 239000006227 byproduct Substances 0.000 description 9
- 230000006315 carbonylation Effects 0.000 description 9
- 238000004821 distillation Methods 0.000 description 9
- 229910052744 lithium Inorganic materials 0.000 description 8
- 150000002903 organophosphorus compounds Chemical group 0.000 description 7
- 238000000746 purification Methods 0.000 description 7
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 6
- XMBWDFGMSWQBCA-UHFFFAOYSA-M iodide Chemical compound [I-] XMBWDFGMSWQBCA-UHFFFAOYSA-M 0.000 description 6
- 150000002897 organic nitrogen compounds Chemical group 0.000 description 6
- 150000004694 iodide salts Chemical class 0.000 description 5
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 238000009835 boiling Methods 0.000 description 4
- 229910017053 inorganic salt Inorganic materials 0.000 description 4
- XIXADJRWDQXREU-UHFFFAOYSA-M lithium acetate Chemical compound [Li+].CC([O-])=O XIXADJRWDQXREU-UHFFFAOYSA-M 0.000 description 4
- 239000000376 reactant Substances 0.000 description 4
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 3
- 125000000217 alkyl group Chemical group 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 230000007423 decrease Effects 0.000 description 3
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 description 3
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 3
- 150000004693 imidazolium salts Chemical class 0.000 description 3
- 239000007791 liquid phase Substances 0.000 description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 3
- 229910052698 phosphorus Inorganic materials 0.000 description 3
- 239000011574 phosphorus Substances 0.000 description 3
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 2
- 150000001351 alkyl iodides Chemical class 0.000 description 2
- 150000008064 anhydrides Chemical class 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 229910002092 carbon dioxide Inorganic materials 0.000 description 2
- 239000001569 carbon dioxide Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 239000011261 inert gas Substances 0.000 description 2
- 229910052740 iodine Inorganic materials 0.000 description 2
- 239000011630 iodine Substances 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- TZIHFWKZFHZASV-UHFFFAOYSA-N methyl formate Chemical compound COC=O TZIHFWKZFHZASV-UHFFFAOYSA-N 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 125000001477 organic nitrogen group Chemical group 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- 239000000243 solution Substances 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
- MCTWTZJPVLRJOU-UHFFFAOYSA-N 1-methyl-1H-imidazole Chemical compound CN1C=CN=C1 MCTWTZJPVLRJOU-UHFFFAOYSA-N 0.000 description 1
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical class [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical class [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 229910021604 Rhodium(III) chloride Inorganic materials 0.000 description 1
- 150000001242 acetic acid derivatives Chemical class 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910001516 alkali metal iodide Inorganic materials 0.000 description 1
- 229910001619 alkaline earth metal iodide Inorganic materials 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 229910052788 barium Inorganic materials 0.000 description 1
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 229910052790 beryllium Inorganic materials 0.000 description 1
- ATBAMAFKBVZNFJ-UHFFFAOYSA-N beryllium atom Chemical compound [Be] ATBAMAFKBVZNFJ-UHFFFAOYSA-N 0.000 description 1
- 229910052792 caesium Inorganic materials 0.000 description 1
- TVFDJXOCXUVLDH-UHFFFAOYSA-N caesium atom Chemical compound [Cs] TVFDJXOCXUVLDH-UHFFFAOYSA-N 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- NEHMKBQYUWJMIP-NJFSPNSNSA-N chloro(114C)methane Chemical compound [14CH3]Cl NEHMKBQYUWJMIP-NJFSPNSNSA-N 0.000 description 1
- 238000001944 continuous distillation Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 239000003085 diluting agent Substances 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000011010 flushing procedure Methods 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 229910052730 francium Inorganic materials 0.000 description 1
- KLMCZVJOEAUDNE-UHFFFAOYSA-N francium atom Chemical compound [Fr] KLMCZVJOEAUDNE-UHFFFAOYSA-N 0.000 description 1
- 238000007710 freezing Methods 0.000 description 1
- 230000008014 freezing Effects 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical class [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 150000002484 inorganic compounds Chemical class 0.000 description 1
- 229910001505 inorganic iodide Inorganic materials 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 229910052741 iridium Inorganic materials 0.000 description 1
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910001507 metal halide Inorganic materials 0.000 description 1
- 150000005309 metal halides Chemical class 0.000 description 1
- 229910001511 metal iodide Inorganic materials 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 239000012457 nonaqueous media Substances 0.000 description 1
- 125000002524 organometallic group Chemical group 0.000 description 1
- 238000005192 partition Methods 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- LSMAIBOZUPTNBR-UHFFFAOYSA-N phosphanium;iodide Chemical compound [PH4+].[I-] LSMAIBOZUPTNBR-UHFFFAOYSA-N 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 229910052705 radium Inorganic materials 0.000 description 1
- HCWPIIXVSYCSAN-UHFFFAOYSA-N radium atom Chemical compound [Ra] HCWPIIXVSYCSAN-UHFFFAOYSA-N 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- MMRXYMKDBFSWJR-UHFFFAOYSA-K rhodium(3+);tribromide Chemical compound [Br-].[Br-].[Br-].[Rh+3] MMRXYMKDBFSWJR-UHFFFAOYSA-K 0.000 description 1
- KXAHUXSHRWNTOD-UHFFFAOYSA-K rhodium(3+);triiodide Chemical compound [Rh+3].[I-].[I-].[I-] KXAHUXSHRWNTOD-UHFFFAOYSA-K 0.000 description 1
- SONJTKJMTWTJCT-UHFFFAOYSA-K rhodium(iii) chloride Chemical compound [Cl-].[Cl-].[Cl-].[Rh+3] SONJTKJMTWTJCT-UHFFFAOYSA-K 0.000 description 1
- 229910052701 rubidium Inorganic materials 0.000 description 1
- IGLNJRXAVVLDKE-UHFFFAOYSA-N rubidium atom Chemical compound [Rb] IGLNJRXAVVLDKE-UHFFFAOYSA-N 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 229910052712 strontium Inorganic materials 0.000 description 1
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 description 1
- 239000011269 tar Substances 0.000 description 1
- 125000005207 tetraalkylammonium group Chemical group 0.000 description 1
- 125000005497 tetraalkylphosphonium group Chemical group 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
- TYLYVJBCMQFRCB-UHFFFAOYSA-K trichlororhodium;trihydrate Chemical compound O.O.O.[Cl-].[Cl-].[Cl-].[Rh+3] TYLYVJBCMQFRCB-UHFFFAOYSA-K 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
- C07C51/54—Preparation of carboxylic acid anhydrides
- C07C51/56—Preparation of carboxylic acid anhydrides from organic acids, their salts, their esters or their halides, e.g. by carboxylation
-
- 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
- C07C51/42—Separation; Purification; Stabilisation; Use of additives
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/42—Separation; Purification; Stabilisation; Use of additives
- C07C51/43—Separation; Purification; Stabilisation; Use of additives by change of the physical state, e.g. crystallisation
- C07C51/44—Separation; Purification; Stabilisation; Use of additives by change of the physical state, e.g. crystallisation by distillation
-
- 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
- C07C51/573—Separation; Purification; Stabilisation; Use of additives
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Crystallography & Structural Chemistry (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Catalysts (AREA)
Description
(a)反応領域において、一酸化炭素を、酢酸メチル、ジメチルエーテルまたはそれらの混合物、第VIII族金属触媒、ヨウ化メチル、酢酸、無水酢酸、0.1重量%以下の濃度の水を含む液体反応組成物と接触させ;
(b)液体反応組成物を反応領域から取り出し、且つ取り出した液体反応組成物の少なくとも一部をフラッシュ分離領域に導入し;そして
(c)フラッシュ分離領域から、無水酢酸、酢酸およびヨウ化メチルを含む気体画分と、無水酢酸および第VIII族金属触媒を含む液体画分とを除去する;
工程を含み、
ここで、液体反応組成物およびフラッシュ分離領域に導入させる取り出した液体反応組成物のうちの少なくとも一つが、第IA族および第IIA族金属の塩から選択された少なくとも一つの金属塩を含み、且つフラッシュ分離領域から除去した気体画分における、酢酸対無水酢酸のモル比が、1より大または1に維持され、好適には1.2より大または1.2に維持される。
(a)反応領域において、一酸化炭素を、酢酸メチル、ジメチルエーテル、またはそれらの混合物と、ロジウム触媒と、ヨウ化メチルと、酢酸と、5〜25重量%の濃度の無水酢酸と、0.1重量%以下の濃度水とを含む液体反応組成物とを接触させ;
(b)反応領域から液体反応組成物を取り出し、且つ取り出した液体反応組成物の少なくとも一部をフラッシュ分離領域に導入し;および
(c)フラッシュ分離領域から、無水酢酸、酢酸およびヨウ化メチルを含む気体画分と、無水酢酸、ロジウム触媒を含む液体画分とを除去する;
工程を含み、
ここで、液体反応組成物、およびフラッシュ分離領域に導入させる取り出した液体反応組成物の少なくとも一つは、第IA族および第IIA族金属の塩から選択される少なくとも一つの金属塩を含み、且つフラッシュ分離領域から除去させる気体画分中の酢酸対無水酢酸のモル比は1より大または1、好適には1.2より大または1.2に維持される。
この参考例では、液体反応領域において、酢酸メチル、メタノール、ロジウム触媒、ヨウ化メチル及びイミダゾリウム塩を、実質無水条件下、約190℃の温度および約35bargの圧力で一酸化炭素と接触させて、無水酢酸および酢酸を含む液体反応組成物を生産した。
これらの実施例において、液体反応組成物を、酢酸リチウムの量を変更して、反応領域に加えたこと以外は、参考例に沿って生産した。液体反応組成物を、反応領域から取り出し、そして約135℃および約2bargの圧力で稼働したフラッシュ分離領域に導入した。無水酢酸および酢酸を含む気体画分を、フラッシュ分離領域からのオーバーヘッドとして除去し、そして無水酢酸、酢酸および触媒成分を含む液体画分をベースストリームとしてそこから除去した。
酢酸メチル、酢酸、ヨウ化メチル、無水酢酸、第VIII族金属触媒、触媒促進剤および任意にヨウ化リチウムを含む液体反応組成物を商業規模の反応器に連続的に供給した。一酸化炭素ガスを反応器において、散布装置を用いて反応組成物と接触させ、無水酢酸と酢酸とを生産した。液体反応混合物を、連続的に反応器から取り出し、そしてフラッシュバルブを介して、反応器と比較して減圧で稼働されたフラッシュ領域に移送し、酢酸および無水酢酸を含むオーバーヘッド気体画分と酢酸および触媒成分を含む液体画分とを生成した。金属塩の存在下および非存在下で生成された酢酸および無水酢酸の量(tpd(1日当りのトン))を表2に示す。
本実施例は、反応器において異なる濃度の無水酢酸を維持しながら、フラッシュ気体画分における、無水酢酸に対する酢酸のモル比を1に維持するために、必要なリチウム濃度を示す。無水酢酸(5〜35重量%)、酢酸(20〜50重量%)、および残部(45重量%)が酢酸メチル、ヨウ化メチル、リチウム塩および第VIII族金属触媒成分を含む液体反応組成物を、実質無水条件下、約190℃の温度および約36bargの圧力で稼働された反応器中で、連続的に一酸化炭素と接触させて、無水酢酸および酢酸を併産させた。反応組成物を、フラッシングバルブを介して約135℃の温度且つ約2bargの圧力で稼働させたフラッシュ容器に供給して、無水酢酸および酢酸を含む気体画分と、酢酸、リチウムおよび触媒成分を含む液体画分を生成するために分離させた。
金属塩と、酢酸対無水酢酸のモル比を、1.2、1.8、2.4および3にする組合せを適用して、実施例5を繰り返した。この結果を、表4〜7にそれぞれ示す。表4〜7には、反応器における所定の固定濃度の無水酢酸に対して、酢酸に対する無水酢酸の相対量を増加させるのに必要な金属塩の量が、フラッシュ気体における酢酸対無水酢酸の特定のモル比における、フラッシュ因子比の減少により示されている。
Claims (15)
- 酢酸および無水酢酸の併産のための連続プロセスは、
(a)反応領域において、一酸化炭素を、酢酸メチルまたはジメチルエーテルと酢酸メチルとの混合物、第VIII族金属触媒、ヨウ化メチル、酢酸、無水酢酸、0.1重量%濃度以下の水を含む液体反応組成物と接触させ、
(b)該反応領域から液体反応組成物を取り出し、且つ取り出した液体反応組成物の少なくとも一部をフラッシュ分離領域に導入し、
(c)該フラッシュ分離領域から、無水酢酸、酢酸およびヨウ化メチルを含む気体画分と、無水酢酸および第VIII族金属触媒を含む液体画分とを除去する
工程を含み、
該フラッシュ分離領域に導入する液体反応組成物は、第IA族および第IIA族金属の塩から選択される少なくとも一つの金属塩を含み、且つ該フラッシュ分離領域から除去される該気体画分における酢酸対無水酢酸のモル比を1.2〜3:1の範囲に維持し、
また、該プロセスは、更に、該気体画分の酢酸の少なくとも一部を、該酢酸がメタノールでエステル化され酢酸メチルを形成するエステル化工程に導き、且つそのように形成された該酢酸メチルの少なくとも一部を、工程(a)における反応のために該反応領域に導く
ことを含む、連続プロセス。 - 前記フラッシュ分離領域から除去される前記気体画分における酢酸対無水酢酸のモル比を1.2〜2.8:1の範囲に維持する、請求項1記載のプロセス。
- 前記フラッシュ分離領域から除去される前記気体画分における酢酸対無水酢酸のモル比を1.2〜1.5:1の範囲に維持する、請求項1記載のプロセス。
- 無水酢酸を、5〜35重量%の範囲の濃度で液体反応組成物中に維持する、請求項1乃至3のいずれか一項に記載のプロセス。
- 金属塩が第IA金属塩である、請求項1乃至4のいずれか一項に記載のプロセス。
- 第IA族および第IIA族金属は、0より大から14000ppmまでの範囲の総濃度で、液体反応組成物中に存在する、請求項1乃至5のいずれか一項に記載のプロセス。
- 金属塩が、反応領域における液体反応組成物中に存在する、請求項1乃至6のいずれか一項に記載のプロセス。
- 前記フラッシュ分離領域における酢酸および無水酢酸は、0.2〜1.4の範囲のフラッシュ因子比を有する、請求項1乃至7のいずれか一項に記載のプロセス。
- 第VIII族金属触媒がロジウム触媒である、請求項1乃至8のいずれか一項に記載のプロセス。
- 液体反応組成物が第VIII族金属触媒用の一つ以上の促進剤を更に含む、請求項1乃至9のいずれか一項に記載のプロセス。
- 液体反応組成物は、5〜35重量%の濃度に維持された無水酢酸と、20〜50重量%の濃度の酢酸と、および残部が酢酸メチル、ヨウ化メチル、金属塩、および第VIII族金属触媒、および任意に第VIII族金属触媒用の一つ以上の促進剤を含む、請求項1乃至10のいずれか一項に記載のプロセス。
- フラッシュ分離領域を、0bargから10bargまでの圧力で稼働させる、請求項1乃至11のいずれか一項に記載のプロセス。
- フラッシュ分離領域を、50℃〜400℃の温度で稼働させる、請求項1乃至12のいずれか一項に記載のプロセス。
- 反応領域を、150℃〜220℃の温度、且つ10〜100baraの全圧で維持する、請求項1乃至13のいずれか一項に記載のプロセス。
- 金属塩がリチウム塩である、請求項1記載のプロセス。
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Family Cites Families (24)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CH152249A (de) | 1931-01-05 | 1932-01-31 | Boehringer & Soehne Gmbh | Verfahren zur Trennung von Essigsäureanhydrid und Essigsäure. |
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 |
DE2836084A1 (de) | 1978-08-17 | 1980-03-06 | Hoechst Ag | Verfahren zur herstellung von essigsaeureanhydrid |
US4252741A (en) | 1978-10-06 | 1981-02-24 | Halcon Research & Development Corp. | Carbonylation with Group VIII noble metal catalysts |
US4264404A (en) | 1979-11-21 | 1981-04-28 | Formica Corporation | Cushion for laminating operations |
US4374070A (en) | 1980-11-21 | 1983-02-15 | Eastman Kodak Company | Preparation of acetic anhydride |
DE3149094A1 (de) * | 1981-12-11 | 1983-06-16 | Hoechst Ag, 6230 Frankfurt | Verfahren zur entfernung von aceton aus reaktionsgemischen von carbonylierungsreaktionen |
NZ203226A (en) | 1982-02-13 | 1985-08-30 | Bp Chemical Ltd | Production of acetic anhydride from methanol and carbon monoxide |
NZ203225A (en) | 1982-02-13 | 1985-01-31 | Bp Chem Int Ltd | Coproduction of monocarboxylic acids and anhydrides |
EP0146291B1 (en) * | 1983-11-30 | 1988-01-13 | The British Petroleum Company p.l.c. | Process for the production of carboxylic acids and/or esters thereof |
US5003104A (en) | 1987-03-03 | 1991-03-26 | Bp Chemicals Limited | Carbonylation process and catalyst |
ATE120444T1 (de) | 1990-12-20 | 1995-04-15 | Eastman Chem Co | Kontinuierliches verfahren zur herstellung von essigsäureanhydrid oder einer mischung von essigsäureanhydrid und essigsäure. |
GB9120902D0 (en) * | 1991-10-02 | 1991-11-13 | Bp Chem Int Ltd | Purification process |
CA2093752C (en) * | 1992-04-15 | 1999-06-15 | David W. Studer | Integrated process for oxygenated acetyl compounds from synthesis gas via dimethyl ether |
GB9521501D0 (en) * | 1995-10-20 | 1995-12-20 | Bp Chem Int Ltd | Process |
GB9802027D0 (en) * | 1998-01-31 | 1998-03-25 | Bp Chem Int Ltd | Chemical process |
US5922911A (en) * | 1998-04-24 | 1999-07-13 | Eastman Chemical Company | Process for the manufacture of acetic anhydride |
GB9930599D0 (en) | 1999-12-23 | 2000-02-16 | Bp Chem Int Ltd | Process |
US7737298B2 (en) * | 2006-06-09 | 2010-06-15 | Eastman Chemical Company | Production of acetic acid and mixtures of acetic acid and acetic anhydride |
US9012683B2 (en) * | 2010-11-12 | 2015-04-21 | Eastman Chemical Company | Coproduction of acetic acid and acetic anhydride |
KR101879006B1 (ko) * | 2010-12-15 | 2018-07-16 | 주식회사 다이셀 | 아세트산의 제조 방법 |
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