WO2018135015A1 - 酢酸の製造方法 - Google Patents
酢酸の製造方法 Download PDFInfo
- Publication number
- WO2018135015A1 WO2018135015A1 PCT/JP2017/019574 JP2017019574W WO2018135015A1 WO 2018135015 A1 WO2018135015 A1 WO 2018135015A1 JP 2017019574 W JP2017019574 W JP 2017019574W WO 2018135015 A1 WO2018135015 A1 WO 2018135015A1
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- WO
- WIPO (PCT)
- Prior art keywords
- acetic acid
- distillation
- mass
- distillation column
- column
- Prior art date
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- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 title claims abstract description 1159
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 80
- 238000004821 distillation Methods 0.000 claims abstract description 356
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 claims abstract description 122
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 claims abstract description 114
- 238000009835 boiling Methods 0.000 claims abstract description 76
- 235000019260 propionic acid Nutrition 0.000 claims abstract description 57
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 claims abstract description 57
- 238000000034 method Methods 0.000 claims abstract description 54
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims abstract description 28
- 239000012535 impurity Substances 0.000 claims abstract description 24
- 239000007788 liquid Substances 0.000 claims description 136
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 129
- 230000008569 process Effects 0.000 claims description 41
- 239000011541 reaction mixture Substances 0.000 claims description 37
- 238000001704 evaporation Methods 0.000 claims description 27
- 239000000463 material Substances 0.000 claims description 27
- 230000008020 evaporation Effects 0.000 claims description 26
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 24
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims description 20
- 229910002091 carbon monoxide Inorganic materials 0.000 claims description 20
- 238000005810 carbonylation reaction Methods 0.000 claims description 20
- 239000010935 stainless steel Substances 0.000 claims description 14
- 229910001220 stainless steel Inorganic materials 0.000 claims description 14
- 229910045601 alloy Inorganic materials 0.000 claims description 12
- 239000000956 alloy Substances 0.000 claims description 12
- 229910052759 nickel Inorganic materials 0.000 claims description 12
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 8
- 229910052782 aluminium Inorganic materials 0.000 claims description 8
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 8
- 229910052719 titanium Inorganic materials 0.000 claims description 8
- 239000010936 titanium Substances 0.000 claims description 8
- 150000001875 compounds Chemical class 0.000 claims description 6
- 238000005260 corrosion Methods 0.000 abstract description 48
- 230000007797 corrosion Effects 0.000 abstract description 48
- 150000001242 acetic acid derivatives Chemical class 0.000 abstract description 4
- IKHGUXGNUITLKF-UHFFFAOYSA-N Acetaldehyde Chemical compound CC=O IKHGUXGNUITLKF-UHFFFAOYSA-N 0.000 description 110
- 238000006243 chemical reaction Methods 0.000 description 81
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 63
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 63
- INQOMBQAUSQDDS-UHFFFAOYSA-N iodomethane Chemical compound IC INQOMBQAUSQDDS-UHFFFAOYSA-N 0.000 description 57
- 239000000047 product Substances 0.000 description 54
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 description 48
- 238000000605 extraction Methods 0.000 description 44
- 229910000043 hydrogen iodide Inorganic materials 0.000 description 42
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 42
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 40
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 35
- KXKVLQRXCPHEJC-UHFFFAOYSA-N acetic acid trimethyl ester Natural products COC(C)=O KXKVLQRXCPHEJC-UHFFFAOYSA-N 0.000 description 35
- 239000007789 gas Substances 0.000 description 32
- 239000000243 solution Substances 0.000 description 27
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 description 26
- 239000003456 ion exchange resin Substances 0.000 description 25
- 229920003303 ion-exchange polymer Polymers 0.000 description 25
- 239000008346 aqueous phase Substances 0.000 description 23
- 239000003054 catalyst Substances 0.000 description 22
- 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 21
- 235000019253 formic acid Nutrition 0.000 description 21
- 239000012074 organic phase Substances 0.000 description 21
- 239000002904 solvent Substances 0.000 description 20
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 19
- 229910052751 metal Inorganic materials 0.000 description 18
- 239000002184 metal Substances 0.000 description 18
- 238000000926 separation method Methods 0.000 description 18
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 16
- SCVFZCLFOSHCOH-UHFFFAOYSA-M potassium acetate Chemical compound [K+].CC([O-])=O SCVFZCLFOSHCOH-UHFFFAOYSA-M 0.000 description 16
- 238000004064 recycling Methods 0.000 description 15
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 14
- IKHGUXGNUITLKF-XPULMUKRSA-N acetaldehyde Chemical compound [14CH]([14CH3])=O IKHGUXGNUITLKF-XPULMUKRSA-N 0.000 description 13
- 239000000203 mixture Substances 0.000 description 13
- 239000006227 byproduct Substances 0.000 description 12
- 238000006297 dehydration reaction Methods 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 10
- 230000018044 dehydration Effects 0.000 description 10
- 239000012071 phase Substances 0.000 description 10
- 238000011144 upstream manufacturing Methods 0.000 description 10
- 239000003513 alkali Substances 0.000 description 9
- 229910052739 hydrogen Inorganic materials 0.000 description 9
- 239000001257 hydrogen Substances 0.000 description 9
- 150000002431 hydrogen Chemical class 0.000 description 9
- 229910052757 nitrogen Inorganic materials 0.000 description 9
- NLKNQRATVPKPDG-UHFFFAOYSA-M potassium iodide Chemical compound [K+].[I-] NLKNQRATVPKPDG-UHFFFAOYSA-M 0.000 description 9
- 238000012360 testing method Methods 0.000 description 9
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 8
- 239000003990 capacitor Substances 0.000 description 8
- 239000001569 carbon dioxide Substances 0.000 description 8
- 229910002092 carbon dioxide Inorganic materials 0.000 description 8
- 238000000895 extractive distillation Methods 0.000 description 8
- 239000007791 liquid phase Substances 0.000 description 8
- 239000001301 oxygen Substances 0.000 description 8
- 229910052760 oxygen Inorganic materials 0.000 description 8
- 235000011056 potassium acetate Nutrition 0.000 description 8
- 238000001816 cooling Methods 0.000 description 7
- 238000000746 purification Methods 0.000 description 7
- 238000001179 sorption measurement Methods 0.000 description 7
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 6
- -1 alkali metal salt Chemical class 0.000 description 6
- 230000006315 carbonylation Effects 0.000 description 6
- 150000002739 metals Chemical class 0.000 description 6
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 5
- 229910052783 alkali metal Inorganic materials 0.000 description 5
- 229910052741 iridium Inorganic materials 0.000 description 5
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 description 5
- 239000010948 rhodium Substances 0.000 description 5
- 229910052726 zirconium Inorganic materials 0.000 description 5
- 238000010521 absorption reaction Methods 0.000 description 4
- 239000002253 acid Substances 0.000 description 4
- 150000001351 alkyl iodides Chemical class 0.000 description 4
- 230000007423 decrease Effects 0.000 description 4
- 238000010586 diagram Methods 0.000 description 4
- 229910000856 hastalloy Inorganic materials 0.000 description 4
- HSZCZNFXUDYRKD-UHFFFAOYSA-M lithium iodide Chemical compound [Li+].[I-] HSZCZNFXUDYRKD-UHFFFAOYSA-M 0.000 description 4
- 230000003472 neutralizing effect Effects 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- 238000010992 reflux Methods 0.000 description 4
- 229910052703 rhodium Inorganic materials 0.000 description 4
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 4
- WAIPAZQMEIHHTJ-UHFFFAOYSA-N [Cr].[Co] Chemical compound [Cr].[Co] WAIPAZQMEIHHTJ-UHFFFAOYSA-N 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 239000011347 resin Substances 0.000 description 3
- 229920005989 resin Polymers 0.000 description 3
- FVAUCKIRQBBSSJ-UHFFFAOYSA-M sodium iodide Chemical compound [Na+].[I-] FVAUCKIRQBBSSJ-UHFFFAOYSA-M 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- SKIDNYUZJPMKFC-UHFFFAOYSA-N 1-iododecane Chemical compound CCCCCCCCCCI SKIDNYUZJPMKFC-UHFFFAOYSA-N 0.000 description 2
- ANOOTOPTCJRUPK-UHFFFAOYSA-N 1-iodohexane Chemical compound CCCCCCI ANOOTOPTCJRUPK-UHFFFAOYSA-N 0.000 description 2
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 159000000021 acetate salts Chemical class 0.000 description 2
- 150000004075 acetic anhydrides Chemical class 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 229910001516 alkali metal iodide Inorganic materials 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 230000005493 condensed matter Effects 0.000 description 2
- 238000001944 continuous distillation Methods 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- MLUCVPSAIODCQM-NSCUHMNNSA-N crotonaldehyde Chemical compound C\C=C\C=O MLUCVPSAIODCQM-NSCUHMNNSA-N 0.000 description 2
- MLUCVPSAIODCQM-UHFFFAOYSA-N crotonaldehyde Natural products CC=CC=O MLUCVPSAIODCQM-UHFFFAOYSA-N 0.000 description 2
- 239000012527 feed solution Substances 0.000 description 2
- 230000002401 inhibitory effect Effects 0.000 description 2
- 239000011630 iodine Substances 0.000 description 2
- 229910052740 iodine Inorganic materials 0.000 description 2
- 238000002955 isolation Methods 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- 229910001511 metal iodide Inorganic materials 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- VSZWPYCFIRKVQL-UHFFFAOYSA-N selanylidenegallium;selenium Chemical compound [Se].[Se]=[Ga].[Se]=[Ga] VSZWPYCFIRKVQL-UHFFFAOYSA-N 0.000 description 2
- 125000000542 sulfonic acid group Chemical group 0.000 description 2
- 239000002351 wastewater Substances 0.000 description 2
- IQGZCSXWIRBTRW-ZZXKWVIFSA-N (2E)-2-ethyl-2-butenal Chemical compound CC\C(=C/C)C=O IQGZCSXWIRBTRW-ZZXKWVIFSA-N 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 239000002250 absorbent Substances 0.000 description 1
- 230000002745 absorbent Effects 0.000 description 1
- 125000000218 acetic acid group Chemical group C(C)(=O)* 0.000 description 1
- ZCHPKWUIAASXPV-UHFFFAOYSA-N acetic acid;methanol Chemical compound OC.CC(O)=O ZCHPKWUIAASXPV-UHFFFAOYSA-N 0.000 description 1
- 239000003377 acid catalyst Substances 0.000 description 1
- 238000010306 acid treatment Methods 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 150000001350 alkyl halides Chemical class 0.000 description 1
- 238000000998 batch distillation Methods 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 239000003729 cation exchange resin Substances 0.000 description 1
- 239000012295 chemical reaction liquid Substances 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 239000003426 co-catalyst Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 150000004696 coordination complex Chemical class 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 150000004694 iodide salts Chemical group 0.000 description 1
- 230000026045 iodination Effects 0.000 description 1
- 238000006192 iodination reaction Methods 0.000 description 1
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical compound II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 description 1
- 235000013675 iodine Nutrition 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- BQZGVMWPHXIKEQ-UHFFFAOYSA-L iron(ii) iodide Chemical compound [Fe+2].[I-].[I-] BQZGVMWPHXIKEQ-UHFFFAOYSA-L 0.000 description 1
- 238000012423 maintenance Methods 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
- 238000005259 measurement Methods 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- 125000000896 monocarboxylic acid group Chemical group 0.000 description 1
- 150000002908 osmium compounds Chemical class 0.000 description 1
- ABLZXFCXXLZCGV-UHFFFAOYSA-N phosphonic acid group Chemical group P(O)(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000008439 repair process Effects 0.000 description 1
- 150000003304 ruthenium compounds Chemical class 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 235000009518 sodium iodide Nutrition 0.000 description 1
- 230000007928 solubilization Effects 0.000 description 1
- 238000005063 solubilization Methods 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 239000012808 vapor phase Substances 0.000 description 1
- 238000011179 visual inspection Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 238000003809 water extraction Methods 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/42—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
- C07C51/10—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
- C07C53/00—Saturated compounds having only one carboxyl group bound to an acyclic carbon atom or hydrogen
- C07C53/08—Acetic acid
Definitions
- the present invention relates to a method for producing acetic acid.
- This application claims the priority of Japanese Patent Application No. 2017-006646 filed in Japan on January 18, 2017 and Japanese Patent Application No. 2017-039390 filed in Japan on March 2, 2017. This is incorporated here.
- Methanol carbonylation process is known as an industrial method for producing acetic acid.
- methanol and carbon monoxide are reacted in the presence of a catalyst in a reaction vessel to produce acetic acid, the reaction mixture is evaporated in an evaporation vessel, and the vapor phase is removed from a low boiling tower followed by dehydration.
- Acetic acid is commercialized by purification in a tower, or acetic acid is commercialized through a dehigh boiling tower and further through a product tower following the dehydration tower (Patent Document 1, etc.).
- an object of the present invention is to provide a method capable of suppressing corrosion of a distillation apparatus in a method of producing acetic acid, which includes a step of purifying acetic acid by distilling acetic acid and a crude acetic acid solution containing impurities having a higher boiling point than acetic acid.
- the present inventors first examined the relationship between the composition of the bottom liquid of the distillation column and the bottom temperature.
- a metal catalyst such as a rhodium catalyst is used as a catalyst, and methyl iodide is used as a co-catalyst. Therefore, hydrogen iodide is by-produced in the reaction system. Most methyl iodide and hydrogen iodide are distilled and separated in the dehydration tower, but hydrogen iodide in the order of ppb and ppm exists in the bottoms of the dehydration tower. Therefore, alkali such as potassium hydroxide is charged in the dehydration tower or the bottoms to neutralize the remaining hydrogen iodide.
- the produced alkali metal salt (alkali metal iodide, alkali metal acetate) is removed by distillation equipment in the next step (for example, a deboiling tower).
- Such an alkali metal salt is concentrated at the bottom of the distillation column and discarded along with acetic acid from the bottom line.
- the amount of waste has been reduced to a minimum to improve the usage rate of acetic acid.
- the alkali metal salt concentration in the bottom liquid of the distillation tower is increased, the boiling point rises due to the salt, and the bottom temperature (bottom temperature) of the distillation tower rises.
- acetic anhydride is generated by the dehydration reaction of acetic acid.
- This acetic anhydride is produced in a larger amount by its catalytic action in the presence of a metal iodide (for example, iron iodide) produced by corrosion of the distillation equipment by hydrogen iodide.
- a metal iodide for example, iron iodide
- the dehydration reaction by the acid catalyst is promoted and acetic anhydride is increased. Therefore, when a distillation column (for example, a product column) for purifying acetic acid is provided downstream of the ion exchange resin treatment step, a large amount of acetic anhydride is present in the bottom liquid of this distillation column, Rises.
- the present invention relates to a method for producing acetic acid comprising a step of purifying acetic acid by distilling acetic acid and a crude acetic acid solution containing impurities having a boiling point higher than that of acetic acid.
- a method for producing acetic acid which is carried out under conditions of a bottom temperature of 165 ° C or lower.
- the acetic acid concentration in the crude acetic acid solution is preferably 90% by mass or more.
- the impurity having a boiling point higher than that of acetic acid preferably includes, for example, at least one compound selected from the group consisting of acetate, acetic anhydride, and propionic acid.
- the acetate concentration in the bottom liquid of the distillation column is preferably 34% by mass or less.
- the acetic anhydride concentration in the bottom liquid of the distillation tower is preferably 90% by mass or less.
- the propionic acid concentration in the bottom liquid of the distillation column is preferably 90% by mass or less.
- the bottom pressure of the distillation tower is 0.01 MPaG or more and less than 0.255 MPaG.
- a carbonylation reaction step of reacting methanol and carbon monoxide to produce acetic acid an evaporation step of separating the reaction mixture obtained in the carbonylation reaction step into a vapor stream and a residual liquid stream, A deboiling step of subjecting the vapor stream to distillation to separate an overhead stream rich in low boiling components and an acetic acid stream rich in acetic acid, and an acetic acid distillation step of purifying acetic acid by distilling the acetic acid stream, It is preferable that the acetic acid distillation step has at least one step of performing distillation of the crude acetic acid solution under the condition that the bottom temperature of the distillation column is 165 ° C. or lower.
- the acetic acid distillation step has at least one distillation step in which the concentration of acetic acid in the crude acetic acid solution to be subjected to distillation is 97% by mass or more. It is preferable to carry out distillation under the condition that the bottom temperature of the distillation column is 165 ° C. or less.
- the material of the distillation tower is preferably at least one selected from the group consisting of nickel-based alloys, stainless steel, aluminum and titanium.
- the concentration of acetate in the bottom liquid of the distillation column is 34% by mass or less
- the concentration of acetic anhydride is 90% by mass or less
- the concentration of propionic acid is 90% by mass or less. Is less than 0.255 MPa
- the material of the distillation column is at least one selected from the group consisting of nickel-based alloys, stainless steel, aluminum and titanium
- the column bottom temperature is preferably less than 165 ° C. .
- distillation when purifying acetic acid by distilling acetic acid and a crude acetic acid solution containing impurities having a boiling point higher than that of acetic acid, distillation is carried out under the condition that the bottom temperature of the distillation column is 165 ° C. or less. Even in the case of distillation under pressure for improvement, the corrosion of the distillation tower can be remarkably suppressed.
- the bottom temperature of the distillation column is 165 ° C. or lower (for example, less than 165 ° C.).
- the tower bottom temperature refers to the temperature of the tower bottom liquid.
- the material is not a highly corrosion-resistant material (zirconium, etc.) Can be used as When the bottom temperature of the distillation column exceeds 165 ° C., the corrosion rate of stainless steel and some nickel-based alloys is high even when acetate, acetic anhydride, and propionic acid are not present in the bottom liquid. These materials are not suitable as materials for the distillation column apparatus.
- the column bottom temperature of the distillation column is preferably 160 ° C. or lower, more preferably 155 ° C. or lower, further preferably 150 ° C. or lower, and particularly preferably 140 ° C. or lower. If the bottom temperature of the distillation column is 160 ° C. or lower, particularly 155 ° C. or lower, stainless steel is used as the material of the distillation apparatus even if a considerable amount of acetate, acetic anhydride, and propionic acid is present in the bottom liquid. Can be used. Furthermore, if the bottom temperature of the distillation column is 155 ° C. or lower, particularly 150 ° C. or lower, corrosion can be remarkably suppressed even if the distillation apparatus is made of stainless steel.
- the lower limit of the tower bottom temperature is, for example, 125 ° C., preferably 130 ° C., more preferably 135 ° C.
- the crude acetic acid solution to be subjected to distillation only needs to contain acetic acid and impurities having a boiling point higher than that of acetic acid, but those containing acetic acid as a main component are preferable, and the acetic acid concentration in the crude acetic acid solution is preferably Is 90% by mass or more (for example, 95% by mass or more), more preferably 97% by mass or more, further preferably 98% by mass or more, and particularly preferably 99% by mass or more.
- the impurity having a higher boiling point than that of acetic acid is not particularly limited, but the present invention particularly includes at least one compound selected from the group consisting of acetate, acetic anhydride and propionic acid as the high boiling point impurity. If you have a great effect.
- the acetate include alkali metal acetates such as potassium acetate.
- the acetate concentration in the bottom liquid of the distillation column is, for example, 34% by mass or less, preferably 23% by mass or less, more preferably 13% by mass or less, still more preferably 10% by mass or less, and particularly preferably 1% by mass or less. is there.
- the lower the acetate concentration in the bottom liquid the slower the corrosion rate.
- the lower limit of the acetate concentration in the bottom liquid is, for example, 0 mass ppm (or 1 mass ppm).
- alkali such as potassium hydroxide is added to neutralize highly corrosive hydrogen iodide by-produced in the reaction system.
- the added alkali not only reacts with hydrogen iodide, but also reacts with acetic acid to form an acetate salt (for example, potassium acetate).
- an acetate salt for example, potassium acetate.
- the concentration of acetate in the bottom liquid of the distillation column can be adjusted, for example, by adjusting the amount of alkali added.
- the concentration of acetic anhydride in the bottom liquid of the distillation column is, for example, 90% by mass or less, preferably 74% by mass or less, more preferably 45% by mass or less, further preferably 10% by mass or less, and particularly preferably 1% by mass or less. is there.
- the lower the concentration of acetic anhydride in the bottom liquid the slower the corrosion rate.
- the lower limit of the concentration of acetic anhydride in the tower bottom liquid is, for example, 0 mass ppm (or 1 mass ppm).
- the acetic anhydride concentration in the bottom liquid of the distillation column is adjusted by, for example, adding water to the piping or device located upstream of the distillation column or adding water into the distillation column to hydrolyze the acetic anhydride. Can do.
- the propionic acid concentration in the bottom liquid of the distillation column is, for example, 90% by mass or less, preferably 75% by mass or less, more preferably 55% by mass or less, still more preferably 29% by mass or less, and particularly preferably 10% by mass or less ( In particular, it is 1% by mass or less.
- the lower the propionic acid concentration in the bottom liquid the slower the corrosion rate.
- the lower limit of the propionic acid concentration in the column bottom liquid is, for example, 0 mass ppm (or 1 mass ppm).
- the concentration of propionic acid in the bottom liquid of the distillation column may be a cause of propionic acid by-product when, for example, reaction conditions are changed to reduce propionic acid by-products or when a part of the process liquid is recycled to the reaction system. This can be reduced by separating and removing the acetaldehyde from the process liquid and recycling it to the reaction system, or by providing a distillation column or an evaporator (depropionic acid column) for separating and removing propionic acid upstream of the distillation column.
- the bottom pressure of the distillation tower is appropriately adjusted according to the desired bottom temperature and bottom liquid composition.
- the tower bottom pressure is, for example, less than 0.255 MPaG, preferably 0.24 MPaG or less, more preferably 0.23 MPaG or less, and particularly preferably 0.21 MPaG or less.
- “G” indicates a gauge pressure.
- the higher the concentration of high-boiling impurities in the bottom liquid the higher the boiling point.
- the concentration of high-boiling impurities in the bottom liquid the lower the bottom pressure is. There is. The lower the bottom pressure, the lower the bottom temperature and the lower the corrosivity, but the lower the bottom pressure, the lower the gas density.
- the lower limit of the bottom pressure of the distillation column is, for example, 0.01 MPaG, preferably 0.02 MPaG, more preferably 0.03 MPaG, and particularly preferably 0.05 MPaG.
- the present invention since the column bottom temperature is adjusted to a specific value or less, acetic acid can be purified by distillation while preventing corrosion of the apparatus even under pressure. Therefore, the present invention is particularly useful when distillation is performed under pressure in order to increase the production efficiency of acetic acid.
- materials for the distillation column include zirconium, nickel-based alloys (Hastelloy B2, Hastelloy C, etc.), stainless steel [for example, SUS304, SUS316, SUS316L (SUS material having a lower carbon ratio than SUS316), SUS317, SUS317L ( SUS material having a carbon ratio lower than that of SUS317, etc.], or a corrosion resistant material equivalent to or lower than them (for example, aluminum, titanium, etc.) can be used.
- the price of materials decreases in the order of zirconium> Hastelloy B2> Hastelloy C> stainless steel. According to the present invention, since corrosion can be remarkably reduced, relatively inexpensive stainless steel can be sufficiently used as the material for the distillation column.
- the acetate concentration in the bottom liquid of the distillation column is 34% by mass or less
- the acetic anhydride concentration is 90% by mass or less
- the propionic acid concentration is 90% by mass or less
- the column bottom pressure of the distillation column is It is preferably less than 0.255 MPa
- the material of the distillation column is preferably at least one selected from the group consisting of nickel-based alloys, stainless steel, aluminum and titanium.
- the form of distillation may be either batch distillation or continuous distillation, but continuous distillation is more preferable in terms of production efficiency and the like.
- the method for producing acetic acid of the present invention is particularly useful in a methanol carbonylation process. That is, a carbonylation reaction step of reacting methanol with carbon monoxide to produce acetic acid, an evaporation step of separating the reaction mixture obtained in the carbonylation reaction step into a vapor stream and a residual liquid stream,
- a carbonylation reaction step of reacting methanol with carbon monoxide to produce acetic acid
- an evaporation step of separating the reaction mixture obtained in the carbonylation reaction step into a vapor stream and a residual liquid stream
- an acetic acid production process comprising a de-low boiling step for separation into an overhead stream rich in low boiling components and an acetic acid stream rich in acetic acid by distillation, and an acetic acid distillation process in which the acetic acid stream is distilled to purify acetic acid
- the acetic acid distillation step has at least one step of obtaining purified acetic acid by distilling acetic acid and a
- the acetic acid distillation step has at least one distillation step in which the concentration of acetic acid in the crude acetic acid solution to be subjected to distillation is 97% by mass or more. It is preferable to obtain purified acetic acid by distillation at a bottom temperature of the distillation column of 165 ° C. or lower.
- FIG. 1 is an example of an acetic acid production flow diagram (methanol carbonylation process) showing an embodiment of the present invention.
- the acetic acid production apparatus includes a reaction tank 1, an evaporation tank 2, a distillation tower 3, a decanter 4, a distillation tower 5, a distillation tower 6, an ion exchange resin tower 7, and a scrubber system 8. And acetaldehyde separation and removal system 9, condensers 1a, 2a, 3a, 5a and 6a, heat exchanger 2b, reboilers 3b, 5b and 6b, lines 11 to 56, and pump 57, and acetic acid is continuously added.
- reaction tank 1 the reaction tank 1, the evaporation tank 2, the distillation tower 3, the distillation tower 5, the distillation tower 6, and the ion exchange resin tower 7, respectively.
- a reaction process an evaporation process (flash process), A 1st distillation process, a 2nd distillation process, a 3rd distillation process, and an adsorption removal process are performed.
- the first distillation step is also called a delow boiling step
- the second distillation step is also called a dehydration step
- the third distillation step is also called a dehigh boiling step.
- the first distillation step, the second distillation step, and the third distillation step are included in the “acetic acid distillation step for purifying acetic acid” in the present invention.
- the process is not limited to the above, and in particular, the equipment of the distillation column 5, the ion exchange resin column 7, and the acetaldehyde separation / removal system 9 (such as a deacetaldehyde column) may not be incidental.
- a product tower may be provided downstream of the ion exchange resin tower 7. This product column is also included in the “acetic acid distillation step for purifying acetic acid” in the present invention.
- the reaction tank 1 is a unit for performing a reaction process.
- This reaction step is a step for continuously generating acetic acid by a reaction (methanol carbonylation reaction) represented by the following chemical formula (1).
- a reaction mixture that is stirred by, for example, a stirrer exists in the reaction tank 1.
- the reaction mixture contains methanol and carbon monoxide as raw materials, a metal catalyst, a cocatalyst, water, acetic acid for production purposes, and various by-products, and the liquid phase and the gas phase are in an equilibrium state. It is in. CH 3 OH + CO ⁇ CH 3 COOH (1)
- the raw materials in the reaction mixture are liquid methanol and gaseous carbon monoxide.
- Methanol is continuously supplied at a predetermined flow rate from the methanol reservoir (not shown) to the reaction tank 1 through the line 11.
- Carbon monoxide is continuously supplied from the carbon monoxide reservoir (not shown) to the reaction tank 1 through the line 12 at a predetermined flow rate.
- Carbon monoxide does not necessarily have to be pure carbon monoxide. For example, it contains a small amount of other gases such as nitrogen, hydrogen, carbon dioxide and oxygen (for example, 5% by mass or less, preferably 1% by mass or less). Also good.
- the metal catalyst in the reaction mixture is for accelerating the carbonylation reaction of methanol.
- a rhodium catalyst or an iridium catalyst can be used.
- a rhodium catalyst for example, a rhodium complex represented by the chemical formula [Rh (CO) 2 I 2 ] ⁇ can be used.
- a iridium catalyst for example, an iridium complex represented by the chemical formula [Ir (CO) 2 I 2 ] ⁇ can be used.
- a metal complex catalyst is preferable as the metal catalyst.
- the concentration of the catalyst in the reaction mixture (in metal conversion) is, for example, 200 to 5000 ppm by mass, preferably 400 to 2000 ppm by mass with respect to the entire liquid phase of the reaction mixture.
- the cocatalyst is an iodide for assisting the action of the above-described catalyst, and for example, methyl iodide or ionic iodide is used.
- Methyl iodide can exhibit an action of promoting the catalytic action of the above-described catalyst.
- the concentration of methyl iodide is, for example, 1 to 20% by mass with respect to the entire liquid phase of the reaction mixture.
- the ionic iodide is an iodide (in particular, an ionic metal iodide) that generates iodide ions in the reaction solution, and can exhibit an effect of stabilizing the above-described catalyst and an effect of suppressing side reactions.
- ionic iodide examples include alkali metal iodides such as lithium iodide, sodium iodide, and potassium iodide.
- concentration of ionic iodide in the reaction mixture is, for example, 1 to 25% by mass, preferably 5 to 20% by mass, based on the entire liquid phase of the reaction mixture.
- a ruthenium compound or an osmium compound can also be used as a promoter.
- the total amount of these compounds used is, for example, 0.1 to 30 mol (metal conversion), preferably 0.5 to 15 mol (metal conversion) with respect to 1 mol of iridium (metal conversion).
- Water in the reaction mixture is a component necessary for generating acetic acid in the reaction mechanism of the carbonylation reaction of methanol, and is also a component necessary for solubilization of water-soluble components in the reaction system.
- the concentration of water in the reaction mixture is, for example, from 0.1 to 15% by mass, preferably from 0.8 to 10% by mass, more preferably from 1 to 6% by mass, with respect to the entire liquid phase of the reaction mixture.
- the amount is preferably 1.5 to 4% by mass.
- the water concentration is preferably 15% by mass or less in order to suppress the energy required for water removal during the purification process of acetic acid and promote the efficiency of acetic acid production.
- a predetermined flow rate of water may be continuously supplied to the reaction tank 1.
- Acetic acid in the reaction mixture contains acetic acid that is charged in advance in the reaction tank 1 before the operation of the acetic acid production apparatus, and acetic acid generated as a main product of methanol carbonylation reaction. Such acetic acid can function as a solvent in the reaction system.
- the concentration of acetic acid in the reaction mixture is, for example, 50 to 90% by mass, preferably 60 to 80% by mass, based on the entire liquid phase of the reaction mixture.
- Examples of main by-products contained in the reaction mixture include methyl acetate. This methyl acetate can be generated by the reaction of acetic acid and methanol.
- the concentration of methyl acetate in the reaction mixture is, for example, 0.1 to 30% by mass, preferably 1 to 10% by mass, with respect to the entire liquid phase of the reaction mixture.
- Examples of by-products contained in the reaction mixture include hydrogen iodide. This hydrogen iodide is inevitably generated due to the reaction mechanism of the carbonylation reaction of methanol when the above-described catalyst or promoter is used.
- the concentration of hydrogen iodide in the reaction mixture is, for example, 0.01 to 2% by mass with respect to the entire liquid phase of the reaction mixture.
- Examples of by-products include hydrogen, methane, carbon dioxide, acetaldehyde, crotonaldehyde, 2-ethylcrotonaldehyde, dimethyl ether, alkanes, formic acid, propionic acid, and iodine such as hexyl iodide and decyl iodide. And alkyl halide.
- the reaction mixture includes metals such as iron, nickel, chromium, manganese, and molybdenum (hereinafter sometimes referred to as “corrosive metals”) generated by corrosion of the apparatus, and other metals such as cobalt, zinc, and copper. Can be included.
- the corrosive metal and other metals may be collectively referred to as “corrosive metal or the like”.
- the reaction temperature is set to 150 to 250 ° C., for example, and the reaction pressure as the total pressure is set to 2.0 to 3.5 MPa (absolute pressure), for example.
- the carbon monoxide partial pressure is set to, for example, 0.4 to 1.8 MPa (absolute pressure), preferably 0.6 to 1.5 MPa (absolute pressure).
- carbon monoxide, hydrogen, methane, carbon dioxide, nitrogen, oxygen, methyl iodide, hydrogen iodide, water, methyl acetate, acetic acid, dimethyl ether can be used as the vapor in the gas phase in the reaction tank 1 when the apparatus is in operation.
- Methanol, acetaldehyde, formic acid and propionic acid can be used as the vapor in the gas phase in the reaction tank 1 when the apparatus is in operation.
- This vapor can be extracted from the reaction vessel 1 through the line 13. It is possible to control the pressure in the reaction tank 1 by adjusting the amount of steam extracted. For example, the pressure in the reaction tank 1 is maintained constant.
- the steam extracted from the reaction tank 1 is introduced into the condenser 1a.
- the condenser 1a divides the vapor from the reaction tank 1 into a condensed component and a gas component by cooling and partially condensing.
- the condensate contains, for example, methyl iodide, hydrogen iodide, water, methyl acetate, acetic acid, dimethyl ether, methanol, acetaldehyde, formic acid, propionic acid, etc., and is introduced into the reaction tank 1 from the condenser 1a through the line 14 and recycled. Is done.
- the gas component includes, for example, carbon monoxide, hydrogen, methane, carbon dioxide, nitrogen, oxygen, methyl iodide, hydrogen iodide, water, methyl acetate, acetic acid, dimethyl ether, methanol, acetaldehyde, formic acid, and the like. It is supplied to the scrubber system 8 through a line 15.
- useful components for example, methyl iodide, water, methyl acetate, acetic acid, etc.
- a wet method is used for the separation and recovery, which is performed using an absorption liquid for collecting useful components in the gas component.
- an absorbing solvent containing at least acetic acid and / or methanol is preferable.
- the absorbing solution may contain methyl acetate.
- a condensate of vapor from the later-described distillation column 6 can be used as the absorbing liquid.
- a pressure fluctuation adsorption method may be used.
- Separated and recovered useful components are introduced from the scrubber system 8 into the reaction tank 1 through the recycling line 48 and recycled.
- the gas after collecting useful components is discarded through line 49.
- the gas discharged from the line 49 can be used as a CO source to be introduced into the bottom of the evaporation tank 2 described later or the residual liquid flow recycling lines 18 and 19.
- the processing in the scrubber system 8 and the subsequent recycling and disposal to the reaction vessel 1 are the same for the gas components described later supplied to the scrubber system 8 from other capacitors.
- acetic acid is continuously produced in the reaction tank 1 when the apparatus is in operation.
- a reaction mixture containing such acetic acid is continuously withdrawn from the reaction tank 1 at a predetermined flow rate and introduced into the next evaporation tank 2 through a line 16.
- the evaporation tank 2 is a unit for performing an evaporation process (flash process).
- a vapor stream (volatile phase) and a residual liquid stream (low volatile phase) are obtained by partially evaporating the reaction mixture continuously introduced into the evaporation tank 2 through the line 16 (reaction mixture supply line). It is a process for dividing into. Evaporation may be caused by reducing the pressure without heating the reaction mixture, or evaporation may be caused by reducing the pressure while heating the reaction mixture.
- the temperature of the vapor stream is, for example, 100 to 260 ° C., preferably 120 to 200 ° C.
- the temperature of the residual liquid stream is, for example, 80 to 200 ° C., preferably 100 to 180 ° C.
- the pressure in the tank is, for example, 50 to 1000 kPa (absolute pressure).
- the ratio of the vapor flow and the residual liquid flow separated in the evaporation step is, for example, 10/90 to 50/50 (vapor flow / residual liquid flow) in mass ratio.
- the steam generated in this step includes, for example, methyl iodide, hydrogen iodide, water, methyl acetate, acetic acid, dimethyl ether, methanol, acetaldehyde, formic acid, propionic acid, and the like.
- Continuously extracted A part of the vapor flow extracted from the evaporation tank 2 is continuously introduced into the condenser 2 a, and the other part of the vapor flow is continuously introduced into the next distillation column 3 through the line 21.
- the acetic acid concentration of the vapor stream is, for example, 40 to 85% by mass (preferably 50 to 85% by mass), more preferably 50 to 75% by mass (for example 55 to 75% by mass), and the methyl iodide concentration is, for example, 2 to 50% by mass (preferably 5 to 30% by mass), water concentration is, for example, 0.2 to 20% by mass (preferably 1 to 15% by mass), and methyl acetate concentration is, for example, 0.2 to 50% by mass (Preferably 2 to 30% by mass).
- the residual liquid stream generated in this step is the catalyst and cocatalyst (methyl iodide, lithium iodide, etc.) contained in the reaction mixture, water remaining without volatilization in this step, methyl acetate, acetic acid, formic acid and It contains propionic acid and the like and is continuously introduced from the evaporation tank 2 to the heat exchanger 2b through the line 18 using the pump 57.
- the heat exchanger 2b cools the residual liquid stream from the evaporation tank 2.
- the cooled residual liquid stream is continuously introduced from the heat exchanger 2b to the reaction tank 1 through the line 19 and recycled.
- the line 18 and the line 19 are collectively referred to as a residual liquid recycle line.
- the concentration of acetic acid in the residual stream is, for example, 55 to 90% by mass, preferably 60 to 85% by mass.
- the gas component includes, for example, carbon monoxide, hydrogen, methane, carbon dioxide, nitrogen, oxygen, methyl iodide, hydrogen iodide, water, methyl acetate, acetic acid, dimethyl ether, methanol, acetaldehyde, formic acid, and the like. It is supplied to the scrubber system 8 through lines 20 and 15.
- the acetic acid production reaction in the above reaction step is an exothermic reaction, and part of the heat accumulated in the reaction mixture is transferred to the vapor generated from the reaction mixture in the evaporation step (flash step).
- the condensed matter generated by the cooling of the steam in the condenser 2 a is recycled to the reaction tank 1. That is, in this acetic acid production apparatus, heat generated by the carbonylation reaction of methanol is efficiently removed by the capacitor 2a.
- the distillation column 3 is a unit for performing the first distillation step, and is positioned as a so-called deboiling tower in this embodiment.
- the first distillation step is a step of separating and removing low boiling components by distillation treatment of the steam stream continuously introduced into the distillation column 3. More specifically, in the first distillation step, the vapor stream is distilled and separated into an overhead stream rich in at least one low-boiling component selected from methyl iodide and acetaldehyde and an acetic acid stream rich in acetic acid. .
- the distillation column 3 is composed of, for example, a rectification column such as a plate column and a packed column.
- the theoretical plate is, for example, 5 to 50 plates, and the reflux ratio is, for example, 0.5 to 3000 depending on the number of theoretical plates.
- the column top pressure is set to 80 to 160 kPaG, for example, and the column bottom pressure is set higher than the column top pressure, for example to 85 to 180 kPaG.
- the column top temperature is set to 90 to 130 ° C., for example, lower than the boiling point of acetic acid at the set column top pressure, and the column bottom temperature is set to, for example, the set column bottom pressure.
- the temperature is equal to or higher than the boiling point of acetic acid and is set to 120 to 165 ° C. (preferably 125 to 160 ° C.).
- the vapor flow from the evaporation tank 2 is continuously introduced through the line 21, and the vapor as an overhead flow is continuously extracted from the top of the distillation column 3 to the line 24. From the bottom of the distillation column 3, the bottoms are continuously extracted into the line 25.
- 3b is a reboiler.
- An acetic acid stream (first acetic acid stream; liquid) as a side stream is continuously extracted from the line 27 from a height position between the top and bottom of the distillation column 3.
- the steam withdrawn from the top of the distillation column 3 contains a larger amount of components having a lower boiling point than that of acetic acid (low-boiling components) compared to the bottoms and side stream from the distillation column 3, such as methyl iodide, Including hydrogen iodide, water, methyl acetate, dimethyl ether, methanol, acetaldehyde and formic acid. This vapor also contains acetic acid.
- acetic acid low-boiling components
- the condenser 3a divides the vapor from the distillation tower 3 into a condensed component and a gas component by cooling and partially condensing.
- the condensate includes, for example, methyl iodide, hydrogen iodide, water, methyl acetate, acetic acid, dimethyl ether, methanol, acetaldehyde, formic acid, and the like, and is continuously introduced from the capacitor 3 a to the decanter 4 through the line 28.
- the condensed matter introduced into the decanter 4 is separated into an aqueous phase (upper phase) and an organic phase (methyl iodide phase; lower phase).
- the aqueous phase includes water and, for example, methyl iodide, hydrogen iodide, methyl acetate, acetic acid, dimethyl ether, methanol, acetaldehyde and formic acid.
- the organic phase includes, for example, methyl iodide and, for example, hydrogen iodide, water, methyl acetate, acetic acid, dimethyl ether, methanol, acetaldehyde and formic acid.
- a part of the aqueous phase is refluxed to the distillation column 3 through the line 29, and the other part of the aqueous phase is introduced into the reaction vessel 1 through the lines 29, 30, and 23 and recycled.
- a part of the organic phase is introduced into the reaction vessel 1 through lines 31 and 23 and recycled.
- the other part of the organic phase and / or the other part of the aqueous phase is introduced into the acetaldehyde separation and removal system 9 through the lines 31, 50 and / or the lines 30, 51.
- acetaldehyde contained in the organic phase and / or the aqueous phase is separated and removed by a known method, for example, distillation, extraction, or a combination thereof.
- the separated acetaldehyde is discharged out of the apparatus through a line 53.
- useful components such as methyl iodide contained in the organic phase and / or the aqueous phase are recycled to the reaction tank 1 through the lines 52 and 23 and reused.
- FIG. 2 is a schematic flow diagram showing an example of an acetaldehyde separation and removal system.
- the organic phase is fed to the distillation column (first deacetaldehyde column) 91 through the line 101 and distilled, and an overhead stream rich in acetaldehyde is obtained. (Line 102) and a residual stream rich in methyl iodide (line 103).
- the overhead stream is condensed in the condenser 91a, a part of the condensate is refluxed to the top of the distillation column 91 (line 104), and the other part of the condensate is supplied to the extraction tower 92 (line 105).
- the condensate supplied to the extraction tower 92 is extracted with water introduced from the line 109.
- the extract obtained by the extraction process is supplied to a distillation tower (second deacetaldehyde tower) 93 through a line 107 and distilled, and an overhead stream rich in acetaldehyde (line 112) and a residual liquid stream rich in water (line 113) To separate.
- the overhead stream rich in acetaldehyde is condensed by the condenser 93a, a part of the condensate is refluxed to the top of the distillation column 93 (line 114), and the other part of the condensate is discharged out of the system (line 115). ).
- a methyl iodide-rich residual liquid stream that is the bottoms of the first deacetaldehyde column 91, a methyl iodide-rich raffinate obtained in the extraction column 92 (line 108), and a second deacetaldehyde column 93 can
- the water-rich residual liquid stream that is the effluent is recycled to the reaction vessel 1 through lines 103, 111, and 113, respectively, or recycled to an appropriate location in the process and reused.
- the methyl iodide rich raffinate obtained in extraction column 92 can be recycled to distillation column 91 through line 110.
- the liquid 113 is usually discharged to the outside as waste water. Gases (lines 106, 116) that have not been condensed by the condensers 91a, 93a are absorbed by the scrubber system 8 or disposed of.
- the aqueous phase is supplied to the distillation column (first deacetaldehyde column) 91 through the line 101 and distilled to enrich the acetaldehyde.
- the overhead stream (line 102) is separated into a water-rich residual liquid stream (line 103).
- the overhead stream is condensed in the condenser 91a, a part of the condensate is refluxed to the top of the distillation column 91 (line 104), and the other part of the condensate is supplied to the extraction tower 92 (line 105).
- the condensate supplied to the extraction tower 92 is extracted with water introduced from the line 109.
- the extract obtained by the extraction process is supplied to a distillation tower (second deacetaldehyde tower) 93 through a line 107 and distilled, and an overhead stream rich in acetaldehyde (line 112) and a residual liquid stream rich in water (line 113) To separate.
- the overhead stream rich in acetaldehyde is condensed by the condenser 93a, a part of the condensate is refluxed to the top of the distillation column 93 (line 114), and the other part of the condensate is discharged out of the system (line 115). ).
- a water-rich residual stream that is the bottoms of the first deacetaldehyde tower 91, a methyl iodide-rich raffinate obtained from the extraction tower 92 (line 108), and a bottoms of the second deacetaldehyde tower 93
- the water-rich residual liquid stream is recycled to the reaction tank 1 through the lines 103, 111, and 113, or recycled to an appropriate part of the process and reused.
- the methyl iodide rich raffinate obtained in extraction column 92 can be recycled to distillation column 91 through line 110.
- the liquid 113 is usually discharged to the outside as waste water. Gases (lines 106, 116) that have not been condensed by the condensers 91a, 93a are absorbed by the scrubber system 8 or disposed of.
- Acetaldehyde derived from a process stream containing at least water, acetic acid (AC), methyl iodide (MeI) and acetaldehyde (AD) can be separated and removed using extractive distillation in addition to the above method.
- the organic phase and / or the aqueous phase (feed solution) obtained by separating the process stream is supplied to a distillation column (extraction distillation column), and methyl iodide and acetaldehyde in the distillation column are concentrated.
- An extraction solvent usually water
- is introduced into the concentration area for example, the space from the top of the column to the feed liquid supply position
- the liquid descending from the concentration area extraction liquid is extracted as a side flow (side cut flow).
- Acetaldehyde can be discharged out of the system by separating the side stream into an aqueous phase and an organic phase and distilling the aqueous phase. If a relatively large amount of water is present in the distillation column, the liquid descending from the concentration zone may be withdrawn as a side stream without introducing the extraction solvent into the distillation column.
- a unit such as a chimney tray
- the extraction solvent introduction position is preferably above the feed liquid supply position, and more preferably near the top of the column.
- the side stream extraction position is preferably lower than the extraction solvent introduction position and higher than the feed liquid supply position in the height direction of the column.
- a high concentration of acetaldehyde can be extracted from the concentrate of methyl iodide and acetaldehyde with an extraction solvent (usually water), and the area between the extraction solvent introduction site and the side cut site is used as an extraction zone. Therefore, acetaldehyde can be extracted efficiently with a small amount of extraction solvent. Therefore, for example, the number of stages of the distillation column can be greatly reduced and the steam load can be reduced as compared with a method of extracting the extract by extraction distillation from the bottom of the distillation column (extraction distillation column).
- the ratio (MeI / AD ratio) of methyl iodide with respect to acetaldehyde in a water extract can be made smaller than the method of combining the dealdehyde distillation and water extraction of the said FIG. 2 using a small amount of extraction solvent, Acetaldehyde can be removed under conditions that can prevent loss of methyl iodide to the outside of the system.
- the concentration of acetaldehyde in the side stream is much higher than the concentration of acetaldehyde in the charged solution and bottoms (bottom solution).
- the ratio of the acetaldehyde with respect to the methyl iodide in the said side stream is larger than the ratio of the acetaldehyde with respect to the methyl iodide in the preparation liquid and the bottom liquid.
- the organic phase (methyl iodide phase) obtained by separating the side stream may be recycled to this distillation column.
- the recycling position of the organic phase obtained by separating the side flow is preferably lower than the side flow extraction position in the height direction of the tower, and preferably higher than the feed liquid supply position.
- a miscible solvent for components (for example, methyl acetate) constituting the organic phase obtained by separating the process stream may be introduced into this distillation column (extraction distillation column).
- miscible solvent examples include acetic acid and ethyl acetate.
- the introduction position of the miscible solvent is preferably lower than the side flow extraction position and higher than the feed liquid supply position in the height direction of the tower.
- the position where the miscible solvent is introduced is preferably lower than the recycling position when the organic phase obtained by separating the side stream is recycled to the distillation column. Recycling the organic phase obtained by separating the side stream into a distillation column or introducing the miscible solvent into the distillation column can reduce the methyl acetate concentration in the extract extracted as a side stream.
- the concentration of methyl acetate in the aqueous phase obtained by separating the extract can be reduced, so that the mixing of methyl iodide into the aqueous phase can be suppressed.
- the theoretical column of the distillation column is, for example, 1 to 100 plate, preferably 2 to 50 plate, more preferably 3 to 30 plate, particularly preferably 5 to 20 plate, and is used for conventional deacetaldehyde.
- acetaldehyde can be separated and removed efficiently with a small number of stages.
- the mass ratio (the former / the latter) of the flow rate of the extraction solvent and the flow rate of the feed liquid (the organic phase and / or the aqueous phase obtained by separating the process stream) is in the range of 0.0001 / 100 to 100/100.
- the top temperature of the distillation column is, for example, 15 to 120 ° C., preferably 20 to 90 ° C., more preferably 20 to 80 ° C., and further preferably 25 to 70 ° C.
- the tower top pressure is an absolute pressure, for example, about 0.1 to 0.5 MPa.
- Other conditions for the distillation column may be the same as those for the conventional distillation column and extraction distillation column used for deacetaldehyde.
- FIG. 3 is a schematic flow diagram showing an example of an acetaldehyde separation and removal system using the above extractive distillation.
- the organic phase and / or the aqueous phase (feed solution) obtained by separating the process stream is supplied to the middle stage of the distillation column 94 (position between the top and the bottom) through the supply line 201.
- water is introduced from the vicinity of the top of the column through the line 202, and extractive distillation is performed in the distillation column 94 (extraction distillation column).
- a chimney tray 200 for receiving a liquid (extracted liquid) descending from a concentration area where methyl iodide and acetaldehyde in the tower are concentrated is disposed above the supply position of the charged liquid in the distillation column 94. .
- the entire amount of the liquid on the chimney tray 200 is preferably withdrawn and introduced into the decanter 95 through the line 208 for liquid separation.
- the aqueous phase (including acetaldehyde) in the decanter 95 is introduced into the cooling cooler 95 a through the line 212 and cooled, and the two phases of methyl iodide dissolved in the aqueous phase are separated and separated in the decanter 96.
- the aqueous phase in the decanter 96 is fed to the distillation column 97 (deacetaldehyde column) through the line 216 and distilled, and the vapor at the top of the column is led to the condenser 97a through the line 217 to be condensed and condensed (mainly acetaldehyde and methyl iodide). ) Is refluxed to the top of the distillation column 97 and the rest is discarded or supplied to the distillation column 98 (extraction distillation column) through the line 220. Water is introduced from the vicinity of the top of the distillation column 98 through the line 222, and extractive distillation is performed.
- the vapor at the top of the column is led to the condenser 98a through the line 223 to be condensed, a part of the condensate (mainly methyl iodide) is refluxed to the top of the column, and the rest is recycled to the reaction system through the line 226.
- the entire amount of the organic phase (methyl iodide phase) in the decanter 95 is preferably recycled below the position of the chimney tray 200 in the distillation column 94 through lines 209 and 210.
- a part of the aqueous phase of the decanter 95 and the organic phase of the decanter 96 are recycled to the distillation column 94 through lines 213 and 210 and lines 214 and 210, respectively, but may not be recycled.
- a part of the aqueous phase of the decanter 95 may be used as an extraction solvent (water) in the distillation column 94.
- a portion of the aqueous phase of the decanter 96 may be recycled to the distillation column 94 through line 210.
- a miscible solvent acetic acid, etc.
- components for example, methyl acetate constituting the organic phase obtained by separating the process stream.
- Ethyl acetate, etc. can be charged into the distillation column 94 through the line 215 to improve the distillation efficiency.
- the supply position of the miscible solvent to the distillation column 94 is above the feed liquid supply unit (connection part of the line 201) and below the connection part of the recycle line 210.
- the bottoms of the distillation column 94 is recycled to the reaction system.
- the vapor at the top of the distillation column 94 is led to the condenser 94a through the line 203 to be condensed, the condensate is separated by the decanter 99, the organic phase is refluxed to the top of the distillation column 94 through the line 206, and the aqueous phase is line.
- the bottoms of the distillation tower 97 (water is the main component) and the bottoms of the distillation tower 98 (extraction distillation tower) (water containing a small amount of acetaldehyde) are removed from the system through lines 218 and 224, respectively, or the reaction system. Recycle to. Gases (lines 211, 2221 and 227) which have not been condensed by the condensers 94a, 97a and 98a are absorbed by the scrubber system 8 or disposed of.
- FIG. 4 is a schematic flow diagram showing another example of an acetaldehyde separation / removal system using the above extractive distillation.
- the vapor condensate at the top of the distillation column 94 is led to the hold tank 100, and the entire amount is refluxed to the top of the distillation column 94 through the line 206.
- the rest is the same as the example of FIG.
- FIG. 5 is a schematic flowchart showing still another example of the acetaldehyde separation and removal system using the above-described extractive distillation.
- the entire amount of the liquid on the chimney tray 200 is extracted, and is directly introduced into the cooling cooler 95 a through the line 208 without passing through the decanter 95, and is supplied to the decanter 96.
- the rest is the same as the example of FIG.
- the gas generated in the capacitor 3a is, for example, carbon monoxide, hydrogen, methane, carbon dioxide, nitrogen, oxygen, methyl iodide, hydrogen iodide, water, methyl acetate, acetic acid, dimethyl ether, methanol, acetaldehyde. And formic acid, etc., are supplied from the condenser 3a to the scrubber system 8 through lines 32 and 15. Methyl iodide, hydrogen iodide, water, methyl acetate, acetic acid, dimethyl ether, methanol, acetaldehyde, formic acid, and the like in the gas component that has reached the scrubber system 8 are absorbed by the absorbent in the scrubber system 8.
- Hydrogen iodide is produced by reaction with methanol or methyl acetate in the absorbing solution. Then, the liquid containing useful components such as methyl iodide is recycled from the scrubber system 8 to the reaction tank 1 through the recycling lines 48 and 23 and reused.
- the bottoms extracted from the bottom of the distillation column 3 contains a larger amount of components having higher boiling points than acetic acid (high-boiling components) as compared to the overhead flow and side flow from the distillation column 3 such as propionic acid.
- the above-mentioned catalyst and cocatalyst accompanied by droplets are included.
- the bottoms include acetic acid, methyl iodide, methyl acetate and water.
- a part of such bottoms is continuously introduced into the evaporation tank 2 through the lines 25 and 26 and recycled, and the other part of the bottoms is passed through the lines 25 and 23. It is continuously introduced into the reaction tank 1 and recycled.
- the first acetic acid stream continuously withdrawn from the distillation column 3 as a side stream is richer in acetic acid than the vapor stream continuously introduced into the distillation column 3. That is, the acetic acid concentration of the first acetic acid stream is higher than the acetic acid concentration of the vapor stream.
- the concentration of acetic acid in the first acetic acid stream is, for example, 90 to 99.9% by mass, preferably 93 to 99% by mass.
- the first acetic acid stream can also contain, for example, methyl iodide, hydrogen iodide, water, methyl acetate, dimethyl ether, methanol, acetaldehyde, formic acid, propionic acid, and the like in addition to acetic acid.
- the methyl iodide concentration is, for example, 8% by mass or less (eg, 0.1-8% by mass), preferably 0.2-5% by mass
- the water concentration is, for example, 8% by mass or less (eg, 0% 0.1-8% by mass), preferably 0.2-5% by mass
- the methyl acetate concentration is, for example, 8% by mass or less (eg, 0.1-8% by mass), preferably 0.2-5% by mass.
- the connecting position of the line 27 to the distillation column 3 may be higher than the connecting position of the line 21 to the distillation column 3 in the height direction of the distillation column 3 as shown in the figure.
- the first acetic acid stream from the distillation column 3 is continuously introduced into the next distillation column 5 through the line 27 at a predetermined flow rate. Note that the first acetic acid stream extracted as a side stream of the distillation column 3, the bottom liquid of the distillation column 3, or the vapor condensate at the bottom of the distillation column 3 remains as it is without passing through the distillation column 5 (dehydration step). It can also be continuously introduced into the distillation column 6 described later.
- Potassium hydroxide can be supplied or added to the first acetic acid stream flowing through the line 27 through a line 55 (potassium hydroxide introduction line). Potassium hydroxide can be supplied or added as a solution such as an aqueous solution. Hydrogen iodide in the first acetic acid stream can be reduced by supplying or adding potassium hydroxide to the first acetic acid stream. Specifically, hydrogen iodide reacts with potassium hydroxide to produce potassium iodide and water. As a result, corrosion of a device such as a distillation tower caused by hydrogen iodide can be reduced. In addition, potassium hydroxide can be supplied or added to an appropriate place where hydrogen iodide is present in this process. Note that potassium hydroxide added during the process also reacts with acetic acid to produce potassium acetate.
- the distillation column 5 is a unit for performing the second distillation step, and is positioned as a so-called dehydration column in this embodiment.
- the second distillation step is a step for further purifying acetic acid by subjecting the first acetic acid stream continuously introduced into the distillation column 5 to a distillation treatment.
- the distillation column 5 is composed of a rectifying column such as a plate column and a packed column.
- the theoretical plate is, for example, 5 to 50 plates, and the reflux ratio is, for example, 0.2 to 3000 depending on the number of theoretical plates.
- the column top pressure and the column bottom pressure are preferably set according to the column bottom liquid composition so that the column bottom temperature is 165 ° C. or lower.
- the column top pressure is, for example, 0.10 to 0.28 MPaG, preferably 0.15 to 0.23 MPaG, and more preferably 0.17 to 0.21 MPaG.
- the tower bottom pressure is higher than the tower top pressure, for example, 0.13 to 0.31 MPaG, preferably 0.18 to 0.26 MPaG, and more preferably 0.20 to 0.24 MPaG.
- the column top temperature is set to 110 to 160 ° C., for example, a temperature higher than the boiling point of water and lower than the boiling point of acetic acid at the set column top pressure
- the bottom temperature is, for example, a temperature equal to or higher than the boiling point of acetic acid at a set tower bottom pressure, and is set to 120 to 165 ° C. (preferably 125 to 160 ° C., more preferably 130 to 155 ° C.).
- the vapor extracted from the top of the distillation column 5 contains more components having a lower boiling point than that of acetic acid (low-boiling components) compared to the above-mentioned bottoms from the distillation column 5, such as methyl iodide and iodide.
- acetic acid low-boiling components
- iodide methyl iodide
- iodide methyl iodide
- iodide iodide
- Such steam is continuously introduced into the condenser 5a through the line 33.
- the condenser 5a cools and partially condenses the steam from the distillation column 5 to separate it into a condensed component and a gas component.
- the condensate includes, for example, water and acetic acid.
- a part of the condensate is continuously refluxed from the condenser 5a through the line 35 to the distillation column 5.
- the other part of the condensate is continuously introduced from the condenser 5a into the reaction tank 1 through the lines 35, 36 and 23 and recycled.
- the gas generated in the capacitor 5a includes, for example, carbon monoxide, hydrogen, methane, carbon dioxide, nitrogen, oxygen, methyl iodide, hydrogen iodide, water, methyl acetate, acetic acid, dimethyl ether, methanol, acetaldehyde and formic acid. And supplied from the capacitor 5a to the scrubber system 8 through lines 37 and 15.
- Hydrogen iodide in the gas component that has reached the scrubber system 8 is absorbed by the absorption liquid in the scrubber system 8, and methyl iodide is generated by the reaction of hydrogen iodide in the absorption liquid with methanol or methyl acetate, and The liquid containing useful components such as methyl iodide is recycled from the scrubber system 8 to the reaction tank 1 through the recycling lines 48 and 23 and reused.
- the bottoms (or side stream) withdrawn from the bottom of the distillation column 5 contains more components with a higher boiling point than acetic acid (high boiling point components) compared to the overhead stream from the distillation column 5, for example, Propionic acid, potassium acetate (when potassium hydroxide is supplied to the line 27 and the like), and the above-mentioned catalyst and cocatalyst accompanied by droplets are included.
- This bottoms can also contain acetic acid.
- Such bottoms will be continuously introduced into the next distillation column 6 through line 34 in the form of a second acetic acid stream.
- the second acetic acid stream is richer in acetic acid than the first acetic acid stream continuously introduced into the distillation column 5. That is, the acetic acid concentration in the second acetic acid stream is higher than the acetic acid concentration in the first acetic acid stream.
- the acetic acid concentration of the second acetic acid stream is, for example, 99.1 to 99.99% by mass as long as it is higher than the acetic acid concentration of the first acetic acid stream.
- the second acetic acid stream can also include, for example, propionic acid, hydrogen iodide, etc., in addition to acetic acid, as described above.
- the side stream extraction position from the distillation column 5 is lower than the introduction position of the first acetic acid stream into the distillation column 5 in the height direction of the distillation column 5.
- Potassium hydroxide can be supplied or added to the second acetic acid stream flowing through the line 34 through a line 56 (potassium hydroxide introduction line). Potassium hydroxide can be supplied or added as a solution such as an aqueous solution. Hydrogen iodide in the second acetic acid stream can be reduced by supplying or adding potassium hydroxide to the second acetic acid stream. Specifically, hydrogen iodide reacts with potassium hydroxide to produce potassium iodide and water. As a result, corrosion of a device such as a distillation tower caused by hydrogen iodide can be reduced.
- the distillation column 6 is a unit for performing the third distillation step, and is positioned as a so-called dehigh boiling tower in this embodiment.
- the third distillation step is a step for further purifying acetic acid by purifying the second acetic acid stream continuously introduced into the distillation column 6.
- the distillation column 6 includes a rectifying column such as a plate column and a packed column.
- the theoretical plate has, for example, 5 to 50 plates, and the reflux ratio is, for example, 0.2 to 3000 depending on the number of theoretical plates.
- the column top pressure and the column bottom pressure are preferably set according to the column bottom liquid composition so that the column bottom temperature is 165 ° C. or lower.
- the pressure at the top of the column is, for example, 0.005 to 0.24 MPaG, preferably 0.01 to 0.22 MPaG, more preferably 0.02 to 0.20 MPaG, and particularly preferably 0.04 to 0.19 MPaG.
- the tower bottom pressure is higher than the tower top pressure, for example, 0.01 MPaG or more and less than 0.255 MPaG, preferably 0.02 to 0.24 MPaG, more preferably 0.03 to 0.23 MPaG, particularly preferably 0.05 to 0. .21 MPaG.
- the column top temperature is set to 50 to 160 ° C., for example, a temperature higher than the boiling point of water and lower than the boiling point of acetic acid at the set column top pressure
- the bottom temperature is, for example, a temperature higher than the boiling point of acetic acid at the set tower bottom pressure, and is set to 70 to 165 ° C. (preferably 120 to 160 ° C., more preferably 130 to 155 ° C.).
- connection position of the line 46 to the distillation column 6 may be higher than the connection position of the line 34 to the distillation column 6, as shown in the figure. The position may be lower than the connection position of 34, or may be the same as the connection position of the line 34 to the distillation column 6.
- the vapor extracted from the top of the distillation column 6 contains more components having a lower boiling point than that of acetic acid (low-boiling components) compared to the above-mentioned bottoms from the distillation column 6, and in addition to acetic acid, for example, iodination Including methyl, hydrogen iodide, water, methyl acetate, dimethyl ether, methanol and formic acid.
- acetic acid for example, iodination Including methyl, hydrogen iodide, water, methyl acetate, dimethyl ether, methanol and formic acid.
- Such steam is continuously introduced into the condenser 6a through the line 38.
- the condenser 6a divides the vapor from the distillation column 6 into a condensed component and a gas component by cooling and partially condensing.
- the condensate contains, for example, methyl iodide, hydrogen iodide, water, methyl acetate, dimethyl ether, methanol and formic acid in addition to acetic acid.
- At least a part of the condensate is continuously refluxed from the condenser 6 a to the distillation column 6 through the line 40.
- a part of the condensate (distillate) can be recycled from the condenser 6a through the lines 40, 41 and 42 to the first acetic acid stream in the line 27 before being introduced into the distillation column 5. is there.
- a part of the condensate is transferred from the condenser 6a through the lines 40, 41, 43 to the steam flow in the line 21 before being introduced into the distillation column 3. And can be recycled. Further, a part of the condensed portion (distilled portion) may be recycled to the reaction tank 1 from the condenser 6a through the lines 40, 44, and 23. Further, as described above, a part of the distillate from the condenser 6a can be supplied to the scrubber system 8 and used as an absorbing liquid in the system.
- the gas component after absorbing the useful component is discharged out of the apparatus, and the liquid component containing the useful component is introduced or recycled from the scrubber system 8 to the reaction tank 1 through the recycle lines 48 and 23. Reused.
- a part of the distillate from the condenser 6a may be led to various pumps (not shown) operating in the apparatus through a line outside the figure and used as a sealing liquid for the pump.
- a part of the distillate from the condenser 6a may be regularly extracted out of the apparatus through an extraction line attached to the line 40, or unsteadily extracted out of the apparatus when necessary. May be.
- the amount of distillate (distillation) is 0.01 to 30 of the condensate produced in the condenser 6a, for example. % By mass, preferably 0.1 to 10% by mass, more preferably 0.3 to 5% by mass, and more preferably 0.5 to 3% by mass.
- the gas generated in the capacitor 6a is, for example, carbon monoxide, hydrogen, methane, carbon dioxide, nitrogen, oxygen, methyl iodide, hydrogen iodide, water, methyl acetate, acetic acid, dimethyl ether, methanol, acetaldehyde, formic acid, and the like. And is supplied from the capacitor 6a to the scrubber system 8 through lines 45 and 15.
- the bottoms extracted from the bottom of the distillation column 6 through the line 39 contains more components having a higher boiling point than acetic acid (high-boiling components) compared to the overhead stream from the distillation column 6 such as potassium acetate.
- Acetate when an alkali such as potassium hydroxide is supplied to the line 34, etc.
- acetic anhydride propionic acid and the like.
- the bottoms extracted from the bottom of the distillation column 6 through the line 39 are corrosive metals such as free metal generated on the inner walls of the components of the acetic acid production apparatus, iodine derived from corrosive iodine, Also includes compounds with corrosive metals. Such bottoms are discharged out of the acetic acid production apparatus in this embodiment.
- the concentrations of acetate, acetic anhydride, and propionic acid in the bottom solution of the distillation column 6 are as small as possible.
- the concentration of acetate in the bottom liquid of the distillation column 6 is, for example, 1 mass ppm to 34 mass%, preferably 100 mass ppm to 25 mass%, more preferably 0.1 to 20 mass% (for example, 1 to 15 mass%).
- the concentration of acetic anhydride in the bottom liquid of the distillation column 6 is, for example, 1 mass ppm to 91 mass%, preferably 10 mass ppm to 74 mass%, more preferably 100 mass ppm to 44 mass%, and still more preferably 0.1 mass ppm. To 20% by mass, particularly preferably 0.2 to 10% by mass (eg 0.5 to 5% by mass).
- the propionic acid concentration in the bottom liquid of the distillation column 6 is, for example, 100 ppm to 91% by mass, preferably 0.1 to 75% by mass, more preferably 0.3 to 55% by mass, and still more preferably 0.5%. It is ⁇ 29% by mass, particularly preferably 1 to 15% by mass.
- the concentration of acetate in the bottom liquid of the distillation column 6 can be reduced, for example, by reducing the amount of alkali used for neutralizing the hydrogen iodide.
- the acetic anhydride concentration in the bottom liquid of the distillation column 6 is determined by, for example, adding water to the piping or device located upstream of the distillation column 6 or adding water into the distillation column 6 to hydrolyze the acetic anhydride. Can be reduced.
- the concentration of propionic acid in the bottom liquid of the distillation column 6 is, for example, when propionic acid is reduced in the reaction vessel by changing reaction conditions or when a part of the process liquid is recycled to the reaction system.
- the side stream continuously extracted from the distillation column 6 to the line 46 is continuously introduced into the next ion exchange resin column 7 as a third acetic acid stream.
- This third acetic acid stream is richer in acetic acid than the second acetic acid stream continuously introduced into the distillation column 6. That is, the acetic acid concentration in the third acetic acid stream is higher than the acetic acid concentration in the second acetic acid stream.
- the acetic acid concentration of the third acetic acid stream is, for example, 99.8 to 99.999% by mass as long as it is higher than the acetic acid concentration of the second acetic acid stream.
- the position for extracting the side stream from the distillation column 6 is higher than the position for introducing the second acetic acid stream into the distillation column 6 in the height direction of the distillation column 6.
- the side stream extraction position from the distillation column 6 is the same as or lower than the introduction position of the second acetic acid stream into the distillation column 6 in the height direction of the distillation column 6.
- the distillation column 6 can be replaced by a single distillation device (evaporator). If the impurities are sufficiently removed by the distillation column 5, the distillation column 6 can be omitted.
- the ion exchange resin tower 7 is a purification unit for performing the adsorption removal step.
- acetic acid is further purified by adsorbing and removing mainly alkyl iodide (hexyl iodide, decyl iodide, etc.) contained in a trace amount in the third acetic acid stream continuously introduced into the ion exchange resin tower 7. It is a process for doing.
- an ion exchange resin having an adsorption ability for alkyl iodide is filled in the tower to form an ion exchange resin bed.
- an ion exchange resin for example, a cation exchange resin in which a part of the detachable protons in the sulfonic acid group, carboxyl group, phosphonic acid group or the like as an exchange group is substituted with a metal such as silver or copper.
- adsorption removal step for example, a third acetic acid stream (liquid) flows through the inside of the ion exchange resin tower 7 filled with such an ion exchange resin, and in the flow process, the alkyl iodide in the third acetic acid stream is passed. And the like are adsorbed on the ion exchange resin and removed from the third acetic acid stream.
- the internal temperature is, for example, 18 to 100 ° C.
- the acetic acid flow rate [acetic acid treatment amount per m 3 of resin volume (m 3 / h)] is, for example, 3 ⁇ 15 m 3 / h ⁇ m 3 (resin volume).
- the fourth acetic acid flow is continuously led out from the lower end of the ion exchange resin tower 7 to the line 47.
- the acetic acid concentration in the fourth acetic acid stream is higher than the acetic acid concentration in the third acetic acid stream. That is, the fourth acetic acid stream is richer in acetic acid than the third acetic acid stream that is continuously introduced into the ion exchange resin tower 7.
- the acetic acid concentration of the fourth acetic acid stream is, for example, 99.9 to 99.999% by mass or more as long as it is higher than the acetic acid concentration of the third acetic acid stream.
- this fourth acetic acid stream can be stored in a product tank (not shown).
- a so-called product tower or finishing tower which is a distillation tower, may be provided as a purification unit for further purifying the fourth acetic acid stream from the ion exchange resin tower 7.
- a product column as defined in the present invention, it is preferable to obtain purified acetic acid by distilling the fourth acetic acid stream supplied through the line 47 under the condition of a column bottom temperature of 165 ° C. or lower.
- the product column is composed of a rectification column such as a plate column and a packed column.
- the theoretical plate has, for example, 5 to 50 plates, and the reflux ratio is, for example, 0.5 to 3000 depending on the number of theoretical plates.
- the column top pressure and the column bottom pressure are preferably set according to the column bottom liquid composition such that the column bottom temperature is 165 ° C. or lower.
- the pressure at the top of the column is, for example, 0.005 to 0.24 MPaG, preferably 0.01 to 0.22 MPaG, more preferably 0.02 to 0.20 MPaG, and particularly preferably 0.04 to 0.19 MPaG.
- the tower bottom pressure is higher than the tower top pressure, for example, 0.01 MPaG or more and less than 0.255 MPaG, preferably 0.02 to 0.24 MPaG, more preferably 0.03 to 0.23 MPaG, particularly preferably 0.05 to 0. .21 MPaG.
- the column top temperature is set to, for example, 50 to 160 ° C. higher than the boiling point of water and lower than the boiling point of acetic acid at the set column top pressure
- the column bottom temperature is For example, the temperature is higher than the boiling point of acetic acid at the set tower bottom pressure and is set to 70 to 165 ° C. (preferably 120 to 160 ° C., more preferably 130 to 155 ° C.).
- the product tower or finishing tower can be replaced by a simple distiller (evaporator).
- all or part of the fourth acetic acid stream (liquid) from the ion exchange resin tower 7 is continuously introduced into the product tower.
- steam as an overhead stream containing trace amounts of low-boiling components eg methyl iodide, water, methyl acetate, dimethyl ether, crotonaldehyde, acetaldehyde and formic acid
- This steam is divided into a condensate and a gas by a predetermined condenser. A part of the condensate may be continuously refluxed to the product column and the other part of the condensate may be recycled to the reactor 1 and / or discarded outside the system.
- the gas component is supplied to the scrubber system 8. From the bottom of the product column, bottoms containing a trace amount of high-boiling components are continuously withdrawn, and this bottoms, for example, into the second acetic acid stream in the line 34 before being introduced into the distillation column 6. And recycled.
- a side stream (liquid) is continuously withdrawn as a fifth acetic acid stream from a height position between the tower top and the tower bottom in the product tower. The extraction position of the side stream from the product tower is lower in the height direction of the product tower, for example, than the introduction position of the fourth acetic acid stream into the product tower.
- the fifth acetic acid stream is richer in acetic acid than the fourth acetic acid stream that is continuously introduced into the product column.
- the acetic acid concentration in the fifth acetic acid stream is higher than the acetic acid concentration in the fourth acetic acid stream.
- the acetic acid concentration of the fifth acetic acid stream is, for example, 99.9 to 99.999% by mass or more as long as it is higher than the acetic acid concentration of the fourth acetic acid stream.
- This fifth acetic acid stream is stored, for example, in a product tank (not shown).
- the ion exchange resin tower 7 may be installed downstream of the product tower to treat the acetic acid stream discharged from the product tower.
- the concentration of acetate, acetic anhydride, and propionic acid in the bottom liquid of the product column is preferably as low as possible.
- the acetate concentration in the bottom liquid of the product column is, for example, 0.1 mass ppb to 1 mass%, preferably 1 mass ppb to 0.1 mass%, more preferably 10 mass ppb to 0.01 mass% (for example, 100 mass ppb to 0.001 mass%).
- the acetic anhydride concentration in the bottom liquid of the product tower is, for example, 0.1 mass ppm to 60 mass%, preferably 1 mass ppm to 10 mass%, more preferably 10 mass ppm to 2 mass% (for example, 50 mass ppm to 0.5 mass%), or 0.2 to 10 mass% (for example, 0.5 to 5 mass%).
- the propionic acid concentration in the bottom liquid of the product column is, for example, 1 mass ppm to 10 mass%, preferably 10 mass ppm to 5 mass%, more preferably 50 mass ppm to 1 mass% (for example, 100 mass ppm to 0.00 mass). 1% by mass).
- the concentration of acetate in the bottom liquid of the product tower can be reduced, for example, by reducing the amount of alkali used for neutralizing the hydrogen iodide.
- the concentration of acetic anhydride in the bottom liquid of the product tower can be reduced by, for example, adding water to the piping or apparatus located upstream of the product tower or the product tower to hydrolyze the acetic anhydride.
- the concentration of propionic acid in the bottom liquid of the product tower can be reduced by, for example, reducing the by-product of propionic acid in the reaction tank by changing the reaction conditions, or recycling a part of the process liquid to the reaction system.
- the column bottom temperature of the distillation column 5 may be set to 165 ° C. or lower (for example, less than 165 ° C.).
- the column bottom temperature may be set to 165 ° C. or less (for example, less than 165 ° C.)
- the column bottom temperature of the product column may be set to 165 ° C. or less (for example, less than 165 ° C.).
- 6 may be set to 165 ° C. or less (for example, less than 165 ° C.)
- the column bottom temperature of the distillation column 6 and the product column may be set to 165 ° C. or less (for example, less than 165 ° C.).
- each of the tower bottom temperatures is preferably 160 ° C. or less, more preferably 155 ° C. or less, and particularly preferably 150 ° C. or less (for example, 140 ° C. or less).
- the distillation column 6 and the product column may not be provided.
- Comparative Example 1 In a 1000 ml zirconium autoclave, 459 g of propionic acid and 46 g of acetic acid are added. Zirconium (Zr), Hastelloy B2 which is a nickel base alloy (“HB2” manufactured by Oda Koki Co., Ltd.), Hastelloy C which is a nickel base alloy (Oda Steel Machine Co., Ltd.) Made of stainless steel, SUS316 (Umetok, "SUS316”) made of various materials (size: 36 mm x 25 mm x 2.5 mm) set in the autoclave, the lid closed, and the autoclave After the inside liquid was bubbled with nitrogen to replace the oxygen dissolved in the liquid, the operation of increasing the atmospheric pressure to 1 MPaG with nitrogen and then depressurizing to atmospheric pressure was performed three times, and then nitrogen gas was filled up to 4 MPaG.
- Zr Zirconium
- Hastelloy B2 which is a nickel base alloy (“HB2” manufactured by Oda Koki Co., Ltd.
- the pressure was released to atmospheric pressure. Thereafter, the autoclave was heated in an oil bath so that the liquid temperature in the autoclave was 165 ° C. The steady pressure after heating was 131 kPaG. After 500 hours under steady conditions, the sample was cooled to room temperature, and after releasing the pressure, the test piece was taken out and the corrosion rate was calculated by weight measurement, and the presence or absence of local corrosion was determined by visual inspection. Tables 1 and 2 show the preparation composition, the corrosion test conditions and the results. In the unit of pressure, “G” indicates a gauge pressure.
- Comparative Example 2 A corrosion test was performed in the same manner as in Comparative Example 1 except that the charged composition was changed to 100% acetic acid. Tables 1 and 2 show the preparation composition, the corrosion test conditions and the results.
- Examples 1 to 15 A corrosion test was performed in the same manner as in Comparative Example 1 except that the charged composition and temperature were changed. Tables 1 and 2 show the preparation composition, the corrosion test conditions and the results.
- the unit “mm / Y” means that the corrosion rate (thickness reduction amount) of the test piece per year is converted to mm.
- the standard of corrosion rate and material selection is as follows. The following is a guide only and depends on the initial thickness of the material and the update frequency. Less than 0.05 mm / Y: suitable for use 0.05-0.1 mm / Y: usable level 0.1 mm / Y-0.2 mm / Y: usable depending on conditions 0.2 mm / Y over: Not suitable for use
- a method for producing acetic acid which comprises a step of purifying acetic acid by distilling acetic acid and a crude acetic acid solution containing impurities having a boiling point higher than that of acetic acid.
- a process for producing acetic acid which is carried out under conditions of not higher than °C (preferably not higher than 155 deg. C, more preferably not higher than 150 deg.
- the acetic acid concentration in the crude acetic acid solution is 90% by mass or more (for example, 95% by mass or more, preferably 97% by mass or more, more preferably 98% by mass or more, and further preferably 99% by mass or more).
- the manufacturing method of acetic acid of description [3] The method for producing acetic acid according to [1] or [2], wherein the impurity having a boiling point higher than that of acetic acid includes at least one compound selected from the group consisting of acetate, acetic anhydride, and propionic acid. [4]
- the acetate concentration in the bottom liquid of the distillation column is 34% by mass or less (preferably 23% by mass or less, more preferably 13% by mass or less, still more preferably 10% by mass or less, particularly preferably 1% by mass or less.
- the concentration of acetic anhydride in the bottom liquid of the distillation column is 90% by mass or less (preferably 74% by mass or less, more preferably 45% by mass or less, further preferably 10% by mass or less, particularly preferably 1% by mass or less.
- the propionic acid concentration in the bottom liquid of the distillation column is 90% by mass or less (preferably 75% by mass or less, more preferably 55% by mass or less, further preferably 29% by mass or less, particularly preferably 10% by mass or less.
- the method for producing acetic acid according to any one of [1] to [5] which is 1% by mass or less.
- the acetic acid distillation step includes at least one step of performing distillation of the crude acetic acid solution under the condition that the bottom temperature of the distillation column is 165 ° C. or lower.
- the method for producing acetic acid according to the description [11] The method for producing acetic acid according to [10], wherein potassium hydroxide is supplied to or added to the first acetic acid stream via a potassium hydroxide introduction line.
- the acetic acid distillation step has at least one distillation step in which the concentration of acetic acid in the crude acetic acid solution subjected to distillation is 97% by mass or more.
- the acetic acid distillation step includes distilling the first acetic acid stream to remove a second acetic acid stream enriched in acetic acid than the first acetic acid stream and a component having a lower boiling point than acetic acid.
- the distillation of the first acetic acid stream is performed under the condition that the bottom temperature of the distillation column is 165 ° C. or lower (preferably 155 ° C. or lower, more preferably 150 ° C. or lower, more preferably 140 ° C. or lower).
- a method for producing acetic acid [15] The method for producing acetic acid according to [13] or [14], wherein potassium hydroxide is supplied to or added to the second acetic acid stream via a potassium hydroxide introduction line.
- the acetic acid distillation step distills the second acetic acid stream so that a vapor as an overhead stream containing more components having a lower boiling point than acetic acid compared to the bottoms and a component having a higher boiling point than acetic acid.
- [13] to [15] which includes a deboiling step that separates the bottom liquid containing a larger amount of the effluent compared to the overhead stream and the third acetic acid stream enriched in acetic acid rather than the second acetic acid stream.
- the manufacturing method of acetic acid as described in any one.
- the distillation of the second acetic acid stream is performed under the condition that the bottom temperature of the distillation column is 165 ° C. or lower (preferably 155 ° C.
- a method for producing acetic acid [18]
- the acetate concentration in the bottom liquid of the distillation column in the dehigh boiling step is 1 mass ppm to 34 mass% (preferably 100 mass ppm to 25 mass%, more preferably 0.1 to 20 mass%). (For example, 1 to 15% by mass)).
- the acetic anhydride concentration in the bottom liquid of the distillation column in the dehigh boiling step is 1 mass ppm to 91 mass% (preferably 10 mass ppm to 74 mass%, more preferably 100 mass ppm to 44 mass%). More preferably 0.1 to 20% by mass, particularly preferably 0.2 to 10% by mass (for example, 0.5 to 5% by mass)), according to any one of [17] to [19] A method for producing acetic acid.
- the acetic anhydride concentration in the bottom liquid of the distillation column in the dehigh boiling step is determined by adding water to the piping or apparatus located upstream of the distillation column or in the distillation column to add acetic anhydride.
- the propionic acid concentration in the bottom liquid of the distillation column in the dehigh boiling step is 100 mass ppm to 91 mass% (preferably 0.1 to 75 mass%, more preferably 0.3 to 55 mass%).
- Propionic acid concentration in the bottom liquid of the distillation column in the dehigh boiling step is changed by changing reaction conditions to reduce by-product of propionic acid in the reaction tank; Acetaldehyde that causes propionic acid as a by-product when it is recycled to the reaction liquid is separated and removed from the process liquid and then recycled to the reaction system, and a distillation column or an evaporator is provided upstream of the distillation column to separate and remove propionic acid.
- the method further includes an ion exchange resin treatment step of introducing the third acetic acid stream into an ion exchange resin tower and adsorbing and removing alkyl iodide in the third acetic acid stream to obtain a fourth acetic acid stream [16].
- the method for producing acetic acid according to [24] further comprising a step of distilling the fourth acetic acid stream at a bottom temperature of 165 ° C.
- the acetate concentration in the bottom liquid of the product tower is 0.1 mass ppb to 1 mass% (preferably 1 mass ppb to 0.1 mass%, more preferably 10 mass ppb to 0.01 mass%). (For example, 100 mass ppb to 0.001 mass%)).
- the acetic anhydride concentration in the bottom liquid of the product tower is 0.1 mass ppm to 60 mass% (preferably 1 mass ppm to 10 mass%, more preferably 10 mass ppm to 2 mass% (eg, 50 mass).
- a method for producing acetic acid is 0.1 mass ppm to 60 mass% (preferably 1 mass ppm to 10 mass%, more preferably 10 mass ppm to 2 mass% (eg, 50 mass).
- the concentration of acetic anhydride in the bottom liquid of the product tower is reduced by adding water to the piping or apparatus located upstream of the product tower or in the product tower to hydrolyze the acetic anhydride [28] ] Or the method for producing acetic acid according to [29].
- the propionic acid concentration in the bottom liquid of the product tower is 1 mass ppm to 10 mass% (preferably 10 mass ppm to 5 mass%, more preferably 50 mass ppm to 1 mass% (for example, 100 mass ppm to The method for producing acetic acid according to any one of [25] to [30], which is 0.1% by mass)).
- Propionic acid concentration in the bottom liquid of the product column is reduced by changing reaction conditions to reduce by-product of propionic acid in the reaction tank, and propionic acid when recycling a part of the process liquid to the reaction system Select from the group consisting of separating and removing acetaldehyde, which is a by-product, from the process liquid, recycling it to the reaction system, and providing a distillation column or an evaporator for separating and removing propionic acid upstream of the product column.
- the method for producing acetic acid according to [31] which is reduced by one or more methods.
- the method for producing acetic acid according to the present invention can be used as an industrial method for producing acetic acid by a methanol carbonylation process (methanol acetic acid process).
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Abstract
Description
CH3OH + CO → CH3COOH (1)
ジルコニウム製オートクレーブ1000mlに、プロピオン酸459g、酢酸46g入れ、ジルコニウム(Zr)、ニッケル基合金であるハステロイB2(小田鋼機社製、「HB2」)、ニッケル基合金であるハステロイC(小田鋼機社製、「HC276」)、ステンレス鋼であるSUS316(ウメトク社製、「SUS316」)の各種材質のテストピース(サイズ:36mm×25mm×2.5mm)をオートクレーブ内にセットして蓋を閉め、オートクレーブ内の液を窒素でバブリングして液中に溶解している酸素を置換した後、窒素で大気圧を1MPaGまで昇圧後、大気圧まで減圧する操作を3回実施後、窒素ガスを4MPaGまで張り込み、大気圧まで放圧した。その後、オートクレーブ内の液温が165℃となるようにオイルバスでオートクレーブを加熱した。加熱後の定常圧力は131kPaGで推移した。定常条件で500時間経過後、室温まで冷却し、放圧後、テストピースを取り出して重量測定により腐食速度を計算し、局部腐食の有無を外観検査で判定した。仕込組成、腐食テストの条件及びその結果を表1、表2に示す。圧力の単位において「G」はゲージ圧を示す。
仕込組成を酢酸100%に変えた以外は、比較例1と同様の方法にて腐食テストを行った。仕込組成、腐食テストの条件及びその結果を表1、2に示す。
仕込組成と温度を変更した以外は、比較例1と同様の方法にて腐食テストを行った。仕込組成、腐食テストの条件及びその結果を表1、2に示す。
比較例、実施例を通して、ジルコニウム(Zr)は全て完全耐食を示した。
比較例1、2の結果より、温度165℃を超える温度では、HB2以上、Zrなどの耐久材質しか使用できないレベルの腐食速度となった。実施例1~15より、HB2は全てにおいて良好な耐食性を示した。また、HC276もHB2ほどではないが、使用に十分な耐食性を示し、165℃では条件によっては使用可能であり、160℃では使用可能なレベルである。SUS316は実施例5~15の155℃以下の条件で使用可能であり、160℃では条件によっては使用可能であり、165℃を超える温度では使用不可能であった。全条件を通し、比較例2、実施例2、6、10、14の純酢酸のみの同じ温度での腐食データと比較した場合、実施例3、7、11の酢酸カリウムが混入した組成では、若干腐食性は悪くなる傾向となるが、それよりも、温度による腐食への影響が顕著であることがわかる。実施例4、8、12の無水酢酸が混入した組成では、純酢酸データよりも、若干腐食速度への影響がある。比較例1、実施例1、5、9、13のプロピオン酸が混入した組成は、純酢酸と同等レベルであった。
0.05mm/Y未満 :使用に適している
0.05~0.1mm/Y :使用可能なレベルである
0.1mm/Y~0.2mm/Y :条件によっては使用可能である
0.2mm/Y超 :使用には適さない
[1]酢酸と酢酸よりも高沸点の不純物を含む粗酢酸液を蒸留して酢酸を精製する工程を含む酢酸の製造方法であって、前記粗酢酸液の蒸留を蒸留塔の塔底温度165℃以下(好ましくは155℃以下、より好ましくは150℃以下、さらに好ましくは140℃以下)の条件で行うことを特徴とする酢酸の製造方法。
[2]前記粗酢酸液中の酢酸濃度が90質量%以上(例えば95質量%以上、好ましくは97質量%以上、より好ましくは98質量%以上、さらに好ましくは99質量%以上)である[1]記載の酢酸の製造方法。
[3]前記酢酸よりも高沸点の不純物が、酢酸塩、無水酢酸及びプロピオン酸からなる群より選択された少なくとも1つの化合物を含む[1]又は[2]に記載の酢酸の製造方法。
[4]前記蒸留塔の塔底液の酢酸塩濃度が34質量%以下(好ましくは23質量%以下、より好ましくは13質量%以下、さらに好ましくは10質量%以下、特に好ましくは1質量%以下)である[1]~[3]のいずれか1つに記載の酢酸の製造方法。
[5]前記蒸留塔の塔底液の無水酢酸濃度が90質量%以下(好ましくは74質量%以下、より好ましくは45質量%以下、さらに好ましくは10質量%以下、特に好ましくは1質量%以下)である[1]~[4]のいずれか1つに記載の酢酸の製造方法。
[6]前記蒸留塔の塔底液のプロピオン酸濃度が90質量%以下(好ましくは75質量%以下、より好ましくは55質量%以下、さらに好ましくは29質量%以下、特に好ましくは10質量%以下、とりわけ1質量%以下)である[1]~[5]のいずれか1つに記載の酢酸の製造方法。
[7]前記蒸留塔の塔底圧力0.255MPaG未満(好ましくは0.24MPaG以下、さらに好ましくは0.23MPaG以下、特に好ましくは0.21MPaG以下)の条件で蒸留を行う[1]~[6]のいずれか1つに記載の酢酸の製造方法。
[8]前記蒸留塔の塔底圧力0.01MPaG以上(好ましくは0.02MPaG以上、さらに好ましくは0.03MPaG以上、特に好ましくは0.05MPaG以上)の条件で蒸留を行う[7]記載の酢酸の製造方法。
[9]前記蒸留塔の塔底圧力0.01MPaG以上0.255MPaG未満の条件で蒸留を行う[1]~[8]のいずれか1つに記載の酢酸の製造方法。
[10]メタノールと一酸化炭素とを反応させて酢酸を生成させるカルボニル化反応工程、前記カルボニル化反応工程で得られた反応混合物を蒸気流と残液流とに分離する蒸発工程、前記蒸気流を蒸留に付して低沸成分に富むオーバーヘッド流と酢酸に富む酢酸流(第1酢酸流)とに分離する脱低沸工程、及び前記酢酸流を蒸留して酢酸を精製する酢酸蒸留工程を含み、前記酢酸蒸留工程が、前記粗酢酸液の蒸留を蒸留塔の塔底温度165℃以下の条件で行う工程を少なくとも1つ有している[1]~[9]のいずれか1つに記載の酢酸の製造方法。
[11]前記第1酢酸流に、水酸化カリウム導入ラインを介して、水酸化カリウムを供給ないし添加する[10]記載の酢酸の製造方法。
[12]前記酢酸蒸留工程が、蒸留に付す前記粗酢酸液中の酢酸濃度が97質量%以上である蒸留工程を少なくとも1つ有しており、そのような工程全てにおいて、前記粗酢酸液の蒸留を蒸留塔の塔底温度165℃以下(好ましくは155℃以下、より好ましくは150℃以下、さらに好ましくは140℃以下)の条件で行う[10]又は[11]に記載の酢酸の製造方法。
[13]前記酢酸蒸留工程が、前記第1酢酸流を蒸留して、前記第1酢酸流よりも酢酸が富化されている第2酢酸流と、酢酸よりも沸点の低い成分を前記第2酢酸流と比較して多く含むオーバーヘッド流の蒸気とに分離する脱水工程を含む[10]~[12]のいずれか1つに記載の酢酸の製造方法。
[14]前記第1酢酸流の蒸留を蒸留塔の塔底温度165℃以下(好ましくは155℃以下、より好ましくは150℃以下、さらに好ましくは140℃以下)の条件で行う[13]記載の酢酸の製造方法。
[15]前記第2酢酸流に、水酸化カリウム導入ラインを介して、水酸化カリウムを供給ないし添加する[13]又は[14]に記載の酢酸の製造方法。
[16]前記酢酸蒸留工程が、前記第2酢酸流を蒸留して、酢酸よりも沸点の低い成分を缶出液と比較して多く含むオーバーヘッド流としての蒸気と、酢酸よりも沸点の高い成分をオーバーヘッド流と比較して多く含む缶出液と、前記第2酢酸流よりも酢酸が富化されている第3酢酸流とに分離する脱高沸工程を含む[13]~[15]のいずれか1つに記載の酢酸の製造方法。
[17]前記第2酢酸流の蒸留を蒸留塔の塔底温度165℃以下(好ましくは155℃以下、より好ましくは150℃以下、さらに好ましくは140℃以下)の条件で行う[16]記載の酢酸の製造方法。
[18]前記脱高沸工程における前記蒸留塔の塔底液中の酢酸塩濃度が1質量ppm~34質量%(好ましくは100質量ppm~25質量%、さらに好ましくは0.1~20質量%(例えば1~15質量%))である[17]記載の酢酸の製造方法。
[19]前記脱高沸工程における前記蒸留塔の塔底液中の酢酸塩濃度を、ヨウ化水素の中和に用いるアルカリの添加量を減らすことにより低減する[18]記載の酢酸の製造方法。
[20]前記脱高沸工程における前記蒸留塔の塔底液中の無水酢酸濃度が1質量ppm~91質量%(好ましくは10質量ppm~74質量%、より好ましくは100質量ppm~44質量%、さらに好ましくは0.1~20質量%、特に好ましくは0.2~10質量%(例えば0.5~5質量%))である[17]~[19]のいずれか1つに記載の酢酸の製造方法。
[21]前記脱高沸工程における前記蒸留塔の塔底液中の無水酢酸濃度を、前記蒸留塔の上流に位置する配管や装置あるいは前記蒸留塔内に水を添加して、無水酢酸を加水分解することにより低減する[20]記載の酢酸の製造方法。
[22]前記脱高沸工程における前記蒸留塔の塔底液中のプロピオン酸濃度が100質量ppm~91質量%(好ましくは0.1~75質量%、より好ましくは0.3~55質量%、さらに好ましくは0.5~29質量%、特に好ましくは1~15質量%)である[17]~[21]のいずれか1つに記載の酢酸の製造方法。
[23]前記脱高沸工程における前記蒸留塔の塔底液中のプロピオン酸濃度を、反応条件を変えて反応槽でのプロピオン酸の副生を低減させること、プロセス液の一部を反応系にリサイクルする際プロピオン酸副生の原因となるアセトアルデヒドを当該プロセス液から分離除去した後に反応系にリサイクルすること、及び前記蒸留塔の上流にプロピオン酸を分離除去する蒸留塔又は蒸発器を設けること、からなる群より選択される1以上の方法により低減する[22]記載の酢酸の製造方法。
[24]さらに、前記第3酢酸流をイオン交換樹脂塔に導入し、前記第3酢酸流中のヨウ化アルキルを吸着除去して第4酢酸流を得るイオン交換樹脂処理工程を含む[16]~[23]のいずれか1つに記載の酢酸の製造方法。
[25]さらに、前記第4酢酸流を蒸留塔である製品塔の塔底温度165℃以下の条件で蒸留して精製酢酸を得る工程を含む[24]記載の酢酸の製造方法。
[26]前記製品塔の塔底液中の酢酸塩濃度が0.1質量ppb~1質量%(好ましくは1質量ppb~0.1質量%、さらに好ましくは10質量ppb~0.01質量%(例えば100質量ppb~0.001質量%))である[25]記載の酢酸の製造方法。
[27]前記製品塔の塔底液中の酢酸塩濃度を、ヨウ化水素の中和に用いるアルカリの添加量を減らすことにより低減する[26]記載の酢酸の製造方法。
[28]前記製品塔の塔底液中の無水酢酸濃度が0.1質量ppm~60質量%(好ましくは1質量ppm~10質量%、さらに好ましくは10質量ppm~2質量%(例えば50質量ppm~0.5質量%)である[25]~[27]のいずれか1つ記載の酢酸の製造方法。
[29]前記製品塔の塔底液中の無水酢酸濃度が0.2~10質量%(例えば0.5~5質量%)である[25]~[27]のいずれか1つに記載の酢酸の製造方法。
[30]前記製品塔の塔底液中の無水酢酸濃度を、製品塔の上流に位置する配管や装置あるいは製品塔内に水を添加して、無水酢酸を加水分解することにより低減する[28]又は[29]に記載の酢酸の製造方法。
[31]前記製品塔の塔底液中のプロピオン酸濃度が1質量ppm~10質量%(好ましくは10質量ppm~5質量%、さらに好ましくは50質量ppm~1質量%(例えば100質量ppm~0.1質量%))である[25]~[30]のいずれか1つに記載の酢酸の製造方法。
[32]前記製品塔の塔底液中のプロピオン酸濃度を、反応条件を変えて反応槽でのプロピオン酸の副生を低減させること、プロセス液の一部を反応系にリサイクルする際プロピオン酸副生の原因となるアセトアルデヒドを当該プロセス液から分離除去した後に反応系にリサイクルすること、及び前記製品塔の上流にプロピオン酸を分離除去する蒸留塔又は蒸発器を設けること、からなる群より選択される1以上の方法により低減する[31]記載の酢酸の製造方法。
[33]前記蒸留塔の材質がニッケル基合金、ステンレス鋼、アルミニウム及びチタンからなる群より選択された少なくとも1種である[1]~[32]のいずれか1つに記載の酢酸の製造方法。
[34]前記蒸留塔の塔底液の酢酸塩濃度が34質量%以下、無水酢酸濃度が90質量%以下、プロピオン酸濃度が90質量%以下であり、前記蒸留塔の塔底圧力が0.255MPa未満であり、且つ前記蒸留塔の材質がニッケル基合金、ステンレス鋼、アルミニウム及びチタンからなる群より選択された少なくとも1種であり、塔底温度は165℃未満である[1]~[33]のいずれか1つに記載の酢酸の製造方法。
2 蒸発槽
3,5,6 蒸留塔
4 デカンタ
7 イオン交換樹脂塔
8 スクラバーシステム
9 アセトアルデヒド分離除去システム
16 反応混合物供給ライン
17 蒸気流排出ライン
18,19 残液流リサイクルライン
54 一酸化炭素含有ガス導入ライン
55,56 水酸化カリウム導入ライン
57 触媒循環ポンプ
91 蒸留塔(第1脱アセトアルデヒド塔)
92 抽出塔
93 蒸留塔(第2脱アセトアルデヒド塔)
94 蒸留塔(抽出蒸留塔)
95 デカンタ
96 デカンタ
97 蒸留塔(脱アセトアルデヒド塔)
98 蒸留塔(抽出蒸留塔)
99 デカンタ
200 チムニートレイ
Claims (12)
- 酢酸と酢酸よりも高沸点の不純物を含む粗酢酸液を蒸留して酢酸を精製する工程を含む酢酸の製造方法であって、前記粗酢酸液の蒸留を蒸留塔の塔底温度165℃以下の条件で行うことを特徴とする酢酸の製造方法。
- 前記粗酢酸液中の酢酸濃度が90質量%以上である請求項1記載の酢酸の製造方法。
- 前記酢酸よりも高沸点の不純物が、酢酸塩、無水酢酸及びプロピオン酸からなる群より選択された少なくとも1つの化合物を含む請求項1又は2に記載の酢酸の製造方法。
- 前記蒸留塔の塔底液の酢酸塩濃度が34質量%以下である請求項1~3のいずれか1項に記載の酢酸の製造方法。
- 前記蒸留塔の塔底液の無水酢酸濃度が90質量%以下である請求項1~4のいずれか1項に記載の酢酸の製造方法。
- 前記蒸留塔の塔底液のプロピオン酸濃度が90質量%以下である請求項1~5のいずれか1項に記載の酢酸の製造方法。
- 前記蒸留塔の塔底圧力0.255MPaG未満の条件で蒸留を行う請求項1~6のいずれか1項に記載の酢酸の製造方法。
- 前記蒸留塔の塔底圧力0.01MPaG以上0.255MPaG未満の条件で蒸留を行う請求項1~7のいずれか1項に記載の酢酸の製造方法。
- メタノールと一酸化炭素とを反応させて酢酸を生成させるカルボニル化反応工程、前記カルボニル化反応工程で得られた反応混合物を蒸気流と残液流とに分離する蒸発工程、前記蒸気流を蒸留に付して低沸成分に富むオーバーヘッド流と酢酸に富む酢酸流とに分離する脱低沸工程、及び前記酢酸流を蒸留して酢酸を精製する酢酸蒸留工程を含み、前記酢酸蒸留工程が、前記粗酢酸液の蒸留を蒸留塔の塔底温度165℃以下の条件で行う工程を少なくとも1つ有している請求項1~8のいずれか1項に記載の酢酸の製造方法。
- 前記酢酸蒸留工程が、蒸留に付す前記粗酢酸液中の酢酸濃度が97質量%以上である蒸留工程を少なくとも1つ有しており、そのような工程全てにおいて、前記粗酢酸液の蒸留を蒸留塔の塔底温度165℃以下の条件で行う請求項9記載の酢酸の製造方法。
- 前記蒸留塔の材質がニッケル基合金、ステンレス鋼、アルミニウム及びチタンからなる群より選択された少なくとも1種である請求項1~10のいずれか1項に記載の酢酸の製造方法。
- 前記蒸留塔の塔底液の酢酸塩濃度が34質量%以下、無水酢酸濃度が90質量%以下、プロピオン酸濃度が90質量%以下であり、前記蒸留塔の塔底圧力が0.255MPa未満であり、且つ前記蒸留塔の材質がニッケル基合金、ステンレス鋼、アルミニウム及びチタンからなる群より選択された少なくとも1種であり、塔底温度は165℃未満である請求項1~11のいずれか1項に記載の酢酸の製造方法。
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JP2017533363A JP6693959B2 (ja) | 2017-01-18 | 2017-05-25 | 酢酸の製造方法 |
US15/540,195 US10428004B2 (en) | 2017-01-18 | 2017-05-25 | Method for producing acetic acid |
BR112019014638-5A BR112019014638A2 (pt) | 2017-01-18 | 2017-05-25 | método para produzir ácido acético |
MX2019008473A MX2019008473A (es) | 2017-01-18 | 2017-05-25 | Metodo para producir acido acetico. |
KR1020197023734A KR102255683B1 (ko) | 2017-01-18 | 2017-05-25 | 아세트산의 제조 방법 |
EP17732013.2A EP3372577B1 (en) | 2017-01-18 | 2017-05-25 | Method for producing acetic acid |
ES17732013T ES2772755T3 (es) | 2017-01-18 | 2017-05-25 | Método para producir ácido acético |
MYPI2019003570A MY186613A (en) | 2017-01-18 | 2017-05-25 | Method for producing acetic acid |
CN201780074653.6A CN110049963B (zh) | 2017-01-18 | 2017-05-25 | 乙酸的制备方法 |
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JP6693959B2 (ja) | 2020-05-13 |
BR112019014638A2 (pt) | 2020-07-07 |
TWI714775B (zh) | 2021-01-01 |
MX2019008473A (es) | 2019-09-18 |
CN110049963A (zh) | 2019-07-23 |
EP3372577B1 (en) | 2020-01-01 |
CN110049963B (zh) | 2022-02-18 |
ES2772755T3 (es) | 2020-07-08 |
TW201827391A (zh) | 2018-08-01 |
KR20190103377A (ko) | 2019-09-04 |
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