CN109467499A - The anticorrosion process and device of methyl acetate hydrolysis and acetic acid refining during polyvinyl alcohol disposing mother liquor - Google Patents
The anticorrosion process and device of methyl acetate hydrolysis and acetic acid refining during polyvinyl alcohol disposing mother liquor Download PDFInfo
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- CN109467499A CN109467499A CN201810880270.4A CN201810880270A CN109467499A CN 109467499 A CN109467499 A CN 109467499A CN 201810880270 A CN201810880270 A CN 201810880270A CN 109467499 A CN109467499 A CN 109467499A
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- tower
- hydrolysis
- acetic acid
- methyl acetate
- hydrolyzate
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- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 title claims abstract description 631
- 230000007062 hydrolysis Effects 0.000 title claims abstract description 208
- 238000006460 hydrolysis reaction Methods 0.000 title claims abstract description 208
- 238000007670 refining Methods 0.000 title claims abstract description 181
- KXKVLQRXCPHEJC-UHFFFAOYSA-N acetic acid trimethyl ester Natural products COC(C)=O KXKVLQRXCPHEJC-UHFFFAOYSA-N 0.000 title claims abstract description 151
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 title claims abstract description 143
- 238000000034 method Methods 0.000 title claims abstract description 56
- 230000008569 process Effects 0.000 title claims abstract description 24
- 239000004372 Polyvinyl alcohol Substances 0.000 title claims abstract description 18
- 229920002451 polyvinyl alcohol Polymers 0.000 title claims abstract description 18
- 239000012452 mother liquor Substances 0.000 title claims abstract description 9
- JMMWKPVZQRWMSS-UHFFFAOYSA-N isopropanol acetate Natural products CC(C)OC(C)=O JMMWKPVZQRWMSS-UHFFFAOYSA-N 0.000 claims abstract description 135
- 229940011051 isopropyl acetate Drugs 0.000 claims abstract description 132
- GWYFCOCPABKNJV-UHFFFAOYSA-N isovaleric acid Chemical compound CC(C)CC(O)=O GWYFCOCPABKNJV-UHFFFAOYSA-N 0.000 claims abstract description 125
- 239000012535 impurity Substances 0.000 claims abstract description 27
- 239000007788 liquid Substances 0.000 claims abstract description 26
- 239000011347 resin Substances 0.000 claims abstract description 25
- 229920005989 resin Polymers 0.000 claims abstract description 25
- 238000012856 packing Methods 0.000 claims abstract description 17
- 229960000583 acetic acid Drugs 0.000 claims description 206
- IKHGUXGNUITLKF-UHFFFAOYSA-N Acetaldehyde Natural products CC=O IKHGUXGNUITLKF-UHFFFAOYSA-N 0.000 claims description 153
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 94
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 79
- 238000000895 extractive distillation Methods 0.000 claims description 74
- 238000011084 recovery Methods 0.000 claims description 73
- 238000010992 reflux Methods 0.000 claims description 69
- 239000012071 phase Substances 0.000 claims description 59
- 238000000926 separation method Methods 0.000 claims description 40
- 239000007789 gas Substances 0.000 claims description 23
- 239000000463 material Substances 0.000 claims description 21
- 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 claims description 20
- 239000002253 acid Substances 0.000 claims description 20
- 238000009833 condensation Methods 0.000 claims description 20
- 230000005494 condensation Effects 0.000 claims description 20
- 238000000605 extraction Methods 0.000 claims description 19
- 239000003729 cation exchange resin Substances 0.000 claims description 18
- 239000000052 vinegar Substances 0.000 claims description 18
- 235000021419 vinegar Nutrition 0.000 claims description 18
- 238000004064 recycling Methods 0.000 claims description 14
- 238000001914 filtration Methods 0.000 claims description 12
- 238000005516 engineering process Methods 0.000 claims description 11
- 238000000746 purification Methods 0.000 claims description 9
- 238000006243 chemical reaction Methods 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 6
- IJMWOMHMDSDKGK-UHFFFAOYSA-N Isopropyl propionate Chemical compound CCC(=O)OC(C)C IJMWOMHMDSDKGK-UHFFFAOYSA-N 0.000 claims description 5
- 229920000784 Nomex Polymers 0.000 claims description 5
- 239000004763 nomex Substances 0.000 claims description 5
- 239000007864 aqueous solution Substances 0.000 claims description 4
- 230000018044 dehydration Effects 0.000 claims description 4
- 238000006297 dehydration reaction Methods 0.000 claims description 4
- 238000011049 filling Methods 0.000 claims description 3
- 239000007792 gaseous phase Substances 0.000 claims description 3
- 239000013589 supplement Substances 0.000 claims description 3
- 239000003456 ion exchange resin Substances 0.000 claims description 2
- 229920003303 ion-exchange polymer Polymers 0.000 claims description 2
- 238000005260 corrosion Methods 0.000 abstract description 17
- 229910052736 halogen Inorganic materials 0.000 abstract description 16
- 230000007797 corrosion Effects 0.000 abstract description 12
- 150000002367 halogens Chemical class 0.000 abstract description 11
- 238000005530 etching Methods 0.000 abstract description 6
- 238000012546 transfer Methods 0.000 abstract description 4
- 230000002708 enhancing effect Effects 0.000 abstract description 3
- 239000000126 substance Substances 0.000 abstract description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 9
- -1 halogen hydride Chemical class 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 7
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 7
- 238000004519 manufacturing process Methods 0.000 description 7
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 5
- 229940006461 iodide ion Drugs 0.000 description 5
- 238000011160 research Methods 0.000 description 5
- 238000009825 accumulation Methods 0.000 description 4
- 238000006136 alcoholysis reaction Methods 0.000 description 4
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 description 4
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 3
- 229940006460 bromide ion Drugs 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000005265 energy consumption Methods 0.000 description 3
- 150000004702 methyl esters Chemical class 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 2
- 235000008733 Citrus aurantifolia Nutrition 0.000 description 2
- QOSMNYMQXIVWKY-UHFFFAOYSA-N Propyl levulinate Chemical compound CCCOC(=O)CCC(C)=O QOSMNYMQXIVWKY-UHFFFAOYSA-N 0.000 description 2
- 235000011941 Tilia x europaea Nutrition 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 2
- 229910052794 bromium Inorganic materials 0.000 description 2
- 238000005352 clarification Methods 0.000 description 2
- 239000002537 cosmetic Substances 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 150000004678 hydrides Chemical group 0.000 description 2
- XMBWDFGMSWQBCA-UHFFFAOYSA-M iodide Chemical compound [I-] XMBWDFGMSWQBCA-UHFFFAOYSA-M 0.000 description 2
- 239000004571 lime Substances 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 229910052719 titanium Inorganic materials 0.000 description 2
- 239000010936 titanium Substances 0.000 description 2
- 241000894006 Bacteria Species 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 239000000571 coke Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000005034 decoration Methods 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000010931 ester hydrolysis Methods 0.000 description 1
- 239000000284 extract Substances 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 230000006870 function Effects 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- GPRLSGONYQIRFK-UHFFFAOYSA-N hydron Chemical compound [H+] GPRLSGONYQIRFK-UHFFFAOYSA-N 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000003317 industrial substance Substances 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 150000002632 lipids Chemical class 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- RECVMTHOQWMYFX-UHFFFAOYSA-N oxygen(1+) dihydride Chemical compound [OH2+] RECVMTHOQWMYFX-UHFFFAOYSA-N 0.000 description 1
- 230000008447 perception Effects 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920002689 polyvinyl acetate Polymers 0.000 description 1
- 239000011118 polyvinyl acetate Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- YKYONYBAUNKHLG-UHFFFAOYSA-N propyl acetate Chemical compound CCCOC(C)=O YKYONYBAUNKHLG-UHFFFAOYSA-N 0.000 description 1
- 238000005086 pumping Methods 0.000 description 1
- 238000010791 quenching Methods 0.000 description 1
- 230000000171 quenching effect Effects 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 239000000523 sample Substances 0.000 description 1
- 238000004904 shortening Methods 0.000 description 1
- 239000001632 sodium acetate Substances 0.000 description 1
- 235000017281 sodium acetate Nutrition 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 125000000542 sulfonic acid group Chemical group 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 239000011800 void material Substances 0.000 description 1
- 229920003169 water-soluble polymer Polymers 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/09—Preparation of carboxylic acids or their salts, halides or anhydrides from carboxylic acid esters or lactones
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/42—Separation; Purification; Stabilisation; Use of additives
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/42—Separation; Purification; Stabilisation; Use of additives
- C07C51/43—Separation; Purification; Stabilisation; Use of additives by change of the physical state, e.g. crystallisation
- C07C51/44—Separation; Purification; Stabilisation; Use of additives by change of the physical state, e.g. crystallisation by distillation
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/42—Separation; Purification; Stabilisation; Use of additives
- C07C51/48—Separation; Purification; Stabilisation; Use of additives by liquid-liquid treatment
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Crystallography & Structural Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention belongs to chemical fields, are related to the anticorrosion process and device of methyl acetate hydrolysis and acetic acid refining during polyvinyl alcohol disposing mother liquor.The anti-corrosive apparatus includes methyl acetate enrichment facility, methyl acetate full gear device, methyl acetate hydrolysis device, hydrolysis liquid separating apparatus, acetic acid refining device and isopropyl acetate recyclable device.Methyl acetate hydrolysis and acetic acid refining technique mainly include that methyl acetate concentration, methyl acetate full gear, methyl acetate hydrolysis, hydrolyzate separate and acetic acid refining and isopropyl acetate recycle.By enhancing the ability of impurity removal containing halogen in the hydrolysis tower side top Cai Kou setting mass transfer unit (i.e. packing section)；By adding accurate filter, the shredded resin of hydrolyzate entrainment is filtered, it is therefore prevented that enter acetic acid refining system with sulfonic shredded resin.It fundamentally solves the problem of that acetic acid refining equipment etching problem significantly solves the corrosion of acetic acid refining process device, extends 1~5 times of the key equipment service life.
Description
Technical field
The invention belongs to chemical fields, and in particular in polyvinyl alcohol production process the recyclable device of disposing mother liquor unit and
Technique, particularly during polyvinyl alcohol disposing mother liquor methyl acetate hydrolysis and acetic acid refining anticorrosion process and device.
Background technique
Polyvinyl alcohol (abbreviation PVA) appearance is white powder, is a kind of water soluble polymer, performance is between plastics
Between rubber, in terms of textile industry, building decoration industry, chemical industry, agricultural, daily cosmetics and high-frequency quenching
It is widely used.PVA be uniquely can polyvinyl by bacterium as carbon source and using energy source, belonging to a kind of biology can drop
High molecular material is solved, can be mass produced by Non oil-based route, cheap, oil resistant, solvent resistant and gas barrier property go out
Crowd has unique advantage in terms of food, Key works Drug packing.
Generate a large amount of alcohol hydrolysis mother liquor during polyvinyl acetate alcoholysis production polyvinyl alcohol, main group become methanol,
Methyl acetate and sodium acetate etc., these are all important industrial chemicals and should be recycled.Methyl acetate is actually by raw material vinegar
What acid and methanol generated, 1 ton of polyvinyl alcohol of every production just generates about 1.5 tons of methyl acetates.Although methyl acetate is also a kind ofization
Work raw material, but demand is small is generally sold not as by-product, need to methyl acetate hydrolysis at acetic acid and methanol, through separation and
Vinyl acetate synthesis and polymerization are used for after purification.In industrial processes, methyl acetate is in storng-acid cation exchange resin
Under effect, be shown below hydrolysis, generates acetic acid and methanol:
CH3COOCH3+H2O===CH3OH+CH3COOH
Equipment seriously corroded often is caused because forming the impure dense acetic acid of high temperature during acetic acid refining.The sector was once attempted
It crosses and equipment material is upgraded into deoxidized cooper or even pure titanium by 316L stainless steel, though it can slightly extend service life, it cannot be thorough
Bottom solves etching problem, annoyings PVA industry development always for a long time.
Document report (Mao Yongsheng, acetic acid concentration tower corrosion research, master thesis, 2000；Xu Zhiqiang, the workshop PVA vinegar
The research of acid tower corrosion mechanism and protection countermeasure, petrochemical equipment technology, 2008,29 (5), 46) generation of acetic acid refining tower is seriously
The main reason for corrosion is to be mixed into chloride ion etc. containing halogen impurities, under its operating condition, halogen in tower charging spirit of vinegar
Ion and hydrogen ion are combined into corresponding hydride and water forms maximum azeotrope object, azeotropic point between feedboard and bottom temperature it
Between, cause halogen hydride to gather in tower.Halogen hydride after accumulation is under high concentration acetic acid, higher temperature environment to gold
Belonging to material corrosion has fairly obvious quickening effect, can cause corrosion failure within a very short time, greatly shortening equipment makes
Use the period.Horse expedition etc. (Ma Yuanzheng, polyvinyl alcohol production in acetic acid concentration tower corrosion research, master thesis, 2005)
It is proposed that chloride ion accumulation region setting side take-off mouth produces the acetic acid of chloride ion-containing out of tower in acetic acid refining tower, to subtract
The anti-corrosion strategy of slow chloride ion accumulation.Although this method can alleviate etching problem to a certain extent, will form largely containing chlorine
Useless acetic acid can not be handled, and problem is not solved effectively.
Currently, although the acetic acid refining equipment material of some process units of polyvinyl alcohol industry has upgraded to corrosion resistance very
Strong titanium, but still unresolved acetic acid etching problem.The new technological flow with enhancing anti-corrosion ability is developed, is eliminated from source
Enhance the corrosive impurity of acetic acid, is of great significance to the long- period safety production of polyvinyl alcohol device, it is same to other industries
Types of devices also has promotional value.
Summary of the invention
The purpose of the present invention is to provide the anti-corrosions of methyl acetate hydrolysis and acetic acid refining during PVA alcoholysis disposing mother liquor
Device and technique eliminate the enhancing corrosive impurity of acetic acid by the way that separator and process flow is rationally arranged from source, from
Fundamentally prevent the corrosion of acetic acid refining equipment.
The anti-corrosive apparatus of methyl acetate hydrolysis and acetic acid refining provided by the invention, including methyl acetate enrichment facility, vinegar
Sour methyl esters full gear device, methyl acetate hydrolysis device, hydrolysis liquid separating apparatus, acetic acid refining device and isopropyl acetate recycling dress
It sets；
The methyl acetate enrichment facility includes extractive distillation column, and the methyl acetate full gear device includes de- acetaldehyde tower,
The methyl acetate hydrolysis device includes hydrolysis tower, and the hydrolysis liquid separating apparatus includes hydrolyzate knockout tower, the acetic acid essence
Device processed includes acetic acid refining tower, and the isopropyl acetate recyclable device includes isopropyl acetate recovery tower；
The extractive distillation column, de- acetaldehyde tower, hydrolysis tower, hydrolyzate knockout tower, acetic acid refining tower and isopropyl acetate return
Tower is received to connect according to flow direction of material；Preferably, the tower top of the extractive distillation column is connect with the middle part of de- acetaldehyde tower, the de- second
The tower reactor of aldehyde tower and the tower top of hydrolysis tower connect, and the tower reactor of the hydrolysis tower is connect with the middle part of hydrolyzate knockout tower, the water
The tower reactor of solution liquid knockout tower is connect with the middle part of acetic acid refining tower, the tower top and isopropyl acetate recovery tower of the acetic acid refining tower
Tower top connection.
Device according to the present invention, the methyl acetate enrichment facility further include extractive distillation column condenser, extractive distillation column
Return tank, extractive distillation column reflux pump, extracting rectifying tower reboiler；
Tower top and extractive distillation column condenser, extractive distillation column return tank, the extractive distillation column of the extractive distillation column return
Stream pump is sequentially connected with；The outlet of extractive distillation column reflux pump is connect with extracting rectifying top of tower, and is arranged and is taken off on connecting line
The branch of acetaldehyde tower connection；
Extracting rectifying tower reboiler is arranged in the tower reactor of the extractive distillation column；
The tower reactor of the extractive distillation column is also connect with refining methanol system；
The methyl acetate enrichment facility further includes extraction water inlet and methyl acetate entrance, it is preferable that the extraction water
The middle part of the connection of the tower top of entrance and extractive distillation column, the methyl acetate entrance and extractive distillation column connects.
Device according to the present invention, the methyl acetate full gear device further include de- acetaldehyde tower condenser, de- acetaldehyde tower reflux
Tank, de- acetaldehyde tower reflux pump, de- acetaldehyde tower reboiler, de- acetaldehyde tower reactor go out to pump；
The tower top of the de- acetaldehyde tower and de- acetaldehyde tower condenser, de- acetaldehyde tower return tank, de- acetaldehyde tower reflux pump are sequentially
Connection；The outlet of de- acetaldehyde tower reflux pump is connect with de- acetaldehyde top of tower, and connecting line is equipped with and connects with acetaldehyde refining system
The branch connect；
De- acetaldehyde tower reboiler is arranged in the tower reactor of the de- acetaldehyde tower；
The tower reactor of the de- acetaldehyde tower goes out to pump, be sequentially connected at the top of hydrolysis tower with de- acetaldehyde tower reactor.
Device according to the present invention, the methyl acetate hydrolysis device further include storng-acid cation exchange resin bed, hydrolysis
Tower condenser, hydrolysis tower return tank, hydrolysis tower reflux pump, hydrolysis tower side adopt pump, hydrolysis tower reboiler, hydrolysis tower reactor and go out pump and essence
Close filter；The tower top of the hydrolysis tower is sequentially connected with hydrolysis tower condenser, hydrolysis tower return tank, hydrolysis tower reflux pump；Water
It solves and is connect at the top of the outlet and hydrolysis tower of tower reflux pump；The hydrolysis tower condenser is also connect with the middle part of de- acetaldehyde tower；
Pump, storng-acid cation exchange resin bed, precision are adopted in the top side take-off mouth of the hydrolysis tower and hydrolysis tower side
Filter is sequentially connected with, and is connect in the middle part of the outlet of accurate filter and hydrolysis tower；
Preferably, packing section is set in the hydrolysis tower, and packing section is located at the top of top side take-off mouth；
Preferably, the packing section is equivalent to 5~10 pieces of theoretical cam curves；
Wherein, the accurate filter is at least arranged one, and the arrangement of accurate filter can be in parallel or series；Such as
It is arranged in parallel on the connecting line of accurate filter A and accurate filter B, the accurate filter A and accurate filter B and installs
Several valves；
The tower reactor setting hydrolysis tower reboiler of the hydrolysis tower；
The tower reactor of the hydrolysis tower goes out to pump, be sequentially connected in the middle part of hydrolyzate knockout tower with hydrolysis tower reactor.
Further, the methyl acetate hydrolysis device further includes methyl acetate hydrolysis water inlet, is arranged in de- acetaldehyde
On connecting line at the top of tower tower reactor and hydrolysis tower.
Device according to the present invention, the hydrolysis liquid separating apparatus further include hydrolyzate knockout tower condenser, hydrolyzate separation
Tower return tank, hydrolyzate knockout tower reflux pump, hydrolyzate separation tower reboiler, hydrolyzate separation tower reactor go out to pump；
The tower top of the hydrolyzate knockout tower is equipped with two branches, connect in the middle part of branch one and extractive distillation column, branch two
It is sequentially connected with hydrolyzate knockout tower condenser, hydrolyzate knockout tower return tank, hydrolyzate knockout tower reflux pump；Hydrolyzate separation
The outlet of tower reflux pump is connect with the top of hydrolyzate knockout tower；
The tower reactor setting hydrolyzate of the hydrolyzate knockout tower separates tower reboiler；
The tower reactor of the hydrolyzate knockout tower separates tower reactor with hydrolyzate and goes out to pump, be sequentially connected in the middle part of acetic acid refining tower.
Device according to the present invention, the acetic acid refining tower further include acetic acid refining tower condenser, acetic acid refining tower phase-splitter,
Acetic acid refining tower reflux pump, acetic acid refining tower reboiler, pump is adopted in acetic acid refining tower side, acetic acid refining tower reactor goes out to pump；
The tower top of the acetic acid refining tower is sequentially connected with acetic acid refining tower condenser, acetic acid refining tower phase-splitter, described
Acetic acid refining tower phase-splitter is equipped with outlet one and outlet two, and outlet one is suitable with acetic acid refining tower reflux pump, acetic acid refining top of tower
Secondary connection；Outlet two is connect with isopropyl acetate recyclable device；
Pump connection is adopted in the outlet of lower part side line and the acetic acid refining tower side of the acetic acid refining tower, produces acetic acid；
Acetic acid refining tower reboiler is arranged in the tower reactor of the acetic acid refining tower；
The tower reactor and acetic acid refining tower reactor of the acetic acid refining tower go out to pump connection, and residue and tar is discharged.
Device according to the present invention, the isopropyl acetate recyclable device further include isopropyl acetate recovery tower condenser, vinegar
Isopropyl propionate recovery tower phase-splitter, isopropyl acetate recovery tower distillate pump, isopropyl acetate water phase pans, isopropyl acetate and return
Tower feed pump, isopropyl acetate recycling tower reboiler, isopropyl acetate recycling tower reactor is received to go out to pump；
The acetic acid refining tower phase-splitter is equipped with oil mutually outlet and water phase outlet；
The outlet two of the acetic acid refining tower phase-splitter and isopropyl acetate water phase pans, isopropyl acetate recovery tower into
It is sequentially connected at the top of material pump, isopropyl acetate recovery tower；
Tower top and isopropyl acetate recovery tower condenser, the isopropyl acetate recovery tower point of the isopropyl acetate recovery tower
Phase device is sequentially connected with；Mutually outlet, isopropyl acetate recovery tower distillate pump, acetic acid refining tower to the oil of the acetic acid refining tower phase-splitter
Phase-splitter is sequentially connected with；The water phase outlet of the acetic acid refining tower phase-splitter is connect with isopropyl acetate water phase pans；
The tower reactor setting isopropyl acetate of the isopropyl acetate recovery tower recycles tower reboiler；
Tower reactor and isopropyl acetate the recycling tower reactor of the isopropyl acetate recovery tower go out to pump connection, send out kettle draining.
The present invention also provides the anticorrosion process of above-mentioned methyl acetate hydrolysis and acetic acid refining, the anticorrosion process is based on upper
The anti-corrosive apparatus stated, the technique mainly include methyl acetate concentration, methyl acetate full gear, methyl acetate hydrolysis, hydrolyzate separation
And acetic acid refining and isopropyl acetate recycle.
Technique according to the present invention, the methyl acetate concentration technology unit includes following operation:
(1) thick methyl acetate enters in extractive distillation column, carries out the separation of methyl acetate and methanol；
(2) extraction water is added to extracting rectifying top of tower, the methyl acetate steam warp volatilized from extracting rectifying column overhead
Condensation is collected, after boosting, and for a portion methyl acetate from extractive distillation column overhead reflux, remaining is sent into de- acetaldehyde tower charging；
(3) methanol aqueous solution that extractive distillation column tower reactor generates, sends to refining methanol system and is recycled；
Preferably, the source of above-mentioned thick methyl acetate includes the thick methyl acetate (concentration from crude methyl acetate sub-unit
60~75%, the thick methyl acetate such as 75%) distillated with methyl acetate hydrolysis workshop section by hydrolyzate knockout tower top gaseous phase；
Preferably, the temperature of above-mentioned extraction water is 2~15 DEG C, and such as 4~10 DEG C, illustratively, temperature is 10 DEG C；
Wherein, the operating parameter of the extractive distillation column are as follows: 0.085~0.15Mpa of pressure, such as 0.1MPa；Tower top temperature
Degree is 50~60 DEG C, such as 55 DEG C；Bottom temperature is 75~85 DEG C, such as 82 DEG C；Overhead reflux flow/overhead extraction flow=
1.3~1.7, such as 1.4~1.6.
Wherein, above-mentioned technique unit destroys acetic acid using the methanol in the method removing alcoholysis liquid for adding water extracting rectifying
The azeotropism of methyl esters and methanol reduces methanol to the inhibiting effect during subsequent methyl acetate hydrolysis.
Technique according to the present invention, the methyl acetate full gear technique unit includes following operation:
(1) methyl acetate enters de- acetaldehyde tower progress gas-liquid mass transfer；
(2) steam that distillates of acetaldehyde tower top is taken off after condensation, collection, boosting, and a portion acetaldehyde is from de- acetaldehyde tower top
Portion's reflux, remaining acetaldehyde send to purification；
(3) hydrolysis tower top feed is sent into after the methyl acetate of tower reactor is boosted；
Preferably, the methyl acetate in step (1) includes the methyl acetate stream stock and come from that extracting rectifying top of tower distillates
The gas phase impurities removal stream stock of hydrolysis tower；
Wherein, the operating parameter of the de- acetaldehyde tower are as follows: 0.085~0.15MPa of pressure, such as 0.1MPa；Tower top temperature
It is 45~55 DEG C, such as 50 DEG C；Bottom temperature is 50~60 DEG C, such as 55 DEG C；Return flow/feed rate=1.2~1.7,
Such as 1.3~1.6.
Wherein, above-mentioned methyl acetate full gear technique unit for will the chloride ion, fluorine ion, bromine that be brought by extraction water from
Son, iodide ion halogen impurities and acetaldehyde impurities are removed from system.
Technique according to the present invention, the hydrolysis process of methyl acetate unit includes following operation:
(1) by taking off the methyl acetate of acetaldehyde tower tower reactor outflow, into hydrolysis tower, steam is distillated through cold from hydrolysis tower top
After solidifying, collection, boosting, from hydrolysis tower overhead reflux, solidifying gas is sent into de- acetaldehyde tower as gas phase impurities removal stream stock and is fed；
(2) it from hydrolysis tower top side take-off methyl acetate, is mixed after boosted with methyl acetate hydrolysis water, is sent into strong acid
Property cation exchange resin bed be hydrolyzed reaction, generate acetic acid and methanol, hydrolyzate be removed by filtration wherein carry secretly it is broken
After resin, returns to hydrolysis tower middle and lower part and separated；
Preferably, the methyl acetate of above-mentioned hydrolysis tower top side take-off is processed through inner-tower filling material section；
Wherein, the operating parameter of the hydrolysis tower are as follows: 0.085~0.15MPa of pressure, such as 0.1MPa；Tower top temperature is
55~65 DEG C, such as 60 DEG C；Bottom temperature is 80~85 DEG C, such as 83 DEG C；60~65 DEG C of temperature at side take-off, such as 61
℃；Return flow/feed rate=3.3~4.2, such as 3.5~4.0.
Preferably, above-mentioned filtering uses accurate filter, and the accurate filter makees filter medium using Nomex, can be right
Shredded resin effectively filters, and shredded resin is avoided to enter acetic acid concentration systems；
Wherein, the operating parameter of the storng-acid cation exchange resin bed are as follows: 65~75 DEG C of feeding temperature, such as 70
℃。
Wherein, the operating condition of the accurate filter are as follows: pressure drop is less than 0.1MPa, such as 0.01~0.09MPa；
20~30mm of thickness of filter medium, the aperture of filter medium is less than 1 μm, such as 0.2~0.9um.
(3) hydrolyzate knockout tower is sent into after the hydrolyzate boosting of hydrolysis tower tower reactor to be separated；
Preferably, the hydrolysis liquid is mainly organized as acetic acid, methanol, water and methyl acetate；
Wherein, above-mentioned hydrolysis process of methyl acetate unit, is hydrolyzed reaction in storng-acid cation exchange resin bed
Methyl acetate stream stock by hydrolysis tower top side take-off, using the mass transfer unit between side take-off mouth and tower top to system
Halogen impurities and acetaldehyde be concentrated, and produced with gas phase to methyl acetate full gear unit, side is adopted theoretical between mouth and tower top
Plate number is 5~10 pieces；
The accurate filter uses Nomex as filter medium, anti-to hydrolyzing using liquid precise clarification filtration mode
Liquid is answered to be filtered, the filter medium of the precision clarification filtration has capillary aperture small, porosity is big, filter medium thickness
Feature, by solid particle intercept in the internal void of filtering medium layer.
Technique according to the present invention, the hydrolyzate separating technology unit includes following operation:
(1) enter hydrolyzate knockout tower by the hydrolyzate that hydrolysis tower tower reactor flows out to be separated, overhead vapours partial gas phase
It is blown into extractive distillation column, rest part flows back after condensation, collection, boosting from hydrolyzate separation column；
(2) it is sent into acetic acid refining tower after the spirit of vinegar of hydrolyzate knockout tower tower reactor is boosted, carries out dehydration purification.
Wherein, the operating parameter of the hydrolyzate knockout tower are as follows: 0.085~0.15MPa of pressure, such as 0.1MPa；Tower top
Temperature is 60~70 DEG C, such as 65 DEG C；Bottom temperature is 110~115 DEG C, such as 113 DEG C, supplement regurgitant volume/feed rate=
0.55~1.1, such as 0.6~1.0.
Technique according to the present invention, the acetic acid refining technique unit includes following operation:
(1) acetic acid refining tower is entered by the spirit of vinegar that hydrolyzate knockout tower tower reactor flows out, distillates water from tower top and acetic acid is different
The azeotropic mixture of propyl ester obtains the isopropyl acetate on upper layer and the separation water of lower layer (containing a small amount of acetic acid isopropyl after condensation, split-phase
Ester)；
Preferably, entrainer is made using isopropyl acetate in acetic acid refining tower；
(2) reflux of acetic acid refining top of tower is sent into after the isopropyl acetate on upper layer is mutually boosted, the separation water of lower layer is (containing few
Measure isopropyl acetate) collect after, be sent into isopropyl acetate recovery tower；
(3) by acetic acid refining tower lower part side take-off acetic acid, the residue and tar transmitting system of tower reactor.
Wherein, the operating parameter of the acetic acid refining tower are as follows: 0.085~0.15MPa of pressure, such as 0.1MPa；Tower top temperature
Degree is 70~80 DEG C, such as 75 DEG C；Bottom temperature is 120~125 DEG C, such as 124 DEG C；Lower part side take-off temperature 120~125
DEG C, such as 123.8 DEG C；Return flow/feed rate=3.7~4.2, such as 3.8~4.1.
Technique according to the present invention, the isopropyl acetate recovery process unit includes following operation:
(1) from the separation water of acetic acid refining technique unit, at the top of isopropyl acetate recovery tower, tower overhead gas is through cold
Solidifying, split-phase obtains water phase and oily phase, collects water phase, and water phase is back at the top of isopropyl acetate recovery tower, returns after oil is mutually boosted
Return acetic acid refining unit；
(2) transmitting system after the tower reactor draining of isopropyl acetate recovery tower is boosted；
Preferably, the isopropyl acetate recovery tower only sets stripping section；
Wherein, the operating parameter of the isopropyl acetate recovery tower are as follows: 0.085~0.15MPa of pressure, such as 0.1MPa；
Tower top temperature is 90~100 DEG C, such as 96 DEG C；Bottom temperature is 95~103 DEG C, such as 100 DEG C；
Wherein, the operation temperature of the split-phase is 35~45 DEG C.
Movement and distribution rule of present inventor's system research halide ion in the PVA alcoholysis mother liquor recovery system
Rule, probes into obtain Accumulation Mechanism of the micro halogen in system.Based on the studies above, develops and remove micro halogen from system
The method of impurity constructs new separation process, removes halogen impurities under compared with low energy consumption, material consumption to realize.
Present inventor is hydrolyzed by Dichlorodiphenyl Acetate methyl esters and the system research of acetic acid refining device has been surprisingly found that, in acetic acid
There is also broken strong-acid ion exchange resin particle and powder in purification tower reactor.Further analysis finds that shredded resin is
It is brought after methyl acetate hydrolysis catalyst breakage with hydrolyzate.The resinoid be have netted stereochemical structure with sulfonic acid group
High molecular polymer, in use process, can because of mechanical external force effect, transition, polymer molecule degradation repeatedly, and regeneration,
The reasons such as backwash extruding, make the macromolecular chain fracture for constituting resin, and the intensity of resin is easy to die down and cause to be crushed.Broken tree
Cosmetics end can enter together hydrolyzate knockout tower and acetic acid refining tower with hydrolysis liquid, decomposite organic acid at relatively high temperatures
Molecule acts synergistically to form the deep-etching source of equipment with acetic acid.This discovery has not been reported in existing publish in document.Into
One step is the study found that the shredded resin granularity is minimum, and medium has corrosivity, and the difficulty removed from system is larger.
Based on this discovery, the application is additionally arranged accurate filter in hydrolysis reactor cation exchange resin bed exit and presss from both sides to hydrolyzate
The shredded resin of band is filtered, it is therefore prevented that is entered acetic acid refining system with sulfonic shredded resin, is avoided shredded resin
It causes equipment to corrode, effectively prevents a kind of source of corrosion.
Beneficial effects of the present invention:
The present invention is based on chloride ion, fluorine ion, bromide ion, iodide ion and the shredded resins of inventor's discovery in methyl acetate
Movement and the regularity of distribution, establish efficient removal measure, effectively control in the dense acetic acid of high temperature in hydrolysis and acetic acid refining system
Impurity content.
Specifically, on the one hand, the present invention in the hydrolysis tower side top Cai Kou setting mass transfer unit (i.e. packing section) by increasing
The strong ability of impurity removal containing halogen, by chloride ion, fluorine ion, bromide ion, iodide ion and hydrogen in the tower reactor hydrolyzate for sending rear system
The hydride content of formation, which is controlled, accumulates appearance because forming maximum azeotrope object hereinafter, avoiding in acetic acid refining tower in 10ppm
High local concentrations area；And original technology produces methyl acetate at the top of hydrolysis tower, halogen impurities enter water together with reaction stream stock
Reactor cation exchange resin bed is solved, and enters acetic acid refining tower together with the acetic acid of generation, is constantly accumulated.
On the other hand, the present invention is additionally arranged accurate filter to water in hydrolysis reactor cation exchange resin bed exit
The shredded resin of solution liquid entrainment is filtered, it is therefore prevented that enters acetic acid refining system with sulfonic shredded resin.
By above-mentioned two measures, the effective removing for aggravating highly concentrated acetic acid corrosive impurity is realized under the conditions of low energy consumption,
Acetic acid refining equipment etching problem is fundamentally solved the problem of to significantly solve the corrosion of acetic acid refining process device, is extended
1~5 times of the key equipment service life.
Detailed description of the invention
Fig. 1 is the apparatus structure schematic diagram of methyl acetate hydrolysis described in the embodiment of the present invention 1 and acetic acid refining；
Appended drawing reference: 01- extractive distillation column, 02- take off acetaldehyde tower, 03- hydrolysis tower, 04- storng-acid cation exchange resin
Bed, 05A- accurate filter A, 05B- accurate filter B, 06- hydrolyzate knockout tower, 07- acetic acid refining tower, 08- acetic acid isopropyl
Ester recovery tower, 09- extractive distillation column condenser, 10- extractive distillation column return tank, 11- extractive distillation column reflux pump, 12- extraction
Rectifying tower reboiler, 13- take off acetaldehyde tower condenser, and 14- takes off acetaldehyde tower return tank, and 15- takes off acetaldehyde tower reflux pump, and 16- takes off acetaldehyde
Tower reboiler, 17- take off acetaldehyde tower reactor and go out to pump, 18- hydrolysis tower condenser, 19- hydrolysis tower return tank, 20- hydrolysis tower reflux pump,
Pump is adopted in 21- hydrolysis tower side, and 22- hydrolyzes tower reboiler, and 23- hydrolyzes tower reactor and goes out to pump, 24- hydrolyzate knockout tower condenser, 25- hydrolysis
Liquid knockout tower return tank, 26- hydrolyzate knockout tower reflux pump, 27- hydrolyzate separate tower reboiler, and 28 hydrolyzates separation tower reactor goes out
Pump, 29- acetic acid refining tower condenser, 30- acetic acid refining tower phase-splitter, 31- acetic acid refining tower reflux pump, 32- acetic acid refining tower
Pump is adopted in reboiler, 33- acetic acid refining tower side, and 34- acetic acid refining tower reactor goes out to pump, 35- isopropyl acetate recovery tower condenser, 36-
Isopropyl acetate recovery tower phase-splitter, 37- isopropyl acetate recovery tower distillate pump, 38- isopropyl acetate water phase pans, 39-
Isopropyl acetate recovery tower feed pump, 40- isopropyl acetate recycle tower reboiler, and 41- isopropyl acetate recycles tower reactor and goes out to pump.
Specific embodiment
Further detailed description is done to the device of the invention structure and technique below in conjunction with specific embodiment.It should
Understand, the following example is merely illustrative the ground description and interpretation present invention, and is not necessarily to be construed as to the scope of the present invention
Limitation.In the range of all technologies realized based on above content of the present invention are encompassed by the present invention is directed to protect.
Unless otherwise indicated, raw materials and reagents used in the following embodiment are commercial goods, or can be by
Perception method preparation.
Embodiment 1
The anti-corrosive apparatus of methyl acetate hydrolysis and acetic acid refining with anti-corrosion function as shown in Figure 1, including tumer
Ester enrichment facility, methyl acetate full gear device, methyl acetate hydrolysis device, hydrolysis liquid separating apparatus, acetic acid refining device and vinegar
Isopropyl propionate recyclable device；
Methyl acetate enrichment facility includes extractive distillation column 01, and methyl acetate full gear device includes de- acetaldehyde tower 02, acetic acid
Methyl esters hydrolysis device includes hydrolysis tower 03, and hydrolysis liquid separating apparatus includes hydrolyzate knockout tower 06, and acetic acid refining device includes vinegar
Acid treating tower 07, isopropyl acetate recyclable device include isopropyl acetate recovery tower 08；
Wherein, extractive distillation column 01, de- acetaldehyde tower 02, hydrolysis tower 03, hydrolyzate knockout tower 06, acetic acid refining tower 07 and vinegar
Isopropyl propionate recovery tower 08 is connected according to flow direction of material；The tower top of extractive distillation column 01 is connect with the middle part of de- acetaldehyde tower 02, is taken off
The tower reactor of acetaldehyde tower 02 is connect with the tower top of hydrolysis tower 03, and the tower reactor of hydrolysis tower 03 is connect with the middle part of hydrolyzate knockout tower 06,
The tower reactor of hydrolyzate knockout tower 06 is connect with the middle part of acetic acid refining tower 07, and the tower top and isopropyl acetate of acetic acid refining tower 07 return
Receive the tower top connection of tower 08.
Wherein, methyl acetate enrichment facility includes extractive distillation column 01, extractive distillation column condenser 09, extractive distillation column time
Flow tank 10, extractive distillation column reflux pump 11, extracting rectifying tower reboiler 12；
The tower top and extractive distillation column condenser 09, extractive distillation column return tank 10, extractive distillation column of extractive distillation column 01
Reflux pump 11 is sequentially connected with；It is connected at the top of the outlet of extractive distillation column reflux pump 11 and extractive distillation column 01, and on connecting line
The branch connecting with de- acetaldehyde tower 02 is set；Extracting rectifying tower reboiler 12 is arranged in the tower reactor of extractive distillation column 01, as heat source；
The tower reactor of extractive distillation column 01 is also connect with refining methanol system；
Wherein, methyl acetate enrichment facility further includes extraction water inlet and methyl acetate entrance, extracts water inlet and extraction
The tower top of rectifying column 01 connects, and methyl acetate entrance is connect with the middle part of extractive distillation column 01.
Wherein, methyl acetate full gear device includes de- acetaldehyde tower 02, de- acetaldehyde tower condenser 13, de- acetaldehyde tower return tank
14, acetaldehyde tower reflux pump 15, de- acetaldehyde tower reboiler 16, de- acetaldehyde tower reactor is taken off to go out to pump 17；The tower top of de- acetaldehyde tower 02 and de- second
Aldehyde tower condenser 13, de- acetaldehyde tower return tank 14, de- acetaldehyde tower reflux pump 15 are sequentially connected with；The outlet of de- acetaldehyde tower reflux pump 15
It is connected at the top of de- acetaldehyde tower 02, and connecting line is equipped with the branch connecting with acetaldehyde refining system；
De- acetaldehyde tower reboiler 16 is arranged in the tower reactor of de- acetaldehyde tower 02, as heat source；
The tower reactor of de- acetaldehyde tower 02 goes out to pump with de- acetaldehyde tower reactor to be sequentially connected at the top of 17, hydrolysis tower 03.
Wherein, methyl acetate hydrolysis device includes hydrolysis tower 03, storng-acid cation exchange resin bed 04, hydrolysis tower condensation
Device 18, hydrolysis tower return tank 19, hydrolysis tower reflux pump 20, hydrolysis tower side adopt pump 21, hydrolysis tower reboiler 22, hydrolysis tower reactor and go out to pump
23 and accurate filter；
The tower top of hydrolysis tower 03 is sequentially connected with hydrolysis tower condenser 18, hydrolysis tower return tank 19, hydrolysis tower reflux pump 20,
It is connected at the top of the outlet of hydrolysis tower reflux pump 20 and hydrolysis tower 03；
Pump 21, storng-acid cation exchange resin bed 04, essence are adopted in the top side take-off mouth of hydrolysis tower 03 and hydrolysis tower side
Close filter is sequentially connected with, and is connected in the middle part of the outlet of accurate filter and hydrolysis tower 03；
Packing section is set in hydrolysis tower 03, and packing section is located at the top of top side take-off mouth, and packing section is equivalent to 5~10
Block number of theoretical plate；
Accurate filter includes the accurate filter 05A and accurate filter 05B of parallel connection, accurate filter 05A and precision
Several valves are installed on the connecting line of filter 05B；Under normal circumstances, a use, another spare.
The tower reactor setting hydrolysis tower reboiler 22 of hydrolysis tower 03, as heat source；
The tower reactor of hydrolysis tower 03 goes out to pump with hydrolysis tower reactor to be sequentially connected in the middle part of 23, hydrolyzate knockout tower 06；
Methyl acetate hydrolysis device further includes methyl acetate hydrolysis water inlet, and setting is in de- 02 tower reactor of acetaldehyde tower and hydrolysis
On the connecting line at 03 top of tower.
Wherein, hydrolysis liquid separating apparatus includes hydrolyzate knockout tower 06, hydrolyzate knockout tower condenser 24, hydrolyzate separation
Tower return tank 25, hydrolyzate knockout tower reflux pump 26, hydrolyzate separation tower reboiler 27, hydrolyzate separation tower reactor go out to pump 28；
The tower top of hydrolyzate knockout tower 06 is equipped with two branches, connects in the middle part of branch one and extractive distillation column 01, branch two
It is sequentially connected with hydrolyzate knockout tower condenser 24, hydrolyzate knockout tower return tank 25, hydrolyzate knockout tower reflux pump 26；Hydrolysis
The outlet of liquid knockout tower reflux pump 26 is connect with the top of hydrolyzate knockout tower 26；
The tower reactor setting hydrolyzate of hydrolyzate knockout tower 06 separates tower reboiler 27, as heat source；
The tower reactor of hydrolyzate knockout tower 06 separates tower reactor with hydrolyzate and goes out to pump 28, be sequentially connected in the middle part of acetic acid refining tower 07.
Wherein, acetic acid refining device includes acetic acid refining tower 07, acetic acid refining tower condenser 29, acetic acid refining tower phase-splitter
30, acetic acid refining tower reflux pump 31, acetic acid refining tower reboiler 32, acetic acid refining tower side are adopted pump 33, acetic acid refining tower reactor and are pumped out
34；
The tower top of acetic acid refining tower 07 is sequentially connected with acetic acid refining tower condenser 29, acetic acid refining tower phase-splitter 30, vinegar
Acid treating tower phase-splitter 30 is equipped with outlet one and outlet two, and outlet one is pushed up with acetic acid refining tower reflux pump 31, acetic acid refining tower 07
Portion is sequentially connected with；
The lower part side line of acetic acid refining tower 07 is adopted pump 33 with acetic acid refining tower side and is connect, and acetic acid is produced；
Acetic acid refining tower reboiler 32 is arranged in the tower reactor of acetic acid refining tower 07, as heat source；
The tower reactor of acetic acid refining tower 07, which goes out to pump 34 with acetic acid refining tower reactor, to be connect, and residue and tar is discharged.
Isopropyl acetate recyclable device includes isopropyl acetate recovery tower 08, isopropyl acetate recovery tower condenser 35, vinegar
It is different that isopropyl propionate recovery tower phase-splitter 36, isopropyl acetate recovery tower distillate pump 37, isopropyl acetate water phase pans 38, acetic acid
Propyl ester recovery tower feed pump 39, isopropyl acetate recycling tower reboiler 40, isopropyl acetate recycling tower reactor go out to pump 41；
Acetic acid refining tower phase-splitter 36 is equipped with oil mutually outlet and water phase outlet；
The outlet two of acetic acid refining tower phase-splitter 30 and isopropyl acetate water phase pans 38, isopropyl acetate recovery tower into
It is sequentially connected at the top of material pump 39, isopropyl acetate recovery tower 08；
Tower top and isopropyl acetate recovery tower condenser 35, the isopropyl acetate recovery tower point of isopropyl acetate recovery tower 08
Phase device 36 is sequentially connected with；Mutually outlet, isopropyl acetate recovery tower distillate pump 37, acetic acid refining to the oil of acetic acid refining tower phase-splitter 36
Tower phase-splitter 30 is sequentially connected with；The water phase outlet of acetic acid refining tower phase-splitter 36 is connect with isopropyl acetate water phase pans 38；
The tower reactor of isopropyl acetate recovery tower 08 goes out to pump 41 with isopropyl acetate recycling tower reactor to be connect, and kettle draining is sent out.
It is specifically described below in conjunction with the hydrolysis of Fig. 1 Dichlorodiphenyl Acetate methyl esters and the process flow of the anti-corrosive apparatus of acetic acid refining:
Methyl acetate concentration technology unit: 06 tower top of 75% thick methyl acetate and hydrolyzate knockout tower from preamble workshop section
The thick methyl acetate that gas phase distillates enters extractive distillation column 01, carries out the separation of methyl acetate and methanol.It is cooled to 10 DEG C of extraction
It fetches water and is added at the top of extractive distillation column 01 to destroy the azeotropism of methyl acetate and methanol, increase methyl acetate and methanol
Relative volatility.01 overhead vapours of extractive distillation column enters extractive distillation column return tank after the condensation of extractive distillation column condenser 09
10, partially by extractive distillation column reflux pump 11 boost after return extractive distillation column 01 flow back, rest part send de- acetaldehyde tower 02 into
Material.Tower reactor heat source is provided by extracting rectifying tower reboiler 12, and tower reactor is methanol aqueous solution, and refining methanol system is sent to refine back
It receives.
Methyl acetate full gear technique unit: the methyl acetate stream stock that is distillated at the top of extractive distillation column 01 and from hydrolysis tower 03
Gas phase impurities removal stream stock, carry out vapour-liquid mass into de- acetaldehyde tower 02, overhead vapours after the de- condensation of acetaldehyde tower condenser 13, into
Enter de- acetaldehyde tower return tank 14, by the de- boosting of acetaldehyde tower reflux pump 15 rear portion reflux, rest part send acetaldehyde refining system
Processing takes off acetaldehyde tower so that chloride ion, fluorine ion, bromide ion, iodide ion halogen impurities and acetaldehyde impurities be removed from system
02 tower reactor heat source is provided by de- acetaldehyde tower reboiler 16, tower reactor by liquid take off acetaldehyde tower reactor go out to pump 17 send 03 top of hydrolysis tower into
Material.
Hydrolysis process of methyl acetate unit: 03 overhead vapor of hydrolysis tower is after 18 partial condensation of hydrolysis tower condenser, lime set
It fully enters hydrolysis tower return tank 19 and is returned in hydrolysis tower 03 through hydrolysis tower reflux pump 19 and flowed back, not solidifying gas is as impurities removal stream
Stock send de- acetaldehyde tower 02 to feed, with chloride ion, fluorine ion, the bromine for removing the acetaldehyde of catalysis hydrolysis system and being brought by extraction water
Ion, iodide ion halogen impurities.21 boosting of pump and and tumer are adopted from 03 top side line production material of hydrolysis tower through hydrolysis tower side
After the mixing of ester hydrolysis water, it is sent into storng-acid cation exchange resin bed 04 and reaction is hydrolyzed.It is arranged on side take-off mouth
8 pieces of theoretical plate high efficiency packing sections are equivalent to, realize the key measures that halogen impurities and aldehyde effectively remove.The acetic acid in 04
The partial hydrolysis under the catalytic action of cation exchange resin of methyl esters and water generates acetic acid and methanol, the hydrolyzate accurate filter
03 middle and lower part of hydrolysis tower is returned to after 05 filtering to be separated.The hydrolyzate accurate filter makees filter medium to broken using Nomex
Broken resin effectively filters, and shredded resin is avoided to enter acetic acid concentration systems.The main composition of 03 tower reactor hydrolysis liquid of hydrolysis tower
For acetic acid, methanol, water and methyl acetate, goes out pumping hydrolyzate knockout tower 06 through hydrolyzate separation tower reactor and separated.Hydrolysis tower
03 tower reactor heat source is provided by hydrolysis tower reboiler 22.
Hydrolyzate separating technology unit: the hydrolyzate of 03 tower reactor of hydrolysis tower, which goes out to pump 23 through hydrolysis tower reactor, is sent into hydrolyzate separation
Tower 06 is separated, and overhead vapours partial gas phase is blown into extractive distillation column 01, and rest part is through hydrolyzate knockout tower condenser 24
Enter hydrolyzate knockout tower return tank 25 after condensation, returns to tower reflux through hydrolyzate knockout tower reflux pump 26；Hydrolyzate separation
06 tower reactor spirit of vinegar of tower goes out to pump 28 through hydrolyzate separation tower reactor send acetic acid refining tower 07 to carry out dehydration purification.Hydrolyzate knockout tower 06
Tower reactor heat source is provided by hydrolyzate separation tower reboiler 27.
Acetic acid refining technique unit: 07 tower of acetic acid refining tower makees entrainer using isopropyl acetate, utilizes isopropyl acetate
With the azeotropism of water, the azeotropic mixture of water and isopropyl acetate is distillated from tower top.Top gaseous phase mixture is through acetic acid refining tower
Enter 30 split-phase of acetic acid refining tower phase-splitter after the condensation of condenser 29, cooling.Upper layer isopropyl acetate is mutually returned through acetic acid refining tower
Stream pump 31 is sent into 07 overhead reflux of acetic acid refining tower；The separation water of 30 lower part of acetic acid refining tower phase-splitter (contains a small amount of acetic acid isopropyl
Ester), after the collection of isopropyl acetate water phase pans 38, send isopropyl acetate recovery tower 08 to feed, it is different to recycle acetic acid therein
Propyl ester.Acetic acid refining tower 07 adopts 33 extraction finished product acetic acid of pump through acetic acid refining tower side by lower part side line, and tower bottoms is residue and coke
Oil is gone out to pump 34 transmitting systems by acetic acid refining tower reactor.The tower reactor heat source of acetic acid refining tower 07 is mentioned by acetic acid refining tower reboiler 32
For.
Isopropyl acetate recovery process unit: the separation water from acetic acid refining tower phase-splitter 30, through isopropyl acetate water
Phase pans 38 and isopropyl acetate recovery tower feed pump 39 send isopropyl acetate recovery tower 08 top-feed, to molten in separation water
The isopropyl acetate of solution recycles, which only sets stripping section, and tower overhead gas is after the condensation of isopropyl acetate recovery tower condenser 35, lime set
Into 36 split-phase of isopropyl acetate recovery tower phase-splitter, water phase send isopropyl acetate water phase pans 38, and oil is mutually by acetic acid isopropyl
Ester recovery tower distillates pump 37 and is sent into the oily phase side charging of acetic acid refining tower phase-splitter 30.The tower reactor heat source of isopropyl acetate recovery tower 08
It is provided by isopropyl acetate recycling tower reboiler 40, kettle draining is gone out to pump 41 transmitting systems by isopropyl acetate recycling tower reactor.
Embodiment 2
The anticorrosion process of methyl acetate hydrolysis and acetic acid refining, the technique mainly include that the methyl acetate worked continuously is dense
Contracting, methyl acetate full gear, methyl acetate hydrolysis, hydrolyzate separation and acetic acid refining and isopropyl acetate recycling.
Methyl acetate concentration technology unit includes following operation:
(1) 75% thick methyl acetate and methyl acetate hydrolysis workshop section from crude methyl acetate sub-unit are separated by hydrolyzate
The thick methyl acetate that column overhead gas phase distillates enters in extractive distillation column, carries out the separation of methyl acetate and methanol；
(2) 10 DEG C of extraction water, the methyl acetate volatilized from extracting rectifying column overhead are added to extracting rectifying top of tower
Steam is after condensation, collection, boosting, and for a portion methyl acetate from extractive distillation column overhead reflux, remaining is sent into de- acetaldehyde
Tower charging；Return flow/overhead extraction flow=1.4；
(3) methanol aqueous solution that extractive distillation column tower reactor generates, sends to refining methanol system and is recycled.
Methyl acetate full gear technique unit includes following operation:
(1) methyl acetate (the methyl acetate stream stock that extracting rectifying top of tower distillates and the gas phase impurities removal stream from hydrolysis tower
Stock) enter de- acetaldehyde tower progress vapour-liquid mass；
(2) steam that distillates of acetaldehyde tower top is taken off after condensation, collection, boosting, and a portion acetaldehyde is from de- acetaldehyde tower top
Portion's reflux, remaining acetaldehyde send to purification；Return flow/feed rate=1.3；
(3) hydrolysis tower top feed is sent into after the methyl acetate of tower reactor is boosted.
Hydrolysis process of methyl acetate unit includes following operation:
(1) by taking off the methyl acetate of acetaldehyde tower tower reactor outflow, into hydrolysis tower, steam is distillated through cold from hydrolysis tower top
After solidifying, collection, boosting, from hydrolysis tower overhead reflux, solidifying gas is sent into de- acetaldehyde tower as gas phase impurities removal stream stock and is fed；Reflux
Flow/feed rate=3.4；
(2) after inner-tower filling material section (packing section is equivalent to 8 pieces of theoretical cam curves) processing, from hydrolysis tower top side take-off
Methyl acetate mixes after boosted with methyl acetate hydrolysis water, feeding storng-acid cation exchange resin bed (feeding temperature 65~
75 DEG C) reaction is hydrolyzed, acetic acid and methanol are generated, after the shredded resin wherein carried secretly is removed by filtration in hydrolyzate, returns to water
The middle and lower part Xie Ta is separated；
Wherein, filtering uses the accurate filter using Nomex as filter medium, and filter medium thickness 30mm, filtering are situated between
Less than 1 μm, pressure drop is less than 0.1MPa in the aperture of matter；(3) hydrolysis tower tower reactor hydrolyzate (main group become acetic acid, methanol, water and
Methyl acetate) boosting after be sent into hydrolyzate knockout tower separated.
Hydrolyzate separating technology unit includes following operation:
(1) enter hydrolyzate knockout tower by the hydrolyzate that hydrolysis tower tower reactor flows out to be separated, overhead vapours partial gas phase
It is blown into extractive distillation column, rest part flows back after condensation, collection, boosting from hydrolyzate separation column, supplement reflux stream
Amount/feed rate=0.6；
(2) it is sent into acetic acid refining tower after the spirit of vinegar of hydrolyzate knockout tower tower reactor is boosted, carries out dehydration purification.
Acetic acid refining technique unit includes following operation:
(1) acetic acid refining tower is entered by the spirit of vinegar that hydrolyzate knockout tower tower reactor flows out, is made in tower using isopropyl acetate
Entrainer distillates the azeotropic mixture of water and isopropyl acetate from tower top, through condensation, after split-phase, obtain upper layer isopropyl acetate and
The separation water (containing a small amount of isopropyl acetate) of lower layer；
(2) reflux of acetic acid refining top of tower is sent into after the isopropyl acetate on upper layer is mutually boosted, the separation water of lower layer is (containing few
Measure isopropyl acetate) collect after, be sent into isopropyl acetate recovery tower；Return flow/feed rate=3.8；
(3) by acetic acid refining tower lower part side take-off acetic acid, the residue and tar transmitting system of tower reactor.
Isopropyl acetate recovery process unit includes following operation:
(1) from the separation water of acetic acid refining technique unit, into isopropyl acetate recovery tower, (recovery tower only sets stripping
Section) at the top of, tower overhead gas obtains water phase and oily phase through condensation, 45 DEG C of split-phases, collects water phase, and water phase is back to isopropyl acetate time
Top of tower is received, returns to acetic acid refining unit after oil is mutually boosted；
(2) transmitting system after the tower reactor draining of isopropyl acetate recovery tower is boosted.
Technique provided in this embodiment realizes the effective de- of the highly concentrated acetic acid corrosive impurity of aggravation under the conditions of low energy consumption
It removes, significant the problem of alleviating the corrosion of acetic acid refining process device, extends 4~5 times of the key equipment service life.Comparative example 1
The process flow of this comparative example is similar to Example 2, and difference is
(1) technological parameter is slightly different and (is shown in Table 1)；
(2) packing section is equivalent to 3 pieces of theoretical cam curves in hydrolysis tower；
(3) not set accurate filter.
The operating condition of capital equipment is shown in Table 1 in embodiment 2 and comparative example 1.
1. capital equipment operating condition of table
From embodiment 2 and comparative example 1: the theoretical cam curve and operating parameter of strict control hydrolysis tower packing section, it can
Enhance the removing ability of halogen impurities and aldehyde, specifically as F in hydrolysis column overhead charging-、Cl-It is respectively with acetaldehyde concentration
When 134ppm, 281ppm and 150ppm, F in kettle material is hydrolyzed in embodiment 2-And Cl-Concentration is respectively 7ppm and 2ppm, water
It is 1ppm that Xie Ta, which adopts side acetaldehyde concentration in material,.And F in kettle material is hydrolyzed in comparative example 1-、Cl-Concentration be respectively 30ppm
And 20ppm, it is 10ppm that acetaldehyde concentration in material is adopted in hydrolysis tower side.The setting of accurate filter can effectively filter hydrolyzate entrainment
Shredded resin, and then avoid shredded resin from entering acetic acid concentration systems and equipment caused to corrode, it is specifically accurate in embodiment 2
Resin content is 1000ppm in filter charging, and resin content is reduced to 1ppm in accurate filter discharging after filtering, accordingly
It is 1ppm that ground, which hydrolyzes resin concentration in tower reactor discharging,；And it hydrolyzes and is set in kettle material because of not set accurate filter in comparative example 1
Lipid concentration is 1000ppm.F in 1 hydrolyzate of comparative example-、Cl-It is apparently higher than embodiment 2 with resin concentration, illustrates skill of the present invention
Art measure achieves good beneficial effect.
More than, embodiments of the present invention are illustrated.But the present invention is not limited to above embodiment.It is all
Within the spirit and principles in the present invention, any modification, equivalent substitution, improvement and etc. done should be included in guarantor of the invention
Within the scope of shield.
Claims (10)
1. the anti-corrosive apparatus of methyl acetate hydrolysis and acetic acid refining during polyvinyl alcohol disposing mother liquor, which is characterized in that described
Anti-corrosive apparatus includes methyl acetate enrichment facility, methyl acetate full gear device, methyl acetate hydrolysis device, hydrolyzate separation dress
It sets, acetic acid refining device and isopropyl acetate recyclable device；
The methyl acetate enrichment facility includes extractive distillation column, and the methyl acetate full gear device includes de- acetaldehyde tower, described
Methyl acetate hydrolysis device includes hydrolysis tower, and the hydrolysis liquid separating apparatus includes hydrolyzate knockout tower, the acetic acid refining dress
It sets including acetic acid refining tower, the isopropyl acetate recyclable device includes isopropyl acetate recovery tower；
Preferably, the extractive distillation column, de- acetaldehyde tower, hydrolysis tower, hydrolyzate knockout tower, acetic acid refining tower and isopropyl acetate
Recovery tower is connected according to flow direction of material.
2. anti-corrosive apparatus according to claim 1, which is characterized in that the tower top of the extractive distillation column and de- acetaldehyde tower
Middle part connection, the tower reactor of the de- acetaldehyde tower and the tower top of hydrolysis tower connect, the tower reactor and hydrolyzate knockout tower of the hydrolysis tower
Middle part connection, the tower reactor of the hydrolyzate knockout tower connect with the middle part of acetic acid refining tower, the tower top of the acetic acid refining tower
It is connect with the tower top of isopropyl acetate recovery tower；
Wherein, the methyl acetate enrichment facility further includes extractive distillation column condenser, extractive distillation column return tank, extracting rectifying
Tower reflux pump, extracting rectifying tower reboiler；
Preferably, the tower top of the extractive distillation column can be with extractive distillation column condenser, extractive distillation column return tank, extraction essence
Tower reflux pump is evaporated to be sequentially connected with；The outlet of extractive distillation column reflux pump can be connect with extracting rectifying top of tower, and connecting line
It is upper that the branch connecting with de- acetaldehyde tower is set；
Preferably, extracting rectifying tower reboiler can be set in the tower reactor of the extractive distillation column；
Preferably, the tower reactor of the extractive distillation column can also be connect with refining methanol system；
Preferably, the methyl acetate enrichment facility can also include extraction water inlet and methyl acetate entrance, it is preferable that described
The tower top for extracting water inlet and extractive distillation column connects, and the middle part of the methyl acetate entrance and extractive distillation column connects.
3. anti-corrosive apparatus according to claim 1 or 2, which is characterized in that the methyl acetate full gear device further includes taking off
Acetaldehyde tower condenser, de- acetaldehyde tower return tank, de- acetaldehyde tower reflux pump, de- acetaldehyde tower reboiler, de- acetaldehyde tower reactor go out to pump；
The tower top of the de- acetaldehyde tower can be with de- acetaldehyde tower condenser, de- acetaldehyde tower return tank, de- acetaldehyde tower reflux pump sequentially
Connection；The outlet of de- acetaldehyde tower reflux pump can be connect with de- acetaldehyde top of tower, and connecting line is equipped with to refine with acetaldehyde and is
The branch of system connection；
De- acetaldehyde tower reboiler can be set in the tower reactor of the de- acetaldehyde tower；
The tower reactor of the de- acetaldehyde tower can go out pump, be sequentially connected at the top of hydrolysis tower with de- acetaldehyde tower reactor.
4. described in any item anti-corrosive apparatus according to claim 1~3, which is characterized in that the methyl acetate hydrolysis device is also
It is adopted including storng-acid cation exchange resin bed, hydrolysis tower condenser, hydrolysis tower return tank, hydrolysis tower reflux pump, hydrolysis tower side
Pump, hydrolysis tower reboiler, hydrolysis tower reactor go out to pump and accurate filter；
Preferably, the tower top of the hydrolysis tower can sequentially connect with hydrolysis tower condenser, hydrolysis tower return tank, hydrolysis tower reflux pump
It connects；The outlet of hydrolysis tower reflux pump can be connect with hydrolysis tower top；The hydrolysis tower condenser can also be with de- acetaldehyde tower
Middle part connection；
Preferably, the top side take-off mouth of the hydrolysis tower can adopt pump, storng-acid cation exchange resin with hydrolysis tower side
Bed, accurate filter are sequentially connected with, and are connect in the middle part of the outlet of accurate filter and hydrolysis tower；
Preferably, packing section can be set in the hydrolysis tower, packing section is located at the top of top side take-off mouth；
Preferably, the packing section is equivalent to 5~10 pieces of theoretical cam curves；
Preferably, hydrolysis tower reboiler can be set in the tower reactor of the hydrolysis tower；
Preferably, the tower reactor of the hydrolysis tower can go out pump, be sequentially connected in the middle part of hydrolyzate knockout tower with hydrolysis tower reactor；
Preferably, the methyl acetate hydrolysis device can also include methyl acetate hydrolysis water inlet, be arranged in de- acetaldehyde tower
On connecting line at the top of tower reactor and hydrolysis tower.
5. anti-corrosive apparatus according to any one of claims 1 to 4, which is characterized in that the hydrolysis liquid separating apparatus also wraps
Hydrolyzate knockout tower condenser, hydrolyzate knockout tower return tank, hydrolyzate knockout tower reflux pump, hydrolyzate knockout tower is included to boil again
Device, hydrolyzate separation tower reactor go out to pump；
Preferably, two branches can be set in the tower top of the hydrolyzate knockout tower, connect in the middle part of branch one and extractive distillation column,
Branch two is sequentially connected with hydrolyzate knockout tower condenser, hydrolyzate knockout tower return tank, hydrolyzate knockout tower reflux pump；Hydrolysis
The outlet of liquid knockout tower reflux pump is connect with the top of hydrolyzate knockout tower；
Preferably, hydrolyzate separation tower reboiler can be set in the tower reactor of the hydrolyzate knockout tower；
Preferably, the tower reactor of the hydrolyzate knockout tower can be separated with hydrolyzate tower reactor go out to pump, in the middle part of acetic acid refining tower sequentially
Connection.
6. described in any item anti-corrosive apparatus according to claim 1~5, which is characterized in that the acetic acid refining tower further includes vinegar
Acid treating tower condenser, acetic acid refining tower phase-splitter, acetic acid refining tower reflux pump, acetic acid refining tower reboiler, acetic acid refining tower
Pump is adopted in side, acetic acid refining tower reactor goes out to pump；
Preferably, the tower top of the acetic acid refining tower can sequentially connect with acetic acid refining tower condenser, acetic acid refining tower phase-splitter
It connects, the acetic acid refining tower phase-splitter can be equipped with outlet one and outlet two, outlet one and acetic acid refining tower reflux pump, acetic acid essence
Top of tower processed is sequentially connected with；
Preferably, the lower part side line outlet of the acetic acid refining tower can adopt pump connection with acetic acid refining tower side, produce acetic acid；
Preferably, acetic acid refining tower reboiler can be set in the tower reactor of the acetic acid refining tower；
Preferably, the tower reactor of the acetic acid refining tower can go out pump connection with acetic acid refining tower reactor, and residue and tar is discharged；
Preferably, the isopropyl acetate recyclable device further includes isopropyl acetate recovery tower condenser, isopropyl acetate recycling
Tower phase-splitter, isopropyl acetate recovery tower distillate pump, isopropyl acetate water phase pans, isopropyl acetate recovery tower feed pump,
Isopropyl acetate recycles tower reboiler, isopropyl acetate recycling tower reactor goes out to pump；
Preferably, the acetic acid refining tower phase-splitter can be equipped with oil mutually outlet and water phase outlet；
Preferably, the outlet two of the acetic acid refining tower phase-splitter can be with isopropyl acetate water phase pans, isopropyl acetate
It is sequentially connected at the top of recovery tower feed pump, isopropyl acetate recovery tower；
Preferably, the tower top of the isopropyl acetate recovery tower can be with isopropyl acetate recovery tower condenser, isopropyl acetate
Recovery tower phase-splitter is sequentially connected with；Mutually outlet, isopropyl acetate recovery tower distillate pump, vinegar to the oil of the acetic acid refining tower phase-splitter
Acid treating tower phase-splitter is sequentially connected with；The water phase outlet of the acetic acid refining tower phase-splitter can receive with isopropyl acetate water phase
Tank connection；
Preferably, isopropyl acetate recycling tower reboiler can be set in the tower reactor of the isopropyl acetate recovery tower；
Preferably, the tower reactor of the isopropyl acetate recovery tower can recycle tower reactor with isopropyl acetate and pump connection out, send out kettle
Draining.
7. the anticorrosion process of methyl acetate hydrolysis and acetic acid refining, which is characterized in that the technique is any using claim 1~6
The item anti-corrosive apparatus, the anticorrosion process mainly includes methyl acetate concentration, methyl acetate full gear, methyl acetate hydrolysis, water
Solve liquid separation and acetic acid refining and isopropyl acetate recycling.
8. anticorrosion process according to claim 7, which is characterized in that the methyl acetate concentration technology unit includes following
Operation:
(1) thick methyl acetate enters in extractive distillation column, carries out the separation of methyl acetate and methanol；
(2) to extracting rectifying top of tower be added extraction water, the methyl acetate steam volatilized from extracting rectifying column overhead through condensation,
It collects, after boosting, for a portion methyl acetate from extractive distillation column overhead reflux, remaining is sent into de- acetaldehyde tower charging；
(3) methanol aqueous solution that extractive distillation column tower reactor generates, sends to refining methanol system and is recycled；
Preferably, the source of above-mentioned thick methyl acetate includes thick methyl acetate and methyl acetate from crude methyl acetate sub-unit
The thick methyl acetate that hydrolysis workshop section is distillated by hydrolyzate knockout tower top gaseous phase；
Preferably, the temperature of above-mentioned extraction water is 2~15 DEG C；
Preferably, the operating parameter of the extractive distillation column are as follows: 0.085~0.15MPa of pressure, tower top temperature are 50~60 DEG C,
Bottom temperature is 75~85 DEG C, overhead reflux flow/overhead extraction flow=1.3~1.7；
Wherein, the methyl acetate full gear technique unit includes following operation:
(1) methyl acetate enters de- acetaldehyde tower progress vapour-liquid mass；
(2) after condensation, collection, boosting, a portion acetaldehyde returns the steam that de- acetaldehyde tower top distillates from de- acetaldehyde top of tower
Stream, remaining acetaldehyde send to purification；
(3) hydrolysis tower top feed is sent into after the methyl acetate of tower reactor is boosted；
Preferably, the methyl acetate in step (1) includes the methyl acetate stream stock and come from hydrolysis that extracting rectifying top of tower distillates
The gas phase impurities removal stream stock of tower；
Preferably, the operating parameter of the de- acetaldehyde tower are as follows: 0.085~0.15MPa of pressure, tower top temperature are 45~55 DEG C, tower
Kettle temperature degree is 50~60 DEG C, return flow/feed rate=1.2~1.7.
9. anticorrosion process according to claim 7 or 8, which is characterized in that the hydrolysis process of methyl acetate unit includes
It operates below:
(1) by taking off the methyl acetate of acetaldehyde tower tower reactor outflow, into hydrolysis tower, from hydrolysis tower at the top of distillate steam and condensed, received
After collection, boosting, from hydrolysis tower overhead reflux, not solidifying gas is sent into de- acetaldehyde tower charging as gas phase impurities removal stream stock；
(2) it from hydrolysis tower top side take-off methyl acetate, is mixed after boosted with methyl acetate hydrolysis water, is sent into highly acid sun
Reaction is hydrolyzed in ion exchange resin bed, generates acetic acid and the shredded resin wherein carried secretly is removed by filtration in methanol, hydrolyzate
Afterwards, hydrolysis tower middle and lower part is returned to be separated；
Preferably, the methyl acetate of above-mentioned hydrolysis tower top side take-off is, the packing section processed through inner-tower filling material section
It is equivalent to 5~10 pieces of theoretical cam curves；
Preferably, the operating parameter of the hydrolysis tower are as follows: 0.085~0.15MPa of pressure, tower top temperature are 55~65 DEG C, tower reactor
Temperature is 80~85 DEG C, 60~65 DEG C of temperature at side take-off, return flow/feed rate=3.3~4.2；
Preferably, above-mentioned filtering uses accurate filter, and the accurate filter makees filter medium, filter medium using Nomex
20~30mm of thickness, the aperture of filter medium is less than 1 μm；
Preferably, the operating condition of the accurate filter are as follows: pressure drop is less than 0.1MPa；
Preferably, the operating parameter of the storng-acid cation exchange resin bed are as follows: 65~75 DEG C of feeding temperature, such as 70 DEG C；
(3) hydrolyzate knockout tower is sent into after the hydrolyzate boosting of hydrolysis tower tower reactor to be separated；
Wherein, the hydrolyzate separating technology unit includes following operation:
(1) enter hydrolyzate knockout tower by the hydrolyzate that hydrolysis tower tower reactor flows out to be separated, overhead vapours partial gas phase is blown into
Extractive distillation column, rest part flow back after condensation, collection, boosting from hydrolyzate separation column；
(2) it is sent into acetic acid refining tower after the spirit of vinegar of hydrolyzate knockout tower tower reactor is boosted, carries out dehydration purification；
Preferably, the operating parameter of the hydrolyzate knockout tower are as follows: 0.085~0.15MPa of pressure, tower top temperature are 60~70
DEG C, bottom temperature is 110~115 DEG C, supplements regurgitant volume/feed rate=0.55~1.1.
10. according to the described in any item anticorrosion process of claim 7~9, which is characterized in that the acetic acid refining technique unit packet
Include following operation:
(1) acetic acid refining tower is entered by the spirit of vinegar that hydrolyzate knockout tower tower reactor flows out, distillates water and isopropyl acetate from tower top
Azeotropic mixture obtain the isopropyl acetate on upper layer and the separation water of lower layer through condensation, after split-phase (containing a small amount of isopropyl acetate)；
Preferably, entrainer is made using isopropyl acetate in acetic acid refining tower；
(2) reflux of acetic acid refining top of tower is sent into after the isopropyl acetate on upper layer is mutually boosted, the separation water of lower layer (contains a small amount of vinegar
Isopropyl propionate) collect after, be sent into isopropyl acetate recovery tower；
(3) by acetic acid refining tower lower part side take-off acetic acid, the residue and tar transmitting system of tower reactor；
Preferably, the operating parameter of the acetic acid refining tower are as follows: 0.085~0.15MPa of pressure, tower top temperature are 70~80 DEG C,
Bottom temperature is 120~125 DEG C, 120~125 DEG C of lower part side take-off temperature, return flow/feed rate=3.7~4.2；
Wherein, the isopropyl acetate recovery process unit includes following operation:
(1) from the separation water of acetic acid refining technique unit, at the top of isopropyl acetate recovery tower, tower overhead gas is condensed, is divided
Phase obtains water phase and oily phase, collects water phase, and water phase is back at the top of isopropyl acetate recovery tower, returns to vinegar after oil is mutually boosted
Acid treating unit；
(2) transmitting system after the tower reactor draining of isopropyl acetate recovery tower is boosted；
Preferably, the operating parameter of the isopropyl acetate recovery tower are as follows: 0.085~0.15MPa of pressure, tower top temperature be 90~
100 DEG C, bottom temperature is 95~103 DEG C；
Preferably, the operation temperature of the split-phase is 35~45 DEG C.
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|---|---|---|---|
| CN201810880270.4A CN109467499A (en) | 2018-08-03 | 2018-08-03 | The anticorrosion process and device of methyl acetate hydrolysis and acetic acid refining during polyvinyl alcohol disposing mother liquor |
| PCT/CN2019/098010 WO2020024886A1 (en) | 2018-08-03 | 2019-07-26 | Anti-corrosive process and device for methyl acetate hydrolysis and acetic acid refining in polyvinyl alcohol mother liquor recovery process |
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| CN201810880270.4A CN109467499A (en) | 2018-08-03 | 2018-08-03 | The anticorrosion process and device of methyl acetate hydrolysis and acetic acid refining during polyvinyl alcohol disposing mother liquor |
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Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN87106904A (en) * | 1986-10-14 | 1988-07-20 | 赫希斯特人造丝公司 | Remove the process for regenerating carbonylation catalyst solution of corrosion metals |
| CN1150583A (en) * | 1995-09-29 | 1997-05-28 | 昭和电工株式会社 | Process for purifying acetic acid |
| CN101186575A (en) * | 2007-12-04 | 2008-05-28 | 南京工业大学 | Methyl acetate catalytic rectification hydrolysis process |
| CN101306981A (en) * | 2007-05-16 | 2008-11-19 | 中国石油化工股份有限公司 | Azeotropy process for catalyzing, rectifying and hydrolyzing methyl acetate |
| CN101910104A (en) * | 2007-10-30 | 2010-12-08 | 塞拉尼斯国际公司 | Acetaldehyde removal from methyl acetate by distillation at elevated pressure |
| CN102757342A (en) * | 2012-07-19 | 2012-10-31 | 安徽皖维高新材料股份有限公司 | Method for purifying by-product methyl acetate generated during production of PVA (polyvinyl acetate) |
| CN102766044A (en) * | 2012-08-07 | 2012-11-07 | 天津凯赛特科技有限公司 | Reaction and rectification system and method for recycling acetic acid from diluted acetic acid solution |
| CN107011169A (en) * | 2017-04-25 | 2017-08-04 | 天津大学 | A kind of process for purification and device of the vinyl acetate of acetylene method synthesis |
| CN110049963A (en) * | 2017-01-18 | 2019-07-23 | 株式会社大赛璐 | The preparation method of acetic acid |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2010017624A1 (en) * | 2008-08-13 | 2010-02-18 | Kuang-Yeu Wu | Process and apparatus for recovery of acetic acid from a feed stream containing the corresponding ester |
| CN102190556A (en) * | 2010-03-03 | 2011-09-21 | 中国石油化工股份有限公司 | Method for hydrolyzing methyl acetate |
| CN106542990A (en) * | 2016-10-13 | 2017-03-29 | 中石化南京工程有限公司 | A kind of method and system of the recovery of acetic acid from aqueous acetic acid |
-
2018
- 2018-08-03 CN CN201810880270.4A patent/CN109467499A/en active Pending
-
2019
- 2019-07-26 WO PCT/CN2019/098010 patent/WO2020024886A1/en active Application Filing
Patent Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN87106904A (en) * | 1986-10-14 | 1988-07-20 | 赫希斯特人造丝公司 | Remove the process for regenerating carbonylation catalyst solution of corrosion metals |
| CN1150583A (en) * | 1995-09-29 | 1997-05-28 | 昭和电工株式会社 | Process for purifying acetic acid |
| CN101306981A (en) * | 2007-05-16 | 2008-11-19 | 中国石油化工股份有限公司 | Azeotropy process for catalyzing, rectifying and hydrolyzing methyl acetate |
| CN101910104A (en) * | 2007-10-30 | 2010-12-08 | 塞拉尼斯国际公司 | Acetaldehyde removal from methyl acetate by distillation at elevated pressure |
| CN101186575A (en) * | 2007-12-04 | 2008-05-28 | 南京工业大学 | Methyl acetate catalytic rectification hydrolysis process |
| CN102757342A (en) * | 2012-07-19 | 2012-10-31 | 安徽皖维高新材料股份有限公司 | Method for purifying by-product methyl acetate generated during production of PVA (polyvinyl acetate) |
| CN102766044A (en) * | 2012-08-07 | 2012-11-07 | 天津凯赛特科技有限公司 | Reaction and rectification system and method for recycling acetic acid from diluted acetic acid solution |
| CN110049963A (en) * | 2017-01-18 | 2019-07-23 | 株式会社大赛璐 | The preparation method of acetic acid |
| CN107011169A (en) * | 2017-04-25 | 2017-08-04 | 天津大学 | A kind of process for purification and device of the vinyl acetate of acetylene method synthesis |
Non-Patent Citations (1)
| Title |
|---|
| V.R.普路德克: "《腐蚀控制与设计》", 28 February 1983, 石油工业出版社, pages: 269 * |
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