CN101186575A - Methyl acetate catalytic rectification hydrolysis process - Google Patents
Methyl acetate catalytic rectification hydrolysis process Download PDFInfo
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- CN101186575A CN101186575A CNA2007101910076A CN200710191007A CN101186575A CN 101186575 A CN101186575 A CN 101186575A CN A2007101910076 A CNA2007101910076 A CN A2007101910076A CN 200710191007 A CN200710191007 A CN 200710191007A CN 101186575 A CN101186575 A CN 101186575A
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- 230000003197 catalytic effect Effects 0.000 title claims abstract description 34
- 238000006460 hydrolysis reaction Methods 0.000 title claims abstract description 22
- 230000007062 hydrolysis Effects 0.000 title claims abstract description 21
- 238000000034 method Methods 0.000 title claims abstract description 21
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 title claims abstract description 15
- KXKVLQRXCPHEJC-UHFFFAOYSA-N acetic acid trimethyl ester Natural products COC(C)=O KXKVLQRXCPHEJC-UHFFFAOYSA-N 0.000 title claims abstract description 15
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 81
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims abstract description 66
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 39
- 238000006243 chemical reaction Methods 0.000 claims abstract description 30
- 238000007599 discharging Methods 0.000 claims abstract description 11
- 238000004519 manufacturing process Methods 0.000 claims abstract description 11
- 238000004821 distillation Methods 0.000 claims abstract description 8
- JUMYIBMBTDDLNG-OJERSXHUSA-N hydron;methyl (2r)-2-phenyl-2-[(2r)-piperidin-2-yl]acetate;chloride Chemical compound Cl.C([C@@H]1[C@H](C(=O)OC)C=2C=CC=CC=2)CCCN1 JUMYIBMBTDDLNG-OJERSXHUSA-N 0.000 claims description 46
- 229940099204 ritalin Drugs 0.000 claims description 46
- 238000010992 reflux Methods 0.000 claims description 21
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims description 13
- 238000005516 engineering process Methods 0.000 claims description 12
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 11
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 11
- 241000282326 Felis catus Species 0.000 claims description 9
- 239000000047 product Substances 0.000 claims description 8
- 238000006555 catalytic reaction Methods 0.000 claims description 7
- 239000006227 byproduct Substances 0.000 claims description 5
- 238000011049 filling Methods 0.000 claims description 4
- 230000002378 acidificating effect Effects 0.000 claims description 2
- 238000005341 cation exchange Methods 0.000 claims description 2
- 239000002994 raw material Substances 0.000 claims description 2
- 230000003245 working effect Effects 0.000 claims description 2
- 239000000463 material Substances 0.000 abstract description 15
- 238000000926 separation method Methods 0.000 abstract description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 abstract description 6
- 238000005265 energy consumption Methods 0.000 abstract description 4
- 239000002253 acid Substances 0.000 abstract 1
- 239000000945 filler Substances 0.000 description 5
- -1 Dichlorodiphenyl Acetate methyl esters Chemical class 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 238000006136 alcoholysis reaction Methods 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 150000002148 esters Chemical class 0.000 description 3
- 238000000895 extractive distillation Methods 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 description 2
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 2
- 150000001733 carboxylic acid esters Chemical class 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 229920001429 chelating resin Polymers 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- 239000000413 hydrolysate Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 235000005135 Micromeria juliana Nutrition 0.000 description 1
- 241000246354 Satureja Species 0.000 description 1
- 235000007315 Satureja hortensis Nutrition 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 150000007942 carboxylates Chemical group 0.000 description 1
- 239000003729 cation exchange resin Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 239000003456 ion exchange resin Substances 0.000 description 1
- 229920003303 ion-exchange polymer Polymers 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 239000012452 mother liquor Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 238000000066 reactive distillation Methods 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 239000003039 volatile agent Substances 0.000 description 1
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/10—Process efficiency
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a methyl acetate catalytic rectification hydrolysis process, which adopts a catalytic rectification tower, an acid removal tower and an alcohol removal tower three-tower process. It comprises the following steps: A. the catalytic rectifying tower is divided into a rectifying section, a reaction section and a stripping section from top to bottom, water enters from the top of the reaction section, methyl acetate enters from the bottom of the reaction section, the top of the catalytic rectifying tower discharges methanol, methyl acetate and a small amount of water, and the bottom of the tower discharges acetic acid and water; B. b, feeding the tower top material of the catalytic distillation tower in the step A into a dealcoholization tower for separation, obtaining a product methanol at the tower bottom of the dealcoholization tower, and returning unreacted methyl acetate, a small amount of water and methanol at the tower top to the catalytic distillation tower for circular reaction; and D, discharging the tower kettle in the step A, feeding the discharged material into a deacidification tower for separation, and obtaining a product acetic acid at the tower kettle of the deacidification tower. The invention can reduce the equipment investment, reduce the operation energy consumption and the operation difficulty, thereby reducing the production cost.
Description
Technical field
The present invention relates to a kind of methyl acetate catalysis rectification hydrolysis technique.
Background technology
Ritalin is a kind of common Chemical Manufacture by product, colourless transparent liquid, savory, be slightly soluble in water, be soluble in most of organic solvents such as ethanol, 56.9 ℃ of boiling points, density are 0.932g/ml, generally appear in the Industrial processes of pure terephthalic acid (PTA) and polyvinyl alcohol (PVA).
In the PTA production process, what adopt at present is high-temperature oxidation mostly, and this technology is solvent with acetic acid, is oxygenant with the air that PTA is produced in the reaction of liquid phase high temperature oxidation, and this technology accounts for more than 90% of present PTA production.In the side reaction that acetic acid takes place, about 75% acetic acid generates CO, CO
2And water, 25% generates ritalin etc.PVA also is a kind of very important and common Chemicals, and during industrial synthetic PVA, owing to PVA can not be got by the monomer direct polymerization, so what adopt mostly is technology by the Vinyl Acetate Copolymer alcoholysis, the alcohol that wherein is used for alcoholysis is generally methyl alcohol.The alcoholysis under catalyst action of Vinyl Acetate Copolymer solution generates PVA and a large amount of pure hydrolysis mother liquors, contains a large amount of ritalin by products in the pure hydrolysis mother liquor, is about 1.7 times of PVA by weight approximately.
At the processing of ritalin, in PTA produces, generally it is recycled in the oxidation reactor and is used; In PVA produces, generally be hydrolyzed and generate acetic acid and methyl alcohol.Because acetic acid and methyl alcohol are important chemical material, compare with ritalin, marketable value is higher, therefore, the processing that is hydrolyzed of Dichlorodiphenyl Acetate methyl esters not only can solve the recycling problem of ritalin by product, also can be other chemical industry dirt product important material, remarkable in economical benefits are provided.
In recent years, the hydrolysis treatment of Dichlorodiphenyl Acetate methyl esters has been carried out a large amount of research both at home and abroad.CN1333204A utilizes water and ritalin in the reactor that possesses the fixed catalytic layer behind the hydrolysis reaction, enter in the ritalin knockout tower, ritalin knockout tower cat head is unreacted ritalin, Returning reactor after the condensation, the tower still is acetic acid, methyl alcohol and less water, deliver to recovery tower, separating acetic acid and methyl alcohol.But adopt reactor hydrolysis ritalin in this technology, hydrolysis conversion is lower.The methyl acetate catalysis rectification hydrolysis technique of reports such as CN1927792A comprises catalytic rectifying tower, extractive distillation column, dealcoholize column, takes off ester tower and extracting tower.All materials of catalytic rectifying tower are only from the discharging of tower still, tower still water content is higher, because water and ritalin, ritalin and methyl alcohol can form azeotrope, separation difficulty must and be taken off the ester tower and ritalin, water and methyl alcohol could be separated fully through extractive distillation column, dealcoholize column.Because all materials of catalytic rectifying tower are only in the discharging of tower still, not discharging of cat head, thus make the later separation difficulty increase, flow process is tediously long, equipment cost increases, energy consumption is higher.CN101012162A Dichlorodiphenyl Acetate methyl esters hydrolysate tripping device is studied, comprise acetic acid separated tower, ritalin extraction tower, methyl alcohol knockout tower, packing tower all adopts regular packed tower, filler is the metal corrugated plate filler, because there are defectives such as flow process is tediously long, equipment cost is high, energy consumption height in all materials of catalytic rectifying tower equally only in the discharging of tower still.CN1213014C has introduced the method that is obtained carboxylic acid and alcohol by corresponding carboxylic acid ester and water hydrolysis.The fluid that contains carboxylicesters enters into pre-reactor, react with water under the first hydrolyst effect, part reacts, and resulting hydrolysate enters into reactive distillation column again, under the second hydrolyst effect, remaining carboxylate moiety is converted into carboxylic acid and alcohol.More volatile compound is derived from the reaction distillation top of tower as top stream, and more difficult evaporable compound is collected as bottom fraction at the reaction distillation tower bottom, but its not the whole technological process of Dichlorodiphenyl Acetate methyl esters hydrolysis study.
Summary of the invention
The objective of the invention is deficiency, a kind of methyl acetate catalysis rectification hydrolysis technique is provided at existing hydrolysis process of methyl acetate.
Technical scheme of the present invention: a kind of methyl acetate catalysis rectification hydrolysis technique, adopt catalytic rectifying tower T1, dealcoholize column T2 and extracting tower T3 three-column process flow technology, its concrete steps are as follows:
A: catalytic rectifying tower T1 is divided into rectifying section, conversion zone and stripping section from top to down, and water enters from the conversion zone top, and ritalin enters from the conversion zone bottom, and the discharging of catalytic distillation column overhead is methyl alcohol, ritalin and less water, and the discharging of tower still is acetic acid and water;
B: the overhead product of catalytic rectifying tower T1 is introduced dealcoholize column T2 and is separated, and dealcoholysis Tata still obtains methyl alcohol, and cat head is unreacted ritalin and less water, methyl alcohol, returns the catalytic rectifying tower circulating reaction again; The tower kettle product of catalytic rectifying tower T1 is introduced extracting tower T3 and is separated, and depickling Tata still obtains acetic acid, and cat head is a water.
Wherein said ritalin generally is the by product that produces in pure terephthalic acid or the polyvinyl alcohol production process.
The water among the above-mentioned steps A and the raw materials components mole ratio of ritalin are (1～10): 1, reflux ratio is (1～8): 1, the ritalin superficial velocity be 0.1～1 cubic metre/(cubic meter reaction zone volume hour), the catalyzer of filling in the conversion zone is a strongly acidic cation-exchange, 1～2 year work-ing life of catalyzer.
Reflux ratio is (0.5～5) among the preferred dealcoholize column T2: 1, and stage number 20～60; Reflux ratio is (3～10) among the preferred extracting tower T3: 1, and stage number 30～100.
The present invention is described in further detail below in conjunction with accompanying drawing.
Catalytic rectifying tower T1 is divided into three parts: upper rectifying section 1, intermediate reaction section 2, bottom stripping section 3, wherein filler is the metal corrugated plate filler in rectifying section and the stripping section, conversion zone filling male ion-exchange resin catalyzer is tied up bag, and described catalyzer is generally selected macroporous network type or gel type cation exchange resin catalyst.Dealcoholize column and depickling inner-tower filling material are the metal corrugated plate filler.
Material water autoreaction section top enters catalytic rectifying tower T1, and ritalin autoreaction section bottom enters, and after the conversion zone reaction, part generates acetic acid and methyl alcohol.Ritalin, water, acetic acid and methyl alcohol are after rectifying separation, and methyl alcohol, ritalin and less water are discharged from the T1 cat head, after the condenser cooling, and partial reflux, part enters dealcoholize column T2; Heavy constituent acetic acid and water are discharged from T1 tower still, enter extracting tower T3.
After material C entered dealcoholize column T2, after rectifying separation, cat head was unreacted ritalin and less water, methyl alcohol, after the condenser cooling, and partial reflux, part is returned catalytic rectifying tower T1 as material E and is continued circulating reaction; Tower still product methyl alcohol is discharged as material F.
After material D entered extracting tower T3, after rectifying separation, cat head was a water, after the condenser cooling, and partial reflux, part is discharged as material G; Tower still product acetic acid is discharged as material H.
Beneficial effect
(1) because the present invention adopts catalytic rectifying tower, extracting tower and dealcoholize column three-column process flow technology, more existing catalytic rectifying tower, extractive distillation column (or extraction tower), dealcoholize column and take off ester tower four-column process flow technology, flow process shortens, and equipment reduces.Compare with existing hydrolysis process, on the basis that guarantees the methyl acetate hydrolysis quality product, the present invention can reduce facility investment, reduces operation energy consumption and operation easier, thereby reduces production costs.
(2) under the operational condition of optimizing, the ritalin total conversion rate reaches more than 98%, and methyl alcohol and acetic acid mass concentration are respectively 99.9% and 95.0%, satisfies the specification of quality of PTA production to solvent acetic acid and fuel methanol substantially.
(3) hydrolysis process of methyl acetate proposed by the invention is not only applicable to the ritalin that produces in PTA and the polyvinyl alcohol production process, is applicable to the ritalin that produces in other production process yet.
Description of drawings
Fig. 1 is a methyl acetate catalysis rectification hydrolysis technique schematic flow sheet provided by the invention;
Wherein, T1 is a catalytic rectifying tower, and T2 is a dealcoholize column, and T3 is an extracting tower; 1 is the catalytic rectifying tower rectifying section, and 2 is the catalytic rectifying tower conversion zone, and 3 is the catalytic rectifying tower stripping section, and 4 is condenser, and 5 is reboiler; A is a feed water, and B is the charging ritalin, and C is the discharging of catalytic distillation column overhead, and D is the discharging of catalytic distillation Tata still, and E is unreacted ritalin and less water, methyl alcohol, and F is a methyl alcohol, and G is a water, and H is an acetic acid.
Embodiment
Concrete application of the present invention is described by the following examples, but range of application of the present invention is not subjected to the restriction of the following example.
Water and ritalin enter reactor in table 1 ratio, implement the hydrolysis of ritalin, among the embodiment 1, water and ritalin mol ratio are 2 among the T1, reflux ratio is 2, the ritalin superficial velocity be 0.2 cubic metre/(cubic meter reaction zone volume hour), catalyzer is a D002 type Zeo-karb; The T2 reflux ratio is 5; The T3 reflux ratio is 8.
Among the embodiment 2, water and ritalin mol ratio are 8 among the T1, and reflux ratio is 4, the ritalin superficial velocity be 0.6 cubic metre/(cubic meter reaction zone volume hour), catalyzer is an Amberlyst 35wet type Zeo-karb; The T2 reflux ratio is 3; The T3 reflux ratio is 5.
Among the embodiment 3, water and ritalin mol ratio are 4 among the T1, and reflux ratio is 7, the ritalin superficial velocity be 0.9 cubic metre/(cubic meter reaction zone volume hour), catalyzer is a D002 type Zeo-karb; The T2 reflux ratio is 1; The T3 reflux ratio is 4.
Table 1
| Detailed | Example 1 | Example 2 | Example 3 |
| Water and ritalin mol ratio among the |
2 | 8 | 4 |
| The |
2 | 4 | 7 |
| Ritalin superficial velocity among the T1 | 0.2 | 0.6 | 0.9 |
| The T1 catalyzer | D002 type Zeo-karb | Amberlyst 35wet type Zeo-karb | D002 type Zeo-karb |
| The |
5 | 3 | 1 |
| The T2 stage number | 20 | 32 | 50 |
| The T3 reflux ratio | 8 | 5 | 4 |
| The T3 stage number | 32 | 45 | 70 |
| Methanol quality concentration/% | 99.9 | 99.9 | 99.7 |
| Quality concentration/% | 99.9 | 99.9 | 99.9 |
| Acetic acid mass concentration/% | 96.4 | 95.8 | 95.1 |
Claims (5)
1. methyl acetate catalysis rectification hydrolysis technique, its concrete steps are as follows:
A: catalytic rectifying tower T1 is divided into rectifying section, conversion zone and stripping section from top to down, and water enters from the conversion zone top, and ritalin enters from the conversion zone bottom, and the discharging of catalytic distillation column overhead is methyl alcohol, ritalin and less water, and the discharging of tower still is acetic acid and water;
B: the overhead product of catalytic rectifying tower T1 is introduced dealcoholize column T2 and is separated, and dealcoholysis Tata still obtains methyl alcohol, and cat head is unreacted ritalin and less water, methyl alcohol, returns the catalytic rectifying tower circulating reaction again; The tower kettle product of catalytic rectifying tower T1 is introduced extracting tower T3 and is separated, and depickling Tata still obtains acetic acid, and cat head is a water.
2. technology according to claim 1 is characterized in that described ritalin is the by product that produces in pure terephthalic acid or the polyvinyl alcohol production process.
3. technology according to claim 1 is characterized in that the raw materials components mole ratio of water in the steps A and ritalin is (1～10): 1, reflux ratio be (1～8): 1, the ritalin superficial velocity be 0.1～1 cubic metre/(cubic metre reaction zone volume hour); The catalyzer of filling in the conversion zone is a strongly acidic cation-exchange, 1～2 year work-ing life of catalyzer.
4. technology according to claim 1 is characterized in that reflux ratio is (0.5～5) among the dealcoholize column T2: 1, and stage number 20～60.
5. technology according to claim 1 is characterized in that reflux ratio is (3～10) among the extracting tower T3: 1, and stage number 30～100.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2007101910076A CN101186575B (en) | 2007-12-04 | 2007-12-04 | Methyl acetate catalytic rectification hydrolysis process |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2007101910076A CN101186575B (en) | 2007-12-04 | 2007-12-04 | Methyl acetate catalytic rectification hydrolysis process |
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| CN101186575A true CN101186575A (en) | 2008-05-28 |
| CN101186575B CN101186575B (en) | 2010-04-14 |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102179059A (en) * | 2011-02-24 | 2011-09-14 | 中国石油大学(华东) | Hydrolysis separation device of methyl acetate and process method thereof |
| CN101481304B (en) * | 2009-02-20 | 2012-07-04 | 南京工业大学 | Process for preparing formic acid by hydrolyzing methyl formate |
| WO2012164573A2 (en) | 2011-05-27 | 2012-12-06 | Reliance Industries Ltd., | Hydrolysis and esterification with acid catalysts |
| CN101792386B (en) * | 2010-02-04 | 2013-04-10 | 南京工业大学 | Method for treating solvent and by-product in aromatic carboxylic acid production |
| CN109467497A (en) * | 2018-08-03 | 2019-03-15 | 内蒙古蒙维科技有限公司 | A kind of recovery process and device of polyvinyl alcohol alcohol hydrolysis mother liquor |
| CN109467499A (en) * | 2018-08-03 | 2019-03-15 | 天津大学 | The anticorrosion process and device of methyl acetate hydrolysis and acetic acid refining during polyvinyl alcohol disposing mother liquor |
| CN114014755A (en) * | 2021-12-07 | 2022-02-08 | 江苏省瑞丰高分子材料有限公司 | Organic chemical methyl acetate and production process thereof |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1213014C (en) * | 1999-10-13 | 2005-08-03 | 苏舍化学技术有限公司 | Process and devices for hydrolytically obtaining carboxylic acid and alcohol from corresponding carboxylate |
| CN1752060A (en) * | 2005-10-24 | 2006-03-29 | 福州大学 | Recovery method of byproduct methyl acetate in paraphthalic acid production |
-
2007
- 2007-12-04 CN CN2007101910076A patent/CN101186575B/en active Active
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101481304B (en) * | 2009-02-20 | 2012-07-04 | 南京工业大学 | Process for preparing formic acid by hydrolyzing methyl formate |
| CN101792386B (en) * | 2010-02-04 | 2013-04-10 | 南京工业大学 | Method for treating solvent and by-product in aromatic carboxylic acid production |
| CN102179059A (en) * | 2011-02-24 | 2011-09-14 | 中国石油大学(华东) | Hydrolysis separation device of methyl acetate and process method thereof |
| WO2012164573A2 (en) | 2011-05-27 | 2012-12-06 | Reliance Industries Ltd., | Hydrolysis and esterification with acid catalysts |
| CN109467497A (en) * | 2018-08-03 | 2019-03-15 | 内蒙古蒙维科技有限公司 | A kind of recovery process and device of polyvinyl alcohol alcohol hydrolysis mother liquor |
| CN109467499A (en) * | 2018-08-03 | 2019-03-15 | 天津大学 | The anticorrosion process and device of methyl acetate hydrolysis and acetic acid refining during polyvinyl alcohol disposing mother liquor |
| CN109467497B (en) * | 2018-08-03 | 2023-11-10 | 内蒙古蒙维科技有限公司 | Recovery process and device for polyvinyl alcohol alcoholysis mother liquor |
| CN114014755A (en) * | 2021-12-07 | 2022-02-08 | 江苏省瑞丰高分子材料有限公司 | Organic chemical methyl acetate and production process thereof |
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| CN101186575B (en) | 2010-04-14 |
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