CN101481293A - A catalytic hydrolysis process of by-product methyl acetate in the production of purified terephthalic acid - Google Patents
A catalytic hydrolysis process of by-product methyl acetate in the production of purified terephthalic acid Download PDFInfo
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- CN101481293A CN101481293A CNA2009100245845A CN200910024584A CN101481293A CN 101481293 A CN101481293 A CN 101481293A CN A2009100245845 A CNA2009100245845 A CN A2009100245845A CN 200910024584 A CN200910024584 A CN 200910024584A CN 101481293 A CN101481293 A CN 101481293A
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- 238000006460 hydrolysis reaction Methods 0.000 title claims abstract description 29
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 title claims abstract description 28
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 title claims abstract description 25
- KXKVLQRXCPHEJC-UHFFFAOYSA-N acetic acid trimethyl ester Natural products COC(C)=O KXKVLQRXCPHEJC-UHFFFAOYSA-N 0.000 title claims abstract description 25
- 230000007062 hydrolysis Effects 0.000 title claims abstract description 25
- 238000000034 method Methods 0.000 title claims abstract description 20
- 230000003197 catalytic effect Effects 0.000 title claims abstract description 19
- 239000006227 byproduct Substances 0.000 title claims abstract description 12
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 8
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 96
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims abstract description 75
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 49
- 238000006243 chemical reaction Methods 0.000 claims abstract description 40
- 239000011259 mixed solution Substances 0.000 claims abstract description 15
- 239000000203 mixture Substances 0.000 claims abstract description 3
- 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 33
- 229940099204 ritalin Drugs 0.000 claims description 33
- 238000010992 reflux Methods 0.000 claims description 16
- 238000007599 discharging Methods 0.000 claims description 13
- 238000004821 distillation Methods 0.000 claims description 12
- 238000005516 engineering process Methods 0.000 claims description 10
- 239000000243 solution Substances 0.000 claims description 10
- 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 8
- 239000002253 acid Substances 0.000 claims description 8
- 239000003729 cation exchange resin Substances 0.000 claims description 8
- 241000282326 Felis catus Species 0.000 claims description 7
- 239000002994 raw material Substances 0.000 claims description 5
- 239000003054 catalyst Substances 0.000 claims description 4
- 239000000376 reactant Substances 0.000 abstract description 4
- 238000000926 separation method Methods 0.000 abstract description 3
- 238000010168 coupling process Methods 0.000 abstract description 2
- 238000005265 energy consumption Methods 0.000 abstract description 2
- 238000011084 recovery Methods 0.000 abstract description 2
- 239000000463 material Substances 0.000 description 9
- 238000000605 extraction Methods 0.000 description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- 150000002148 esters Chemical class 0.000 description 4
- 238000011049 filling Methods 0.000 description 4
- 238000000895 extractive distillation Methods 0.000 description 3
- 238000000066 reactive distillation Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 238000006555 catalytic reaction Methods 0.000 description 2
- 239000000945 filler Substances 0.000 description 2
- 229910021645 metal ion Inorganic materials 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- -1 Dichlorodiphenyl Acetate methyl esters Chemical class 0.000 description 1
- URLKBWYHVLBVBO-UHFFFAOYSA-N Para-Xylene Chemical compound CC1=CC=C(C)C=C1 URLKBWYHVLBVBO-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 238000011027 product recovery Methods 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 238000004904 shortening Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 230000003245 working effect Effects 0.000 description 1
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Abstract
本发明公开了一种精对苯二甲酸生产中副产物醋酸甲酯的催化水解工艺，采用固定床反应器与萃取—催化精馏塔耦合工艺，醋酸甲酯与水混合首先进入固定床反应器进行水解反应；水解液进入萃取—催化精馏塔，该塔由上至下分为萃取—精馏段、反应段、提馏段，未水解的醋酸甲酯与萃取—催化精馏塔顶部加入的水在该塔反应段反应，水作为反应物也作为醋酸甲酯与甲醇共沸物分离的萃取剂，塔顶馏出未反应的醋酸甲酯与少量的水循环至固定床反应器，塔釜得到水、醋酸和甲醇混合液；该混合液进入甲醇回收塔，塔顶馏出甲醇，塔釜采出醋酸与水混合物。本发明可使醋酸甲酯水解率达到50.0％至99.9％，同时可以降低设备投资、能耗和操作难度。
The invention discloses a catalytic hydrolysis process of methyl acetate, a by-product in the production of purified terephthalic acid, which adopts a coupling process between a fixed bed reactor and an extraction-catalytic rectification tower, and the methyl acetate mixed with water first enters the fixed bed reactor The hydrolysis reaction is carried out; the hydrolyzate enters the extraction-catalytic rectification tower, which is divided into extraction-rectification section, reaction section and stripping section from top to bottom, and unhydrolyzed methyl acetate is added to the top of the extraction-catalytic rectification tower The water reacts in the reaction section of the tower, and water is used as a reactant and also as an extractant for the separation of methyl acetate and methanol azeotrope. The unreacted methyl acetate and a small amount of water are distilled from the top of the tower and circulated to the fixed-bed reactor. A mixed solution of water, acetic acid and methanol is obtained; the mixed solution enters the methanol recovery tower, methanol is distilled from the top of the tower, and a mixture of acetic acid and water is extracted from the tower still. The invention can make the hydrolysis rate of methyl acetate reach 50.0% to 99.9%, and can reduce equipment investment, energy consumption and operation difficulty at the same time.
Description
Technical field
The present invention relates to catalytic hydrolysis process for by-product methyl acetate in a kind of pure terephthalic acid's production.
Background technology
In pure terephthalic acid (PTA) production process, what adopt at present mostly is the liquid phase high-temperature oxidation, this technology is raw material with the p-Xylol, acetic acid is solvent, wherein acetic acid incomplete combustion generation ritalin is one of main side reaction, and this is the big and higher major cause of PTA production cost of acetic acid consumption amount.PTA manufacturer generally is recycled to ritalin in the oxidation reactor at present, to suppress the generation of ritalin, reduce the consumption of acetic acid, but this can not fundamentally solve the recycling problem of by-product methyl acetate.And methyl acetate hydrolysis is generated acetic acid and methyl alcohol, not only can solve the ritalin by-product recovery and utilize problem, and can provide important chemical material for Chemical Manufacture, acetic acid can be used as the raw material continuation recycle that PTA produces, and methyl alcohol also is important chemical material.The hydrolysis process of methyl acetate of domestic and foreign current mainly adopts exchange resin catalyzed hydrolysis process of fixed bed cation and reactive distillation catalytic hydrolysis process at present.
In recent years, Dichlorodiphenyl Acetate methyl esters catalytic hydrolysis has carried out a large amount of research both at home and abroad.CN1171174A has reported the method for ritalin reactive distillation hydrolysis system acetic acid and methyl alcohol, this reaction and rectification device comprises rectifying section, conversion zone and stripping section, under high water to ester ratio and high reflux ratio, the discharging of tower still, the methyl acetate hydrolysis rate reaches more than 99.5%, but the tower bottoms water content that this method for hydrolysis obtains is higher.The methyl acetate catalysis hydrolysis process of CN1927792A report comprises catalytic rectifying tower, hydrolyzed solution knockout tower, extractive distillation column, methanol rectifying tower, and wherein dilute acetic acid is delivered to the acetic acid concentration tower and carried dense.Because this technology catalytic distillation column overhead adopts total reflux operation, the discharging of tower still is only arranged, contain methyl alcohol, water, ritalin and acetic acid quaternary mixed solution in the tower bottoms, wherein methyl alcohol and ritalin, water and ritalin all form azeotrope, cause the later separation difficulty.
Summary of the invention
The objective of the invention is deficiencies such as, later separation difficulty higher at the existing tower bottoms water content of existing hydrolysis process of methyl acetate, and provide a kind of fixed-bed reactor and extraction-catalytic rectifying tower coupled pure terephthalic acid produce in catalytic hydrolysis process for by-product methyl acetate.
Technical scheme of the present invention is: catalytic hydrolysis process for by-product methyl acetate during a kind of pure terephthalic acid produces, and concrete steps are as follows:
1) by-product methyl acetate in pure terephthalic acid's production process and hydromassage you enter the fixed-bed reactor FBR that contains strong acid cation exchange resin catalyst than the mixed mixture A in 1:1～6 and carry out catalytic hydrolysis reaction;
2) the hydrolyzed solution B in the fixed-bed reactor introduces in the extraction-catalytic rectifying tower, and wherein extraction-catalytic rectifying tower T1 is followed successively by extraction-rectifying section 1, conversion zone 2, stripping section 3 from top to bottom; The water C that unhydrolysed ritalin and extraction-rectifying section 1 top add among the hydrolyzed solution B is in these tower conversion zone 2 reactions, cat head distillates ritalin and a spot of water E, be recycled in the fixed-bed reactor and react, the discharging of tower still is the mixed solution D of water, acetic acid and methyl alcohol;
3) extraction-catalytic rectifying tower T1 tower still discharging mixed solution D introducing methanol distillation column T2 separates, and cat head distillates methyl alcohol F, and the discharging of tower still is the mixed solution G of acetic acid and water.
Wherein temperature of reaction is 50～65 ℃ in the step 1) fixed-bed reactor, air speed be 0.5～1.5 cubic metre/(cubic meter reaction volume hour).Wherein loading catalyst is a storng-acid cation exchange resin in the fixed-bed reactor bed, 1～2 year work-ing life of catalyzer.
In the step 1; owing to contain some metal ion in the ritalin raw material from last workshop section; at first enter fixed-bed reactor; Zeo-karb in the fixed-bed reactor is on the one hand as hydrolyst; in addition can also be as the ion-exchanger of metal ion; thereby can protect the catalyzer in the conversion zone in extraction-catalytic rectifying tower, make the catalyst life of conversion zone filling in extraction-catalytic rectifying tower extend to 2～3 years greatly.The replacing of catalyzer is changed with respect to catalyzer in the extraction-catalytic rectifying tower and is wanted a lot of easily in the fixed-bed reactor, so this technology can reduce operation easier.
Hydrolyzed solution B in the said fixing bed bioreactor is 1/5～1/2 introducing from extraction-catalytic rectifying tower T1 stripping section top.
Among above-mentioned extraction-catalytic rectifying tower T1, the theoretical plate number of extraction-rectifying section 1 is 1～15, and conversion zone 2 theoretical plate numbers are 15～45, and stripping section 3 theoretical plate numbers are 10～20.
Above-mentioned steps 2) raw materials components mole ratio of ritalin is 2～8:1 in the water of extraction-rectifying section 1 top adding and the step 1); Reflux ratio is 1～5:1, the charging air speed be 0.05～0.5 cubic metre/(cubic meter reaction volume hour).Water as reactant simultaneously also as ritalin and the isolating extraction agent of methanol azeotrope.
Above-mentioned steps 3) among the methanol distillation column T2, reflux ratio is 0.5～5:1, theoretical plate number 15～50.
1 couple of the present invention describes in further detail below in conjunction with accompanying drawing.
Filling storng-acid cation exchange resin in the fixed-bed reactor FBR, extraction-catalytic rectifying tower T1 is divided into three parts: top extraction-rectifying section 1, middle part conversion zone 2, bottom stripping section 3, wherein extraction-rectifying section and stripping section load conventional fillers or column plate, and conversion zone filling storng-acid cation exchange resin is tied up bag or other catalytic distillation elements.Filling conventional fillers or column plate in the methanol distillation column.
Material A ritalin and water at first enter fixed-bed reactor FBR and carry out catalytic hydrolysis reaction.
Hydrolyzed solution in the fixed-bed reactor is that material B enters extraction-catalytic rectifying tower T1 stripping section top, material C (water) adds from extraction-rectifying section top, water as reactant simultaneously also as ritalin and the isolating extraction agent of methanol azeotrope, cat head extraction ritalin and a spot of water, partial reflux, partial material E (cat head extraction ritalin and a spot of water) is circulated among the fixed-bed reactor FBR; The mixed solution of tower still extraction acetic acid, first alcohol and water.
Material D (mixed solution of acetic acid, first alcohol and water) enters methanol distillation column T2 to be separated, and overhead product methyl alcohol is discharged as material F, and the mixed solution of tower still product acetic acid and water is discharged as material G.
Beneficial effect:
(1) owing to adopts fixed bed and extraction-catalytic distillation coupling and catalyzing hydrolysis process, more existing catalytic rectifying tower, hydrolyzed solution knockout tower, extractive distillation column, methanol rectifying tower four-column process flow technology, flow process shortening, equipment minimizing.And operation is easier, can cut down the consumption of energy greatly simultaneously.
(2) in the methyl acetate hydrolysis process, the charging water to ester ratio is the important factor that influences the methyl acetate hydrolysis rate, and ritalin separates with methanol azeotrope and often makes water as extraction agent, the total reflux operation that catalytic rectifying tower adopts in the off the beaten track ritalin reactive distillation of the present invention hydrolysis process is provided with extraction-rectifying section.In extraction-catalytic rectifying tower, water is added by extraction-rectifying section top, water at extraction-rectifying section as ritalin and the isolating extraction agent of methanol azeotrope, as the reactant reaction that is hydrolyzed, promptly a tower plays two towers, is extractive distillation column at conversion zone, it is again catalytic rectifying tower, obviously can obtain obvious energy-saving effect, thereby can realize that the cat head discharging is ritalin and a spot of water, the discharging of tower still is the mixed solution of acetic acid, first alcohol and water.Methanol Recovery Tata still extraction aqueous acetic acid, directly be sent to PTA produce in existing acetic acid recycle section carry out acetic acid and reclaim.
(3) the present invention reduces the extracting rectifying tower in the existing methyl acetate catalysis rectification hydrolysis technique, thereby reduces facility investment and energy consumption.
(4) under operation conditions optimization, the ritalin total conversion rate generally reaches 50%-95%, is up to more than 99%, and the mass concentration of methyl alcohol is for generally reaching 80%-99.5%, and is the highest by 99.9%, satisfy PTA produce in to the specification of quality of fuel methanol.
Description of drawings
Fig. 1 is a by-product methyl acetate catalytic hydrolysis new technological flow synoptic diagram during pure terephthalic acid provided by the invention produces:
Wherein: FBR is fixed-bed reactor, T1 is an extraction-catalytic rectifying tower, T2 is a methanol distillation column, 1 is extraction-rectifying section, 2 is conversion zone, and 3 is stripping section, and 4 is condenser, 5 is reboiler, A is ritalin and water charging, and B is the fixed-bed reactor hydrolyzed solution, and C is an extraction-catalytic rectifying tower water, D is the discharging of extraction-catalytic distillation Tata still, be the mixed solution of acetic acid, first alcohol and water, E is the discharging of extraction-catalytic distillation column overhead, is ritalin and a spot of water, F is a methyl alcohol, and G is the mixed solution discharging of acetic acid and water.
Embodiment
The invention will be further described below by specific embodiment, and each example operation condition is pressed in the table 1 and implemented.
Embodiment 1
Water and ritalin 6:1 in molar ratio enter fixed-bed reactor, 57 ℃ of temperature of reaction, air speed be 0.6 cubic metre/(cubic meter reaction volume hour), catalyzer is an Amberlyst35 type storng-acid cation exchange resin.T1 tower water and ritalin be 3:1 in molar ratio, T1 extraction-rectification section theoretical plate number 4, T1 conversion zone theoretical plate number 20, T1 stripping section theoretical plate number 15, reflux ratio 4.2,0.1 cubic metre of T1 tower air speed/(cubic meter reaction volume hour), T2 theoretical plate number 18, reflux ratio 4.5.
Embodiment 2
Water and ritalin 3:1 in molar ratio enter fixed-bed reactor, 52 ℃ of temperature of reaction, air speed be 0.9 cubic metre/(cubic meter reaction volume hour), catalyzer is 001 * 7 type storng-acid cation exchange resin.T1 tower water and ritalin be 5:1 in molar ratio, T1 extraction-rectification section theoretical plate number 13, T1 conversion zone theoretical plate number 31, T1 stripping section theoretical plate number 11, reflux ratio 1.4,0.3 cubic metre of T1 tower air speed/(cubic meter reaction volume hour), T2 theoretical plate number 34, reflux ratio 2.9.
Water and ritalin 1:1 in molar ratio enter fixed-bed reactor, 63 ℃ of temperature of reaction, air speed be 1.4 cubic metres/(cubic meter reaction volume hour), catalyzer is a D001 type storng-acid cation exchange resin.T1 tower water and ritalin be 7:1 in molar ratio, T1 extraction-rectification section theoretical plate number 8, T1 conversion zone theoretical plate number 43, T1 stripping section theoretical plate number 17, reflux ratio 3.0,0.4 cubic metre of T1 tower air speed/(cubic meter reaction volume hour), T2 theoretical plate number 45, reflux ratio 1.3.
Table 1
| Detailed | Example 1 | Example 2 | Example 3 |
| FBR water ester mol ratio | 6.0 | 3.0 | 1.0 |
| Temperature of reaction | 57℃ | 52℃ | 63℃ |
| T1 tower water ester mol ratio | 3.0 | 5.0 | 7.0 |
| The FBR air speed | 0.6 | 0.9 | 1.4 |
| The T1 air speed | 0.1 | 0.3 | 0.4 |
| The T1 reflux ratio | 4.2 | 1.4 | 3.0 |
| T1 extraction-rectification section |
4 | 13 | 8 |
| T1 conversion zone theoretical plate number | 20 | 31 | 43 |
| T1 stripping section theoretical plate number | 15 | 11 | 17 |
| Catalyzer | Amberlyst35 type Zeo-karb | 001 * 7 type Zeo-karb | D001 type Zeo-karb |
| The T2 reflux ratio | 4.5 | 2.9 | 1.3 |
| The T2 theoretical plate number | 18 | 34 | 45 |
| Methanol quality concentration/% | 93.5 | 98.5 | 99.9 |
| Methyl acetate hydrolysis rate/% | 83.6 | 94.8 | 99.9 |
Claims (6)
1. the catalytic hydrolysis process of by-product methyl acetate during a pure terephthalic acid produces, its concrete steps are as follows:
1) by-product methyl acetate in pure terephthalic acid's production process and hydromassage you enter the fixed-bed reactor that contain strong acid cation exchange resin catalyst than the mixed mixture A in 1:1～6 and carry out catalytic hydrolysis reaction;
2) the hydrolyzed solution B in the fixed-bed reactor introduces in the extraction-catalytic rectifying tower, wherein extraction-catalytic rectifying tower (T1) is followed successively by extraction-rectifying section (1), conversion zone (2), stripping section (3) from top to bottom, the water C that unhydrolysed ritalin and extraction-rectifying section (1) top adds among the hydrolyzed solution B is in this tower conversion zone (2) reaction, cat head distillates ritalin and a spot of water E, be recycled in the fixed-bed reactor and react, the discharging of tower still is the mixed solution D of water, acetic acid and methyl alcohol;
3) extraction-catalytic rectifying tower (T1) tower still discharging mixed solution D introducing methanol distillation column (T2) separates, and cat head distillates methyl alcohol F, and the discharging of tower still is the mixed solution G of acetic acid and water.
2. technology according to claim 1 is characterized in that temperature of reaction is 50～65 ℃ in the step 1) fixed-bed reactor, air speed be 0.5～1.5 cubic metre/(cubic meter reaction volume hour).
3. technology according to claim 1 is characterized in that hydrolyzed solution B 1/5～1/2 introducing from extraction-catalytic rectifying tower (T1) stripping section top in the fixed-bed reactor.
4. technology according to claim 1, it is characterized in that in step 2) in the extraction-catalytic rectifying tower (T1), extraction-rectifying section (1) theoretical plate number is 1～15, conversion zone (2) theoretical plate number is 15～45, stripping section (3) theoretical plate number is 10～20.
5. technology according to claim 1 is characterized in that in step 2) raw materials components mole ratio of ritalin is 2～8:1 in the water that adds of extraction-rectifying section (1) top and the step 1); Reflux ratio is 1～5:1, the charging air speed be 0.05～0.5 cubic metre/(cubic meter reaction volume hour).
6. technology according to claim 1 is characterized in that in step 3) methanol distillation column (T2), reflux ratio is 0.5～5:1, theoretical plate number 15～50.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102060655A (en) * | 2010-12-13 | 2011-05-18 | 陈越峰 | Hydrolysis method of methyl acetate |
| 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 |
| WO2013132507A1 (en) | 2012-03-05 | 2013-09-12 | Reliance Industries Ltd., | An integrated process for the recovery of metal catalysts during the manufacture of purified terephthalic acid |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1057079C (en) * | 1996-02-09 | 2000-10-04 | 福州大学 | Catalystic rectification and hydrolization technology and equipment for methyl acetate |
| CN100526284C (en) * | 2005-08-31 | 2009-08-12 | 中国石化仪征化纤股份有限公司 | Recovering device for oxidization low pressure end gas in process of preparing terephthalic acid |
| CN100418939C (en) * | 2006-09-15 | 2008-09-17 | 福州大学 | Hydrolysis process and equipment of by-product methyl acetate in the production of purified terephthalic acid |
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2009
- 2009-02-20 CN CN2009100245845A patent/CN101481293B/en not_active Expired - Fee Related
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
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| 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 |
| CN102060655A (en) * | 2010-12-13 | 2011-05-18 | 陈越峰 | Hydrolysis method of methyl acetate |
| WO2012164573A2 (en) | 2011-05-27 | 2012-12-06 | Reliance Industries Ltd., | Hydrolysis and esterification with acid catalysts |
| WO2013132507A1 (en) | 2012-03-05 | 2013-09-12 | Reliance Industries Ltd., | An integrated process for the recovery of metal catalysts during the manufacture of purified terephthalic acid |
| 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 alcoholysis 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 |
| CN115181019A (en) * | 2022-08-26 | 2022-10-14 | 东华工程科技股份有限公司 | Process for preparing electronic grade glycolic acid solution by hydrolyzing methyl glycolate |
| CN115181019B (en) * | 2022-08-26 | 2024-03-19 | 东华工程科技股份有限公司 | Process for preparing electronic grade glycollic acid solution by methyl glycolate hydrolysis |
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| CN101481293B (en) | 2012-05-30 |
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