CN104144906A - An integrated process for the recovery of metal catalysts during the manufacture of purified terephthalic acid - Google Patents
An integrated process for the recovery of metal catalysts during the manufacture of purified terephthalic acid Download PDFInfo
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- CN104144906A CN104144906A CN201280071156.8A CN201280071156A CN104144906A CN 104144906 A CN104144906 A CN 104144906A CN 201280071156 A CN201280071156 A CN 201280071156A CN 104144906 A CN104144906 A CN 104144906A
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- 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
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/16—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation
- C07C51/21—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen
- C07C51/255—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen of compounds containing six-membered aromatic rings without ring-splitting
- C07C51/265—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen of compounds containing six-membered aromatic rings without ring-splitting having alkyl side chains which are oxidised to carboxyl groups
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/41—Preparation of salts of carboxylic acids
- C07C51/412—Preparation of salts of carboxylic acids by conversion of the acids, their salts, esters or anhydrides with the same carboxylic acid part
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- 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
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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
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Abstract
The present disclosure provides a process for recovering PTA (purified terephthalic acid) oxidation catalysts during the manufacture of PTA, using an acid catalyst containing reaction stream resulting from the hydrolysis of an organic ester.
Description
The application augments in a patent of the Indian patent application 1585/MUM/2011 of application on May 27th, 2011, and its full content will be incorporated to herein by specifically quoting.
Technical field
The present invention relates to a kind of integrated process, this technique is involved in the process of producing high purity terephthalic acid (PTA) and reclaims metal catalyst, has utilized a kind of acid catalyst that contains organic ester hydrolysis gained reactant flow.
Background technology
A large amount of methyl acetates that produce are by products of high purity terephthalic acid (PTA) factory and polyvinyl alcohol (PVA) factory.Because methyl acetate is the solvent that a kind of value is lower, methyl acetate or to sell at a low price, or be hydrolyzed to methyl alcohol and the acetic acid that value is higher, after hydrolysis reaction, need through conventional distil process.Hydrolysis is not easy to reach balance, and a large amount of unconverted methyl acetates need to carry out separation and recirculation, and reason is the low equilibrium constant and disturbs the existence of azeotrope to cause inhibition to being hydrolyzed methyl acetate by common process.
Acetic acid (HOAc) and methyl alcohol (MeOH) can make by methyl acetate (MeOAc) and the liquid phase reaction of water.MeOAc hydrolysis reaction is reversible reaction, and K is relatively little for reaction equilibrium constant.Therefore, H+ ion is used as catalyzer to promote speed of reaction.The strong acid such as sulfuric acid and hydrochloric acid can be used for producing H+ ion catalyzed reaction.Yet strong acid can cause corrosion to whole technique.In order to eliminate described shortcoming, a kind of sulfonic acid (SO that contains
3h) strong cation-exchanging resin is commonly used for the acid catalyst of hydrolysis.
Reported in the prior art the hydrolysis process of various methyl acetates.For example, TWI322801B has described a kind of technique, is involved in reactive distillation system and is hydrolyzed methyl acetate solution, with two kinds of mixtures of generation in the presence of heterogeneous catalyst.By a kind of return-flow system that heterogeneous catalyst is housed, by mixture condensation and be back to reactive distillation system.
Korean Patent KR888065B1 has explained a kind of method that is hydrolyzed methyl acetate, and wherein, hydrolysis is to complete in a kind of reactor that solid catalyst is housed.
In GB687902, described under higher than barometric point and the high temperature lower than boiling point, under the existence of hydrolyst, be hydrolyzed methyl acetate.The catalyzer adopting is a kind of strong acid, for example, equals 0.05 to 2%, the sulfuric acid of preferably approximately 1% reactant weight, and other reaction parameter is 48 to 1400 ℃ of temperature, maximum 10 normal atmosphere of pressure.
In CN101481293A, disclose a kind of in producing high purity terephthalic acid the technique of catalytic hydrolysis by-product acetic acid methyl esters.According to disclosed content in CN101481293A, hydrolysis methyl acetate catalyzer used is heterogeneous catalyst.Although this technique can be said to be complete, CN101481293A does not refer to the relevant problem that reclaims metal catalyst used in synthetic PTA.
Another Chinese patent CN100418939C also discloses in the technique of purified terephthalic, the methyl acetate that hydrolysis produces as by product.This technique (described in CN100418939C) has adopted Zeo-karb in catalytic rectifying tower.
Although hydrolysis methyl acetate and the related process of producing terephthalic acid are explained, the relevant particular problem that reclaims metal catalyst used in synthesizing terephthalic acid that there is no which process discussion.
Summary of the invention
Object of the present disclosure:
Part object of the present disclosure is described below:
An object of the present disclosure is to provide a kind of integrated process, and it involves the methyl acetate in hydrolysis methyl acetate and remanufacture PTA process.
Another object of the present disclosure is to provide a kind of technique of simple economy, to reclaim the methyl acetate of PTA in producing, its used a kind of from hydrolysis organic ester separated and restored acid catalyzer.
Other objects of the present disclosure and advantage are by reflection more significantly the description from below in conjunction with accompanying drawing, and its purpose is not to limit scope of the present invention.
Disclosure general introduction:
According to the disclosure, a kind of technique that reclaims PTA oxide catalyst in PTA production process is provided, it has used a kind of acid catalyst that contains hydrolysis organic ester gained reactant flow; Described technique comprises the following steps:
I) under the first catalyzer exists, a kind of organic ester of carboxylic acid is hydrolyzed into respectively to Carboxylic acid and alcohol, to produce a kind of effluent stream that contains described carboxylic acid, described alcohol, water and described the first catalyzer, wherein, described the first catalyzer is a kind of an acidic catalyst;
Ii), as option, from described effluent stream, remove water and alcohol;
Iii) Alkylaromatics that is selected from p-Xylol and m-xylene is done in oxidation liquid phase, there is at that time the second catalyzer, comprising: at least one metal-salt that i) is selected from cobaltous acetate and manganous acetate, and ii) hydrogen bromide, is intended to obtain a kind of reaction mixture that contains terephthalic acid (TA);
Iv) from reaction mixture, separate out described terephthalic acid, obtain a kind of mother liquor that comprises described the second catalyzer;
V) with described effluent stream, process described mother liquor, by oxalate denominationby, from described the first catalyzer, isolate the acetic acid pair anion of described the second catalyzer, obtain the mixture that contains described second each insoluble salt of catalyzer; And
Vi) by described the second catalyzer of centrifugal recovery, the not dissolved salt of separated described the second catalyzer.
Conventionally, described the first catalyzer is oxalic acid.
Conventionally, described carboxylic acid with at method steps i) in the ratio of the first catalyzer described in gained effluent stream be 9:1.
Conventionally, carboxylic acid is selected from least one at least acetic acid, propionic acid and butyric acid.
Conventionally, alcohol is selected from least one at least methyl alcohol, ethanol, Virahol, propyl carbinol, amylalcohol and hexanol.
Conventionally, ester is from the arbitrary combination of carboxylic acid and alcohol.
As preferably, ester includes but not limited to methyl acetate, ethyl acetate, isopropyl acetate, n-butyl acetate, pentyl acetate and hexyl acetate.
According to one of them scheme of the present disclosure, ester is methyl acetate, and effluent stream contains acetic acid, methyl alcohol, oxalic acid and water.
Accompanying drawing explanation
Fig. 1 is according to the technology and equipment schema of disclosure hydrolysis methyl acetate; And
Fig. 2 illustrates a kind of integration schema that is hydrolyzed methyl acetate and reclaims catalyzer.
Embodiment
The technique that is hydrolyzed organic acid acetic under acid catalyst exists is open in common co-pending application 1585/MUM/2011 by the inventor, and its full content will be incorporated to herein by specifically quoting.
The disclosure provides the integration of a kind of hydrolysis process and high purity terephthalic acid (PTA) production technique, to reclaim in process of production PTA oxide catalyst.As can be seen here, according to the disclosure, provide a kind of technique that reclaims PTA oxide catalyst in PTA production process, it has used a kind of acid catalyst that contains hydrolysis organic ester gained reactant flow.
The organic ester of hydrolysis is from the arbitrary combination of carboxylic acid and alcohol in a first step.As preferably, ester includes but not limited to methyl acetate, ethyl acetate, isopropyl acetate, n-butyl acetate, pentyl acetate and hexyl acetate.
According to one of them scheme of the present disclosure, the weak acid such as carboxylic acid are as the first catalyzer.
As preferably, used catalyst is to contain 5 to 40% oxalic acid or acetic acid or both the aqueous solution.
The aqueous solution all having, according to one of them exemplary scenario of the present disclosure, the following describes as producing acetic acid the methyl acetate hydrolysis reaction under acid catalyst exists.
Organic ester methyl acetate (MeOAc) and water (H
2o) react on single continuous reaction tower, it is as the combination of a kind of reactor and distillation tower, the sufficient residence time is provided, usings in the presence of the oxalic acid as catalyzer, reach the high conversion to methyl alcohol (MeOH) and acetic acid (HOAc) by methyl acetate.The methyl acetate newly adding is sent into mixing tank with water with supplementary oxalic acid.From the mixture flow of mixing tank, send into the middle part of reaction tower (RD).Conventionally, from the overhead product logistics (containing having an appointment 88.2% methyl acetate, 11.4% methyl alcohol and 0.4% water) of RD, send into continuously mixing tank.Bottoms product stream from RD contains 29.5%HOAc, 45.2% methyl acetate, 15.7% methyl alcohol and 9.6% oxalic acid conventionally.Unless otherwise prescribed, all per-cent used herein is all weight percentage.Utilize distillation tower (D1) from the bottoms product stream of RD, to isolate the methyl alcohol of 98.3% purity.In view of the boiling point of methyl alcohol, acetic acid and water differs greatly, at the bottom of RD tower, there is not the azeotrope of methyl acetate and the formation of methanol, in D1, separation of methanol is comparatively light.Bottom product in D1 (containing 53.4% water, 35.1% acetic acid, 0.1% methyl alcohol and 11.4% oxalic acid) is sent into distillation tower D2.The overhead product of D2 contains 97.9% pure water and a small amount of acetic acid and methyl alcohol.The bottom product of D2 comprises 73.6% acetic acid and 24.6% oxalic acid.Utilize the oxalic acid in this logistics of crystallizer (C1) crystallization.Utilize filter F 1 that crystallisate is separated from acetic acid.
The function mode of reaction tower makes it that intimate contact between methyl acetate and water, acetic acid and methyl acetate/water azeotrope and acetic acid and methanol/methyl acetate azeotrope is provided.By intimate contact between reactant and product being provided and removing continuously product at the bottom of the tower top of reaction tower and tower, reached high conversion.
Methyl acetate and water are sent into reaction tower by the molar ratio range of 1:1 to 1:10, preferred 1:1 to 1:5, and the ratio of 1:3 to 1:5 is even more excellent.
Reaction tower routine operates on the temperature of approximately 40 to 90 ℃.Yet, for the ideal temperature of special process, depend on desirable productivity, running pressure.Conventional running pressure is about 1 to 2 normal atmosphere.Conventionally, wish to operate on low temperature and low pressure.The residence time of reaction mixture in reaction tower is also an important parameter of disclosure technique.The required residence time of higher conversion is depended on catalyzer and catalyst concn.
The catalyst concn that offers reaction tower is enough to the catalytic effect that provides desirable.To reaction tower, providing the advantageous manner of catalyzer is in the higher part position of tower, to send into the aqueous solution of oxalic acid.As option, a part of acetic acid or the acetic acid/water mixtures that are wherein dissolved with oxalic acid are sent into by the higher part position of tower.Had 30% oxalic acid aqueous solution as catalyzer, the residence time of disclosure technique is at least 30 minutes.As preferably, the residence time in reaction tower is about 30 to 45 minutes.The reflux ratio of disclosure technique is at least about 1.32.Term reflow is than the ratio that is defined as trim the top of column rate and overhead product flow rate.
Equipment M1 shown in accompanying drawing 1 comprises a mixing tank that agitator A is housed.This mixing tank is labeled as M1, is connected with pipeline 3 with pipeline 2.RD is a reaction tower, by pipeline 4, is connected with the outlet of M1.The return line of RD is labeled as pipeline 5 and pipeline 6, and H1 is connected with condenser.Another recirculating line 7 is connected to condenser H2, and its export pipeline 8 is connected to pipeline 9.Pipeline 9 is connected to M1.At the bottom of pipeline 10 and 11 is connected to the tower of RD by reboiler H3.The export pipeline 12 of RD is connected to distillation tower D1.Pipeline 13 is communicated with condenser H4, and pipeline 14 is connected to D1.The tower top outlet pipeline of D1 is labeled as pipeline 15.Article two, at the bottom of tower, return line is communicated with reboiler H5, is labeled as respectively pipeline 16 and 17.Similarly, the tower bottom outlet pipeline 18 of D1 is connected to distillation tower D2.Trim the top of column pipeline 19 and 20 is communicated with condenser H6.The tower top outlet pipeline of D2 is labeled as pipeline 21.Article two, at the bottom of tower, return line is communicated with reboiler H7, is labeled as respectively pipeline 22 and 23.At the bottom of crystallizer C1 is connected to the tower of D2 by pipeline 24.Filter F 1 is connected with crystallizer by pipeline 25.Pipeline 26 and 27 is also connected to filter F 1.
Methyl acetate is sent into mixing tank M1 by pipeline 9.Water is sent into mixing tank M1 by water inlet pipeline 2, and catalyzer is introduced by pipeline 3.The mixture that contains methyl acetate, water and catalyzer is sent into reaction tower RD by pipeline 4.Reaction is at 30 to 120 ℃, to carry out in reaction tower, preferably 90 to 100 ℃.Distillation tower D1 is used for distilling out methyl alcohol (pipeline 15), and it is the tower base stream from reaction tower by pipeline 12.Similarly, distillation tower D2 is for separating of going out acetic acid and oxalic acid (pipeline 24), and it is the tower base stream from D1 by pipeline 18.The mixture of oxalic acid and acetic acid (pipeline 24) is sent into crystallizer C1, at this, is settled out oxalic acid.Mould temperature keeps 10 to 25 ℃, preferably 15 to 18 ℃.The catalyzer of precipitation separation is by filter F 1, isolates as far as possible many catalyzer and acetic acid, and by pipeline 26 and 27, send respectively at this.
The effluent stream that hydrolysis carboxylic acid organic ester produces contains respectively carboxylic acid, alcohol, water and acid catalyst conventionally.According to involved ester class, the carboxylic acid being present in effluent stream can be acetic acid, propionic acid and butyric acid, and corresponding alcohol may be methyl alcohol, ethanol, Virahol, propyl carbinol, amylalcohol and hexanol.As option, water and methyl alcohol remove from this logistics, thereby obtain a kind of effluent stream of containing carboxylic acid and acid catalyst.Conventionally, in effluent stream, the ratio of carboxylic acid and described the first catalyzer (acid catalyst) is 9:1.This is the logistics 27 in Fig. 1.
The production of terephthalic acid is by the temperature range at 150 to 210 ℃, in acetic acid, use air oxidation in liquid phase aromatic substance, it is selected from p-Xylol and m-xylene, and there is a kind of metal catalyst system (the second catalyzer), comprising cobalt manganese bromide catalysts system (cobaltous acetate, manganous acetate and hydrogen bromide).
The relative proportion of cobalt, manganese and bromide importantly, representative value is manganese: cobalt ratio is 3:1, cobalt: bromide ratio is 1:5.In reaction tower and crystallizer, the crystallization from mother liquor of most of terephthalic acid is also passed through filtering separation out.
Mother liquor mainly contains acetic acid, organic compound (as m-phthalic acid, phenylformic acid) and mineral compound (as the compound of cobalt and manganese), and iron, nickel, chromium and sodium.
According to exemplary scenario of the present disclosure, then process the mother liquor that contains the second catalyzer (metal catalyst) and adopted effluent stream, it contains carboxylic acid and acid catalyst (oxalic acid), i.e. logistics in Fig. 1 27 is intended to recovery and is present in the metal catalyst in mother liquor with oxalate form.Conventionally, by oxalate denominationby, the acetic acid pair anion of metal catalyst is separated from acid catalyst.This is shown in Fig. 2, and wherein, the hydrolyzable moiety of methyl acetate shows the separated of hydrolysis process and product, catalyzer (oxalic acid) and acetic acid (logistics 27 in Fig. 1).Come from the logistics 27 (containing 90% acetic acid and 10% oxalic acid) of hydrolyzable moiety for the recovery of catalyzer.
Logistics 27 in Fig. 1 mixes with the mother liquor that contains inorganic metal catalyzer in mixing zone.Oxalic acid in this logistics reacts with the acetate of cobalt and manganese, forms oxalate separately, and it,, by centrifugation recovery, also may be recycled to oxidizing reaction tower.
Now quote following non-limiting example and further describe the disclosure:
example 1:
Example 1:
In a kind of exemplary apparatus of accompanying drawing 1, methyl acetate and water by weight proportion 1:5 add reaction tower the stirring that has oxalic acid to.Reaction continues 30 minutes at 65 ℃.After having reacted, whole mixture distillation by cooling and isolating oxalic acid.The acetic acid and the methyl alcohol per-cent that form are respectively 55 and 45.
example 2:
A kind of exemplary apparatus in accompanying drawing 2 is divided into the catalyst recovery unit of methyl acetate hydrolysis part and high purity terephthalic acid (PTA) technique.This example is followed the step of example 1.10% oxalic acid solution that contains acetic acid is separated by process for cooling, then sends to high purity terephthalic acid's catalyst recovery unit, at this cobalt and manganese with the isolated in form of oxalate out.
In this specification, the implication that should understand " comprising " or " a containing " word is to comprise stated individual element, integral body or step, also can be to comprise a plurality of elements, integral body or step, but do not get rid of any other individual element, integral body or step, do not get rid of other a plurality of elements, integral body or step yet.
Use wording " at least " or " at least one " to represent to use one or more elements, batching or quantity, this usage may appear in the solution of the present invention, is intended to reach one or more desirable objects or result.
In this specification sheets, about any discussion of file, bill, material, equipment, document etc., its sole purpose is to provide a kind of background for the disclosure.It should not do to admit that any or all this type of item has formed the part on prior art basis, or in present patent application, before preferential day, has had the general general knowledge that becomes association area of the present invention because of it.
The numerical value of mentioned various physical parameter, size or quantity is only approximation, imagine any one numerical value, if be greater than/be less than the numerical value of distributing to this type of parameter, size or quantity, must be in disclosure scope of invention, unless there is contrary statement in detailed description.
Above the description of concrete scheme has fully been disclosed to the general aspects of scheme herein, make other people can apply existing knowledge, do not departing from universal situation, easily revise and/or adjust this type of concrete scheme to be applicable to various application, therefore, should and attempt to understand, this type of adjustment and modification are within being equal to the meaning and scope of disclosed scheme.Should be appreciated that wording used herein or term are non-limiting object for description.Therefore, although herein scheme is described with term " preferred version ", those skilled in the art should appreciate that, in the spirit and scope of scheme described herein, scheme can be revised and implement herein.
Claims (7)
1. in PTA production process, reclaim a technique for PTA oxide catalyst, it has used a kind of acid catalyst that contains hydrolysis organic ester gained reactant flow; Described technique comprises the following steps:
I. under the first catalyzer exists, a kind of organic ester of carboxylic acid is hydrolyzed into respectively to Carboxylic acid and alcohol, to produce a kind of effluent stream that contains described carboxylic acid, described alcohol, water and described the first catalyzer, wherein, described the first catalyzer is a kind of an acidic catalyst;
Ii. as option, from described effluent stream, remove water and alcohol;
Iii. the Alkylaromatics that is selected from p-Xylol and m-xylene is done in oxidation liquid phase, there is at that time the second catalyzer, comprising: at least one metal-salt that i) is selected from cobaltous acetate and manganous acetate, and ii) hydrogen bromide, is intended to obtain a kind of reaction mixture that contains terephthalic acid (TA);
Iv. from reaction mixture, separate out described terephthalic acid, obtain a kind of mother liquor that comprises described the second catalyzer;
V. with described effluent stream, process described mother liquor, by oxalate denominationby, from described the first catalyzer, isolate the acetic acid pair anion of described the second catalyzer, obtain the mixture that contains described second each insoluble salt of catalyzer; And
Vi. by described the second catalyzer of centrifugal recovery, the not dissolved salt of separated described the second catalyzer.
2. technique according to claim 1, wherein said the first catalyzer is oxalic acid.
3. according to the technique described in aforementioned claim any one, wherein said carboxylic acid with at method steps i) in the ratio of the first catalyzer described in gained effluent stream be 9:1.
4. technique according to claim 1, wherein said carboxylic acid is selected from least one at least acetic acid, propionic acid and butyric acid.
5. technique according to claim 1, wherein alcohol is selected from least one at least methyl alcohol, ethanol, Virahol, propyl carbinol, amylalcohol and hexanol.
6. technique according to claim 1, wherein said ester is from the arbitrary combination of the Carboxylic acid and alcohol of advocating respectively in claim 4 and 5.
7. according to the technique described in aforementioned claim any one, wherein said ester is methyl acetate, and described effluent stream contains acetic acid, methyl alcohol, oxalic acid and water.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| IN577/MUM/2012 | 2012-03-05 | ||
| IN577MU2012 | 2012-03-05 | ||
| PCT/IN2012/000291 WO2013132507A1 (en) | 2012-03-05 | 2012-04-20 | An integrated process for the recovery of metal catalysts during the manufacture of purified terephthalic acid |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN104144906A true CN104144906A (en) | 2014-11-12 |
| CN104144906B CN104144906B (en) | 2016-08-17 |
Family
ID=46888517
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201280071156.8A Expired - Fee Related CN104144906B (en) | 2012-03-05 | 2012-04-20 | The integrated process of metallic catalyst is reclaimed during producing high purity terephthalic acid |
Country Status (5)
| Country | Link |
|---|---|
| CN (1) | CN104144906B (en) |
| BR (1) | BR112014021765A2 (en) |
| HK (1) | HK1203479A1 (en) |
| PT (1) | PT2013132507W (en) |
| WO (1) | WO2013132507A1 (en) |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4490297A (en) * | 1981-12-24 | 1984-12-25 | Dynamit Nobel Ag | Method for the recovery and reuse of cobalt and/or manganese components of catalysts |
| US4587355A (en) * | 1984-08-22 | 1986-05-06 | Amoco Corporation | Oxidation with a solid catalyst |
| CN101531588A (en) * | 2008-03-13 | 2009-09-16 | 周向进 | Method for preparing new purified terephthalic acid |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB687902A (en) | 1950-04-27 | 1953-02-25 | Melle Usines Sa | Improvements in or relating to processes for the hydrolysis of methyl acetate and the treatment of aqueous mixtures of methyl acetate, methyl alcohol and acetic acid so obtained |
| CN100418939C (en) | 2006-09-15 | 2008-09-17 | 福州大学 | Hydrolysis process of methyl acetate as by-product of producing refined terephthalic acid and apparatus thereof |
| TWI322801B (en) | 2006-12-05 | 2010-04-01 | Univ Nat Taiwan | Separation system and method for hydrolysis of methyl acetate |
| KR100888065B1 (en) | 2007-11-15 | 2009-03-11 | 아신기술 주식회사 | Improvedprocess for methyl acetate hydrolysis |
| CN101481293B (en) | 2009-02-20 | 2012-05-30 | 南京工业大学 | Catalytic hydrolysis process for byproduct methyl acetate in production of purified terephthalic acid |
-
2012
- 2012-04-20 WO PCT/IN2012/000291 patent/WO2013132507A1/en active Application Filing
- 2012-04-20 PT PT2012000291A patent/PT2013132507W/en unknown
- 2012-04-20 CN CN201280071156.8A patent/CN104144906B/en not_active Expired - Fee Related
- 2012-04-20 BR BR112014021765A patent/BR112014021765A2/en not_active IP Right Cessation
-
2015
- 2015-04-21 HK HK15103834.7A patent/HK1203479A1/en unknown
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4490297A (en) * | 1981-12-24 | 1984-12-25 | Dynamit Nobel Ag | Method for the recovery and reuse of cobalt and/or manganese components of catalysts |
| US4587355A (en) * | 1984-08-22 | 1986-05-06 | Amoco Corporation | Oxidation with a solid catalyst |
| CN101531588A (en) * | 2008-03-13 | 2009-09-16 | 周向进 | Method for preparing new purified terephthalic acid |
Also Published As
| Publication number | Publication date |
|---|---|
| WO2013132507A1 (en) | 2013-09-12 |
| CN104144906B (en) | 2016-08-17 |
| HK1203479A1 (en) | 2015-10-30 |
| BR112014021765A2 (en) | 2017-08-22 |
| PT2013132507W (en) | 2015-05-20 |
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