CN104144906B - The integrated process of metallic catalyst is reclaimed during producing high purity terephthalic acid - Google Patents
The integrated process of metallic catalyst is reclaimed during producing high purity terephthalic acid Download PDFInfo
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- CN104144906B CN104144906B CN201280071156.8A CN201280071156A CN104144906B CN 104144906 B CN104144906 B CN 104144906B CN 201280071156 A CN201280071156 A CN 201280071156A CN 104144906 B CN104144906 B CN 104144906B
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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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Abstract
Present disclose provides a kind of technique reclaiming PTA oxidation catalyst in PTA (high purity terephthalic acid) production process, it use a kind of acid catalyst containing hydrolysis organic ester gained reaction logistics.
Description
The application is a patent supplement of Indian patent application 1585/MUM/2011 filed in 27 days Mays in 2011, its
Full content will be by being specifically incorporated herein by reference.
Technical field
The present invention relates to a kind of integrated process, this technique reclaims during being involved in production high purity terephthalic acid (PTA)
Metallic catalyst, make use of a kind of acid catalyst containing organic ester hydrolysis gained reaction logistics.
Background technology
A large amount of methyl acetates produced are high purity terephthalic acid (PTA) factory and polyvinyl alcohol (PVA) factory
Accessory substance.Owing to methyl acetate is a kind of to be worth relatively low solvent, methyl acetate or with sale at low prices, or be hydrolyzed to be worth
Higher methyl alcohol and acetic acid, need after hydrolysis through conventional distil-lation technique.Hydrolysis is not easy to reach balance, the most unconverted
Methyl acetate needs to separate and recycle, and reason is that the existence of the low equilibrium constant and interference azeotropic mixture is to by common process water
Solve methyl acetate and cause suppression.
It is prepared with the liquid phase reactor of water that acetic acid (HOAc) and methyl alcohol (MeOH) can pass through methyl acetate (MeOAc).
MeOAc hydrolysis is reversible reaction, and reaction equilibrium constant K is relatively small.Therefore, H+ ion is used as catalyst to carry
Rise reaction rate.The strong acid such as sulfuric acid and hydrochloric acid can be used for producing H+ ion catalytic reaction.But, strong acid can be to whole technique
Cause corrosion.In order to eliminate described shortcoming, a kind of containing sulfonic acid (SO3H) strong cation-exchanging resin is commonly used for the acid of hydrolysis
Catalyst.
In the prior art it has been reported that the hydrolysis process of various methyl acetate.Such as, TWI322801B describes a kind of work
Skill, is involved in reactive distillation system hydrolysis methyl acetate solution, to produce two kinds of mixing in the presence of heterogeneous catalysis
Thing.By a kind of return-flow system equipped with heterogeneous catalysis, mixture is condensed and is back to reactive distillation system.
Korean Patent KR888065B1 has explained a kind of method hydrolyzing methyl acetate, and wherein, hydrolysis is equipped with solid in one
The reactor of catalyst completes.
GB687902 describe under superatmospheric power and the high temperature less than boiling point, water in the presence of hydrolyst
Solve methyl acetate.The catalyst used is a kind of strong acid, such as, equal to 0.05 to 2%, preferably approximately 1% reactant weight
Sulfuric acid, and other response parameter is temperature 48 to 1400 DEG C, maximum 10 atmospheric pressure of pressure.
CN101481293A discloses and a kind of is producing catalyzing hydrolysis by-product acetic acid methyl esters in high purity terephthalic acid
Technique.According to the content disclosed in CN101481293A, hydrolysis catalyst used by methyl acetate is heterogeneous catalysis.To the greatest extent
Managing this technique and can be said to be complete, CN101481293A does not refer to about reclaiming the problem of metallic catalyst used in synthesis PTA.
Another Chinese patent CN100418939C also discloses that in the technique of purified terephthalic, and hydrolysis is as accessory substance
The methyl acetate produced.This technique (as described in CN100418939C) have employed cation exchange tree in catalytic rectifying tower
Fat.
Although the related process of hydrolysis methyl acetate and production terephthalic acid (TPA) is explained, which process discussion is not had to have
Close the particular problem reclaiming metallic catalyst used in synthesis terephthalic acid (TPA).
Summary of the invention
The purpose of the disclosure:
The part purpose of the disclosure is described as follows:
One purpose of the disclosure is to provide a kind of integrated process, during it involves hydrolysis methyl acetate and remanufacture PTA
Methyl acetate.
Another object of the present disclosure is to provide the technique of a kind of simple economy, and to reclaim the methyl acetate during PTA produces, it makes
With a kind of acid catalyst being separated and recovered from from hydrolysis organic ester.
The other objects and advantages of the disclosure significantly more will reflect from following description with reference to the accompanying drawings, and it is not intended to be intended to limit
Determine the scope of the present invention.
The disclosure is summarized:
According to the disclosure, it is provided that a kind of technique reclaiming PTA oxidation catalyst in PTA production process, it use one
Acid catalyst containing hydrolysis organic ester gained reaction logistics；Described technique comprises the following steps:
I) in the presence of the first catalyst, the organic ester of a kind of carboxylic acid is hydrolyzed into carboxylic acid and alcohol respectively, to produce one containing
Stating carboxylic acid, described alcohol, water and the effluent stream of described first catalyst, wherein, described first catalyst is a kind of acidic catalyst
Agent；
Ii) alternatively, from described effluent stream, water and alcohol are removed；
Iii) Alkylaromatics selected from paraxylene and meta-xylene is done in oxidation liquid phase, there is the second catalysis at that time
Agent, including: i) selected from cobalt acetate and at least one slaine of manganese acetate, and ii) hydrogen bromide, it is intended to obtain one
Reactant mixture containing terephthalic acid (TPA) (TA)；
Iv) from reactant mixture, separate out described terephthalic acid (TPA), obtain a kind of mother liquor including described second catalyst；
V) process described mother liquor by described effluent stream, by oxalate denominationby, from described first catalyst, isolate described the
The acetic acid pair anion of two catalyst, obtains the mixture containing described second each insoluble salt of catalyst；And
Vi) it is recovered by centrifugation described second catalyst, separates the insoluble salt of described second catalyst.
Generally, described first catalyst is oxalic acid.
Generally, described carboxylic acid is 9:1 with the ratio of the first catalyst described in gained effluent stream in method step i).
Generally, at least one at least acetic acid, propionic acid and butyric acid of carboxylic acid.
Generally, at least one at least methyl alcohol, ethanol, isopropanol, n-butanol, amylalcohol and hexanol of alcohol.
Generally, ester is from any combination of carboxylic acid Yu 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 disclosure, ester is methyl acetate, and effluent stream contains acetic acid, methyl alcohol, oxalic acid and water.
Accompanying drawing explanation
Fig. 1 is the technique according to disclosure hydrolysis methyl acetate and equipment flowsheet；And
Fig. 2 illustrates a kind of integration flow chart hydrolyzing methyl acetate and reclaiming catalyst.
Detailed description of the invention
Hydrolyze in presence of an acid catalyst the technique of organic acid esters by the present inventor at co-pending application 1585/MUM/2011
Disclosed in, entire contents will be by being specifically incorporated herein by reference.
Present disclose provides the integration of a kind of hydrolysis process and high purity terephthalic acid (PTA) production technology, to produce
Journey reclaims PTA oxidation catalyst.As can be seen here, according to the disclosure, it is provided that a kind of recovery PTA in PTA production process
The technique of oxidation catalyst, it uses a kind of acid catalyst containing hydrolysis organic ester gained reaction logistics.
The organic ester hydrolyzed in a first step is from any combination of carboxylic acid Yu alcohol.As preferably, ester includes but not limited to second
Acid methyl esters, ethyl acetate, isopropyl acetate, n-butyl acetate, pentyl acetate and hexyl acetate.
According to one of them scheme of the disclosure, the weak acid such as carboxylic acid is used as the first catalyst.
As preferably, used catalyst is containing 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 disclosure, is described as below producing acetic acid, deposits at acid catalyst
Methyl acetate hydrolysis reaction under.
Organic ester methyl acetate (MeOAc) and water (H2O) react on single continuous reaction tower, its as a kind of reactor and
The combination of destilling tower, it is provided that sufficient holdup time, in the presence of the oxalic acid of catalyst, to reach by methyl acetate to first
Alcohol (MeOH) and the high conversion of acetic acid (HOAc).The methyl acetate and the water that newly add send into blender with supplementary oxalic acid.
Mixture streaming from blender enters the middle part of reaction tower (RD).Generally, the overhead product logistics from RD (contains about
88.2% methyl acetate, 11.4% methyl alcohol and 0.4% water) it is continuously introduced into blender.Bottoms product stream from RD usually contains
29.5%HOAc, 45.2% methyl acetate, 15.7% methyl alcohol and 9.6% oxalic acid.Unless otherwise prescribed, used herein all hundred
Proportion by subtraction is all weight percentage.Destilling tower (D1) is utilized to isolate the methyl alcohol of 98.3% purity from the bottoms product stream of RD.
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 azeotropic mixture that methyl acetate is formed with methyl alcohol,
D1 separates methyl alcohol the lightest.Tower bottom product in D1 is (containing 53.4% water, 35.1% acetic acid, 0.1% methyl alcohol and 11.4%
Oxalic acid) send into destilling tower D2.The overhead product of D2 contains 97.9% pure water and a small amount of acetic acid and methyl alcohol.The tower bottom product of D2
Comprise 73.6% acetic acid and 24.6% oxalic acid.Crystallizer (C1) is utilized to crystallize the oxalic acid in this logistics.Filter F 1 is utilized to tie
Brilliant thing is separated from acetic acid.
The function mode of reaction tower make its provide methyl acetate and water, acetic acid and methyl acetate/water azeotropic mixture and acetic acid and methyl alcohol/
Intimate contact between methyl acetate azeotropic mixture.By providing the intimate contact between reactant and product and from the tower of reaction tower
Remove product continuously at the bottom of top and tower, reach high conversion.
Methyl acetate and water are pressed the molar ratio range of 1:1 to 1:10 and are sent into reaction tower, preferably 1:1 to 1:5, and 1:3 to 1:5
Ratio is the most excellent.
Reaction tower routine operates on the temperature of about 40 to 90 DEG C.But, the ideal temperature for special process depends on ideal
Productivity ratio, working pressure.Conventional working pressure is about 1 to 2 atmospheric pressure.Generally it is desirable that operate on low temperature and low pressure.
The reactant mixture holdup time in reaction tower is also an important parameter of disclosure technique.Delay needed for higher conversion
Time depends on catalyst and catalyst concn.
The catalyst concn being supplied to reaction tower be enough to provide preferable catalytic effect.The most favourable side of catalyst is provided to reaction tower
Formula is to send into the aqueous solution of oxalic acid in the higher part position of tower.Alternatively, be wherein dissolved with a part of acetic acid of oxalic acid or acetic acid/
Aqueous mixtures is sent into by the higher part position of tower.There is 30% oxalic acid aqueous solution as catalyst, during the delay of disclosure technique
Between be at least 30 minutes.As preferably, the holdup time in reaction tower is about 30 to 45 minutes.Returning of disclosure technique
Stream ratio is at least about 1.32.Term reflow is than the ratio being defined as overhead reflux rate and overhead product flow rate.
Equipment M1 shown in accompanying drawing 1 includes a blender equipped with agitator A.This blender is labeled as M1, with pipe
Road 2 and pipeline 3 connect.RD is a reaction tower, is connected with the outlet of M1 by pipeline 4.The return duct road sign of RD
It is designated as pipeline 5 and pipeline 6, is connected with condenser H1.Another recirculating line 7 is connected to condenser H2, its outlet
Pipeline 8 is connected to pipeline 9.Pipeline 9 is connected to M1.Pipeline 10 and 11 is connected to by reboiler H3 at the bottom of the tower of RD.
The export pipeline 12 of RD is connected to destilling tower D1.Pipeline 13 connects condenser H4, and pipeline 14 is connected to D1.The tower of D1
Top export pipeline is labeled as pipeline 15.Article two, return line connection reboiler H5 at the bottom of tower, is respectively labeled as pipeline 16 and 17.Class
As, the tower bottom outlet pipeline 18 of D1 is connected to destilling tower D2.Overhead reflux pipeline 19 connects condenser H6 with 20.D2
Tower top outlet pipeline be labeled as pipeline 21.Article two, return line connection reboiler H7 at the bottom of tower, is respectively labeled as pipeline 22 and 23.
Crystallizer C1 is connected to by pipeline 24 at the bottom of the tower of D2.Filter F 1 is connected with crystallizer by pipeline 25.Pipeline 26 He
27 are also connected to filter F 1.
Methyl acetate sends into blender M1 by pipeline 9.Water sends into blender M1 by water inlet pipeline 2, and catalyst leads to
Cross pipeline 3 to introduce.Mixture containing methyl acetate, water and catalyst sends into reaction tower RD by pipeline 4.Reaction is instead
Carry out at Ying Tazhong 30 to 120 DEG C, preferably 90 to 100 DEG C.Destilling tower D1 is used for distilling out methyl alcohol (pipeline 15), and it leads to
Cross the pipeline 12 tower base stream from reaction tower.Similarly, destilling tower D2 is used for isolating acetic acid and oxalic acid (pipeline 24),
It passes through the pipeline 18 tower base stream from D1.The mixture of oxalic acid and acetic acid (pipeline 24) sends into crystallizer C1, at this
It is settled out oxalic acid.Mould temperature keeps 10 to 25 DEG C, preferably 15 to 18 DEG C.The catalyst of precipitation and separation is to pass through filter
F1, is isolated as far as possible many catalyst and acetic acid, and is sent by pipeline 26 and 27 respectively at this.
The effluent stream that hydrolysing carboxylic's organic ester produces contains carboxylic acid, alcohol, water and acid catalyst the most respectively.According to involved
Esters, the carboxylic acid being present in effluent stream can be acetic acid, propionic acid and butyric acid, and the alcohol of correspondence be probably methyl alcohol, ethanol,
Isopropanol, n-butanol, amylalcohol and hexanol.Alternatively, water and methyl alcohol remove from this logistics, thus obtain containing carboxylic acid and
A kind of effluent stream of acid catalyst.Generally, carboxylic acid and the ratio of described first catalyst (acid catalyst) in effluent stream
It is 9:1.This is the logistics 27 in Fig. 1.
The production of terephthalic acid (TPA) is by the temperature range of 150 to 210 DEG C, with air oxidation in liquid phase aromatics in acetic acid
Compound, it is selected from paraxylene and meta-xylene, and there is a kind of metal catalyst system (the second catalyst), including cobalt
Manganese bromide catalysts system (cobalt acetate, manganese acetate and hydrogen bromide).
It is important that the relative scale of cobalt, manganese and bromide, representative value is manganese: cobalt ratio is 3:1, cobalt: bromide ratio is 1:5.
In reaction tower and crystallizer, major part terephthalic acid (TPA) crystallizes from mother liquor and is isolated by filtration out.
Mother liquor mainly contains acetic acid, organic compound (such as M-phthalic acid, benzoic acid) and inorganic compound (such as cobalt and manganese
Compound), Yi Jitie, nickel, chromium and sodium.
According to the exemplary scenario of the disclosure, then process the mother liquor containing the second catalyst (metallic catalyst) and have employed effluent
Stream, it contains carboxylic acid and acid catalyst (oxalic acid), i.e. logistics 27 in Fig. 1, it is intended to reclaims and is present in mother with oxalate form
Metallic catalyst in liquid.Generally, by oxalate denominationby, the acetic acid pair anion of metallic catalyst is divided from acid catalyst
Separate out.This is shown in Fig. 2, and wherein, the hydrolyzable moiety of methyl acetate shows hydrolysis process and product, catalyst (oxalic acid)
Separation with acetic acid (logistics 27 in Fig. 1).Come from the logistics 27 (containing 90% acetic acid and 10% oxalic acid) of hydrolyzable moiety
Recovery for catalyst.
Logistics 27 in Fig. 1 mixes with the mother liquor containing inorganic metal catalyst in mixed zone.Oxalic acid in this logistics and cobalt and
The acetate reaction of manganese, forms respective oxalates, and it is by centrifugation and reclaims, it is also possible to be recycled to oxidation reaction tower.
Now quote following non-restrictive example to further describe the disclosure:
Example 1:
Example 1:
In a kind of exemplary apparatus of accompanying drawing 1, methyl acetate and water 1:5 by weight proportion adds to and there is the reaction tower of oxalic acid also
Stirring.Reaction continues 30 minutes at 65 DEG C.After having reacted, whole mixture distills and by cooling and isolating oxalic acid.
The acetic acid and the percentage methanol that are formed are respectively 55 and 45.
Example 2:
A kind of exemplary apparatus in fig 2 is divided into methyl acetate hydrolysis part and high purity terephthalic acid (PTA) technique
Catalyst recovery unit.This example follows the step of example 1.10% oxalic acid solution containing acetic acid is separated by cooling technique,
It is then sent for high purity terephthalic acid's catalyst recovery unit, separates with the form of oxalates at this cobalt and manganese.
In this specification, it should be understood that " including " or " containing " word be meant that include stated individual element, entirety or
Step, it is also possible to be to include multiple element, entirety or step, but be not precluded from any other individual element, entirety or step,
Also other multiple elements, entirety or step it are not excluded for.
Using wording " at least " or " at least one " to represent and use one or more elements, dispensing or quantity, this usage is likely to occur
In the solution of the present invention, it is intended to reach one or more preferable purpose or result.
About any discussion of file, bill, material, equipment, document etc. in this specification, its sole purpose is for the disclosure
A kind of background is provided.It should not make to recognize that any or all this type of item defines the part on prior art basis, or because of its
Present patent application had existed before preferential day and has become the common sense of relevant art.
The numerical value of mentioned various physical parameters, size or quantity is only approximation, it is contemplated that any one numerical value, if greater than/
Be less than the numerical value distributing to this type of parameter, size or quantity, then must be in the range of the disclosed invention, unless illustrated
Book has contrary statement.
Description to concrete scheme fully discloses the general aspects of scheme herein above so that it is other people can apply existing knowledge,
In the case of without departing from universal, easily revise and/or adjust this type of concrete scheme to be suitable for various application, therefore, it should and
Attempting to understand, this type of adjusts and amendment is in the meaning being equal to disclosed scheme and scope.Should be appreciated that wording used herein
Or term is non-limiting purpose for description.Therefore, although scheme is described with term " preferred version " herein, this area
Technical staff should appreciate that, in the spirit and scope of scheme described herein, scheme can be revised and implement herein.
Claims (21)
1. the technique reclaiming PTA oxidation catalyst in PTA production process, it uses a kind of anti-containing hydrolysis organic ester gained
Answer the acid catalyst of logistics；Described technique comprises the following steps:
I. in the presence of the first catalyst, the organic ester of a kind of carboxylic acid is hydrolyzed into carboxylic acid and alcohol respectively, contains producing one
Described carboxylic acid, described alcohol, water and the effluent stream of described first catalyst, wherein, described first catalyst is grass
Acid；
The most alternatively, from described effluent stream, water and alcohol are removed；
Iii. paraxylene is done in oxidation liquid phase, there is the second catalyst at that time, including: i) selected from cobalt acetate and
At least one slaine of manganese acetate, and ii) hydrogen bromide, it is intended to obtain a kind of containing terephthalic acid (TPA)
(PTA) reactant mixture；
Iv. from reactant mixture, separate out described terephthalic acid (TPA), obtain a kind of mother liquor including described second catalyst；
V. process described mother liquor by described effluent stream, by oxalate denominationby, isolate described from described first catalyst
The acetic acid pair anion of the second catalyst, obtains the mixture containing described second each insoluble salt of catalyst；With
And
Vi. it is recovered by centrifugation the insoluble salt of described second catalyst, separates the insoluble salt of described second catalyst.
Technique the most according to claim 1, wherein said oxalic acid provides to be dissolved in the aqueous solution or acetic acid or both oxalic acid.
Technique the most according to claim 2, wherein said oxalic acid provides with the oxalic acid being dissolved in the 5%-40% of the aqueous solution.
Technique the most according to claim 1, wherein carboxylic acid described in gained effluent stream and described first catalyst in method step i)
Ratio be 9:1.
Technique the most according to claim 1, at least one in acetic acid, propionic acid and butyric acid of wherein said carboxylic acid.
Technique the most according to claim 1, during wherein alcohol is selected from methyl alcohol, ethanol, isopropanol, n-butanol, amylalcohol and hexanol extremely
Few one.
Technique the most according to claim 1, wherein said ester is any from the carboxylic acid advocated respectively in claim 5 and 6 and alcohol
Combination.
Technique the most according to claim 7, wherein said ester is methyl acetate, ethyl acetate, isopropyl acetate, the positive fourth of acetic acid
Ester, pentyl acetate or hexyl acetate.
Technique the most according to claim 1, wherein the reaction tower temperature of hydrolysis is 40 to 90 DEG C, and pressure is 1 to 2 air
Pressure, in reaction tower, the holdup time is 30 to 45 minutes, and reflux ratio is at least 1.32.
Technique the most according to claim 1, described effluent stream contains carboxylic acid, alcohol, water and acid catalyst, and wherein said carboxylic acid is
Acetic acid, propionic acid or butyric acid, described alcohol is methyl alcohol, ethanol, isopropanol, n-butanol, amylalcohol or hexanol.
11. techniques according to claim 1, wherein said ester is methyl acetate, and described effluent stream contains acetic acid, methyl alcohol, oxalic acid
And water.
12. techniques according to claim 11, wherein in step i, methyl acetate and water are carried out by the molar ratio range of 1:1 to 1:10
Reaction.
13. techniques according to claim 11, wherein the removing alcohol from described effluent stream described in step ii is at destilling tower (D1)
In complete, the methanol purity distilled out is 98.3%, from destilling tower (D1) tower top outlet flow out.
14. techniques according to claim 13, wherein the removing water from described effluent stream described in step ii is at destilling tower (D2)
In complete, the water that obtains of distillation flows out from destilling tower (D2) tower top, and purity is 97.9%, destilling tower (D2) tower bottom product
For oxalic acid and the mixture of acetic acid, wherein destilling tower (D2) is connected with destilling tower (D1).
15. techniques according to claim 14, after wherein removing water and alcohol from described effluent stream, by the oxalic acid obtained and acetic acid
The crystallized device of mixture (C1) and filter (F1) process.
16. techniques according to claim 1, wherein manganese in step iii: cobalt ratio is 3:1, cobalt: hydrogen bromide ratio is 1:5.
17. techniques according to claim 1, wherein the reaction temperature of step iii is 150 to 210 DEG C.
18. according to the technique described in claim 1 or 14 or 15, and the mother liquor that wherein said step iv obtains contains acetic acid, organic compound
Thing, inorganic compound, iron, nickel, chromium and sodium, wherein said organic compound is M-phthalic acid and/or benzoic acid, described
Inorganic compound is the compound of cobalt and manganese.
19. techniques according to claim 18, the insoluble salt of the second catalyst described in wherein said step v and step vi is cobalt
Oxalates with manganese.
20. include one equipped with agitator (A) according to the technique described in claim 1 or 14 or 15, the equipment that wherein this technique uses
Blender, this blender is labeled as (M1), is connected with pipeline 2 and pipeline 3；(RD) it is a reaction tower, passes through
Pipeline 4 is connected with the outlet of (M1), and the return line of (RD) is labeled as pipeline 5 and pipeline 6, with condenser H1
Being connected, another recirculating line 7 is connected to condenser H2, and its export pipeline 8 is connected to pipeline 9, and pipeline 9 connects
To (M1), pipeline 10 and 11 is connected at the bottom of the tower of (RD) by reboiler H3, and the export pipeline 12 of (RD) is even
Receiving destilling tower D1, pipeline 13 connects condenser H4, and pipeline 14 is connected to the tower top outlet pipeline of D1, D1 and is labeled as pipe
Road 15, at the bottom of two towers, return line connection reboiler H5, is respectively labeled as pipeline 16 and 17, the tower bottom outlet pipeline of D1
18 are connected to destilling tower D2, and overhead reflux pipeline 19 connects the tower top outlet pipeline of condenser H6, D2 and is labeled as pipe with 20
Road 21, at the bottom of two towers, return line connection reboiler H7, is respectively labeled as pipeline 22 and 23；Crystallizer (C1) is by pipe
Road 24 is connected at the bottom of the tower of D2, and filter (F1) is connected with crystallizer (C1) by pipeline 25, and pipeline 26 and 27 is also
It is connected to filter (F1).
21. techniques according to claim 20, wherein said ester passes through pipeline 9 and sends into blender (M1), and water passes through entrance pipe
2 send into blender (M1), and catalyst is introduced by pipeline 3, and the mixture containing described ester, water and catalyst passes through pipeline
4 send into reaction tower (RD).
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| IN577MU2012 | 2012-03-05 | ||
| IN577/MUM/2012 | 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 CN104144906A (en) | 2014-11-12 |
| CN104144906B true 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 BR BR112014021765A patent/BR112014021765A2/en not_active IP Right Cessation
- 2012-04-20 WO PCT/IN2012/000291 patent/WO2013132507A1/en active Application Filing
- 2012-04-20 CN CN201280071156.8A patent/CN104144906B/en not_active Expired - Fee Related
- 2012-04-20 PT PT2012000291A patent/PT2013132507W/en unknown
-
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 |
|---|---|
| PT2013132507W (en) | 2015-05-20 |
| CN104144906A (en) | 2014-11-12 |
| BR112014021765A2 (en) | 2017-08-22 |
| WO2013132507A1 (en) | 2013-09-12 |
| HK1203479A1 (en) | 2015-10-30 |
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