CN105237390B - Recycling method of available substances in terephthalic acid industrial residue - Google Patents
Recycling method of available substances in terephthalic acid industrial residue Download PDFInfo
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- CN105237390B CN105237390B CN201510655342.1A CN201510655342A CN105237390B CN 105237390 B CN105237390 B CN 105237390B CN 201510655342 A CN201510655342 A CN 201510655342A CN 105237390 B CN105237390 B CN 105237390B
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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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- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/02—Preparation of carboxylic acids or their salts, halides or anhydrides from salts of carboxylic acids
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- 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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- C07C51/42—Separation; Purification; Stabilisation; Use of additives
- C07C51/487—Separation; Purification; Stabilisation; Use of additives by treatment giving rise to chemical modification
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- C07D233/00—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings
- C07D233/54—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members
- C07D233/56—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members with only hydrogen atoms or radicals containing only hydrogen and carbon atoms, attached to ring carbon atoms
- C07D233/58—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members with only hydrogen atoms or radicals containing only hydrogen and carbon atoms, attached to ring carbon atoms with only hydrogen atoms or radicals containing only hydrogen and carbon atoms, attached to ring nitrogen atoms
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Abstract
The invention discloses a recycling method of available substances in a terephthalic acid industrial residue, wherein the recycling method comprises the steps: 1) taking the PTA residue, adding an activated alumina auxiliary agent, heating, successively collecting a gasification product A (namely a mixture of benzoic acid and p-toluylic acid), a gasification product B (namely a mixture of o-phthalic acid and m-phthalic acid) and a gasification product C (namely terephthalic acid); taking the gasification product A, mixing with imidazole and a derivative thereof, taking deionized water as a solvent and zinc chloride as a catalyst, keeping constant temperature at the temperature of 100 DEG C for 1.0-1.5 hours, and thus obtaining a benzoic acid insoluble solid and a solution containing p-toluylic acid and imidazole or the derivative thereof; and mixing the gasification product B with a hydroxide, adding deionized water, keeping constant temperature at the temperature of 90 DEG C for 1.0-1.5 hours, filtering, to obtain a o-phthalate solution and a m-phthalate insoluble solid, filtering, then respectively acidifying to the pH value of 1.0, and precipitating to obtain o-phthalic acid and m-phthalic acid. The by-products in the residue are effectively separated, and secondary pollution is avoided from being caused.
Description
Technical field
The present invention relates to method at chemical products residue, refers in particular to p-phthalic acid industrial residu（PTA）In using thing
The recovery method of matter.
Background technology
With regard to the processing mode to PTA residues, at present major part enterprise or published processing method be using burning method,
Partially recycled utilization method and relatively sufficiently recycle method.
(1) burning method is adopted
Shen Fuchang application with regard to《PTA draff processing methods》（Application number：99114298.5）With《P-phthalic acid
(PTA) process for burning residual dregs》（Application number：01134015.0）, the two methods are substantially to adopt to be included being dried, lumps broken
It is broken, sieve, blasting jet, burning and vent gas treatment.Liu Meng application with regard to《A kind of high-moisture percentage PTA residue as resources is utilized
Method》（Application number：201310106761.0）, the method is ground to high-moisture percentage PTA residues, levigate and classification, is obtained
Pretreated high-moisture percentage PTA residue powder is mixed and is pressed into filter cake with activated sludge, then being burnt or
Pyrolysis.
The advantage of this several method is to efficiently solve PTA residue treatment problems, while can effectively make PTA residues
For the fuel of Industrial Boiler, it is allowed to turn waste into wealth, but its shortcoming is exactly that the utilization rate to resource is low.
(2) partially recycled utilization method
Wang Yong side application with regard to《A kind of method of recovery of benzoic acid in oxidation residua from PTA》（Application number：
201010185826.1）, the method includes residue hot water dissolving, filtration, hot filtrate is cooled down, crude benzol formic acid serosity is filtered, crude benzol
Six processes such as formic acid eliminating water, crude benzol formic acid rectifying, so as to industry benzoic acid and pure mixed phthalic acid product is obtained.Into promising Shen
Please with regard to《The method for reclaiming p-phthalic acid from coloured terephthalic acid residue using complexation-crystallization（Application number：
200810062425.X）, the method first mixes terephthalic acid residue in complexation-crystallization device with complexation-crystallization solvent, then
Control temperature at 10～120 DEG C, make pure terephthalate product with solvent complex thing crystallization in the form of separate out c and it is coloured miscellaneous
Matter is then enriched with the solution.Song Guoqiang application with regard to《One kind prepares pure mixed phthalic acid 2-glycidyl using PTA residues
The method of ester》（Application number：201410018692.2）, the method with PTA residues and epoxychloropropane as initiation material, add one
, in the presence of heating and catalyst, there is open loop and the esterification of epoxy first, then again in nothing in quantitative organic solvent
In the presence of machine alkali, there is ring-closure reaction, generate the sour water glyceride of final product pure mixed phthalic acid two.
Although being reclaimed to a certain extent to the side-product in PTA residues in this several method, generally reclaim
Rate is not high.
(3) relatively sufficiently recycle
Block up literary refined application with regard to《A kind of method of the recycling of PTA oxidation residuas（Application number：
201310410895.1）, the method mixes PTA oxidation residuas, water and oil phase extractant, after beating 0.1-5 hours, 20-200
At DEG C, 0.1-5 hours are extracted, obtain the material of solid phase, oil phase and water phase three phase separation；2）By step 1）The solid phase of resulting material,
Oil phase mutually is individually separated out with water；3）By step 2）Gained oil phase rectification respectively obtains benzoic acid and p-methylbenzoic acid, essence
Oil phase after evaporating is recycled；4）By step 2）Gained solid phase recrystallization obtains the mixture of M-phthalic acid and p-phthalic acid；
5）By step 2）Gained water is mutually removed after cobalt, manganese Metal ionic catalyst, the acid of flash separation aromatic acid, the premenstrual water stated after processing
Mutually recycle.Said method can be to the recycling of PTA oxidation residua systems, recyclable benzoic acid therein, isophthalic diformazan
Acid, p-phthalic acid and p-methylbenzoic acid component.
Xie Gang application with regard to《Extraction extracts benzoic acid, p-methylbenzoic acid, the terephthaldehyde in PTA oxidation residuas
Acid and M-phthalic acid》（Application number：201210321034.1, the method is first organic solvent A to be added in PTA oxidation residuas
Extracted, then filtered, filtrate is gone decanter to be layered as oil phase and water phase, and filtration cakes torrefaction is obtained and slightly mix phthalic acid；By oil phase
Solvent evaporator is pumped into, the discharging of solvent evaporator bottom send benzoic acid rectifying column, the discharging of benzoic acid rectifying column bottom to send to methylbenzene first
Sour rectifying column, benzoic acid rectifying tower top distillation is high-purity benzene formic acid product, and p-methylbenzoic acid rectifying tower top distillation is
High-purity p-methylbenzoic acid product；Add solvent B to be extracted in thick mixed phthalic acid, filter, filter cake adds solvent B
Extracted, filtered, mixed phthalic acid product is obtained after filtration cakes torrefaction；
In both approaches, be all to be that based on extraction and the way of distillation, it has the disadvantage to be easily caused secondary pollution, and
It is relatively costly.
In recent years, as petrochemical enterprise in China PTA (p-phthalic acid) is newly-built and expands the successive operation of energy project, I
State's PTA industries obtain fast development.2010 gross annual output amounts reach 10,000,000 tons, it is contemplated that the PTA production capacity of China in 2015
It is up to 20,000,000 tons.The raising of PTA yield causes the yield of PTA device oxidized byproducts also to increase year by year.PTA oxygen
Change PTA Equipment xylol (PX) the oxidative synthesis p-phthalic acid (PTA) that residue is petrochemical enterprise
The by-product of process, the Organic substance for containing mainly has benzoic acid, p-methylbenzoic acid, phthalic acid, M-phthalic acid and right
Five kinds of materials of phthalic acid, discharge capacity accounts for the 1.0% of PTA production capacities.It is domestic at present main using burning, extraction or way of distillation etc.
Processing method, although this several method solves to a certain extent the pollution problem of PTA residues, generally not to PTA
By-product effectively utilizes in residue, but also easily cause a certain degree of secondary pollution.
The content of the invention
It is an object of the invention to provide using the recovery method of material in a kind of p-phthalic acid industrial residu, it can be with
Efficiently separate the by-product in residue, it is to avoid cause secondary pollution.
For achieving the above object, solution of the invention is：
Using the recovery method of material in a kind of p-phthalic acid industrial residu, its step includes：
Step 1, PTA residues are taken, it is 1 to add with PTA mass of residue ratio：0.4 activated alumina auxiliary agent, then in nitrogen
Under protection, it is heated to 150 DEG C and collects gasification product A, i.e. benzoic acid and p-methylbenzoic acid mixture；When the gasification for obtaining is produced
When the quality of thing keeps constant, continue to be heated to 220-230 DEG C and collect gasification product B, i.e. phthalic acid and isophthalic diformazan
Acid blend；When the quality of the gasification product for obtaining keeps constant, continue to be heated to 290-300 DEG C and collect gasification product
DEG C, i.e. p-phthalic acid, until the quality of the gasification product for obtaining keeps constant, stopping is heated and cooled down；
The separation of step 2, gasification product A：
It is 1 that gasification product A and imidazoles or derivatives thereof are taken according to mass ratio:The ratio of 1-4 is mixed, and is added and gasification
Generation A mass ratio is 1:The deionized water of 1-3, and 1:0.01-0.05 zinc chloride, then under the protection of nitrogen, in 80-
Constant temperature 1.0-1.5 hours at 120 DEG C, filter, and obtain final product benzoic acid insoluble solids and the saline solution of imidazoles containing p-methylbenzoic acid, mistake
Filter, obtains final product benzoic acid insoluble solids and the saline solution of imidazoles containing p-methylbenzoic acid, then will contain p-methylbenzoic acid imidazole salts molten
Liquid is acidified, i.e., pH value is 1.0-2.0, obtains final product p-methylbenzoic acid precipitate；
The separation of step 3, gasification product B：
It is 1 according to mol ratio by gasification product B and hydroxide：1 ratio is mixed, and adds deionized water quality
Than：1:10-20, and the constant temperature 1.0-1.5 hours at 60-100 DEG C, filter, and obtain final product the solution and isophthalic two of phthalate
The insoluble solids of formates, are then respectively acidified them, i.e., pH value is 0.5-3.0, you can separate out phthalic acid and isophthalic
Dioctyl phthalate.
Imidazoles of the step 2 or derivatives thereof is imidazoles, methylimidazole or diethyl tetramethyl imidazoles.
The hydroxide of the step 3 is calcium hydroxide, barium hydroxide, Copper hydrate or cobalt hydroxide.
After such scheme, the present invention has mainly been fully understood by the excellent of the existing handling process to PTA residues and has lacked
Point, while fully analyzing and have studied the construction featuress of five kinds of by-products in PTA residues, proposes following some separation thinking：
(1) when structure or the different position of the substituent group on phenyl ring, its fusing point or gasification temperature to material also can
Have a certain impact（The different vapourizing temperatures of five kinds of materials are as shown in Figure 2）, so as to propose first with thermal analysis system to five
The initial gross separation of by-product is planted, by controlling different gasification temperatures, so as to respectively obtain benzoic acid and p-methylbenzoic acid,
Three kinds of separators of phthalic acid and M-phthalic acid and p-phthalic acid（Heat analysis separating resulting is as shown in Figure 3）, and PTA
Metal compound as catalyst is separated due to difficult gasification in residue.
(2) separation of benzoic acid and p-methylbenzoic acid：Whether contain alkyl substituent on phenyl ring, be synthesis imidazole type
The key character of ionic liquid, based on the principle, adopts with zinc chloride as catalyst, p-methylbenzoic acid and benzoic acid and miaow
Azoles or derivatives thereof carries out reacting by heating, so as to obtain the class ionic liquid of p-methylbenzoic acid-imdazole derivatives, and benzene first
Acid cannot generate class ionic liquid with imidazole and its derivants, it is achieved thereby that p-methylbenzoic acid and benzoic separation.
(3) separation of phthalic acid and M-phthalic acid：The structure of phthalic acid and M-phthalic acid is distinguished
The difference of the position of two carboxylic acid substituents on its phenyl ring.Two carboxylic acids on phthalic acid it is closer to the distance, easily with
Some metal ions form the coordination compound with chelate ring；And two carboxylic acids on M-phthalic acid is distant, Zhi Nengyu
Some catenulate coordination polymers of metal ion shape, and the difference of structure, have largely shadow to the dissolubility of coordination compound
Ring.Therefore, based on features described above, the present invention is using metal hydroxidess and phthalic acid and the water of M-phthalic acid complex
Solution is reacted, it is achieved thereby that the separation of phthalic acid and M-phthalic acid.
Description of the drawings
Fig. 1 is the process flow diagram of the present invention；
Fig. 2 is the graph of a relation of the quality with gasification temperature of five kinds of pure materials；
（A benzoic acid b p-methylbenzoic acids c phthalic acid d M-phthalic acid e p-phthalic acids in figure）
Fig. 3 is the relation of the quality with gasification temperature of three kinds of different mixture.
（A in figure:The mixture of benzoic acid and p-methylbenzoic acid
b:The mixture of phthalic acid, M-phthalic acid and p-phthalic acid
c:Benzoic acid, p-methylbenzoic acid, phthalic acid, five kinds of materials of M-phthalic acid and p-phthalic acid it is mixed
Compound).
Specific embodiment
Coordinate shown in Fig. 1, present invention is disclosed using the recovery method of material in a kind of p-phthalic acid industrial residu,
Its step includes：
Step 1, PTA residues are taken, it is 1 to add with PTA mass of residue ratio：0.4 activated alumina auxiliary agent, then in nitrogen
Under protection, it is heated to 150 DEG C and collects gasification product A, i.e. benzoic acid and p-methylbenzoic acid mixture；When the gasification for obtaining is produced
When the quality of thing keeps constant, continue to be heated to 220-230 DEG C and collect gasification product B, i.e. phthalic acid and isophthalic diformazan
Acid blend；When the quality of the gasification product for obtaining keeps constant, continue to be heated to 290-300 DEG C and collect gasification product
DEG C, i.e. p-phthalic acid, until the quality of the gasification product for obtaining keeps constant, stopping is heated and cooled down；
The separation of step 2, gasification product A：
It is 1 that gasification product A and imidazoles or derivatives thereof are taken according to mass ratio:The ratio of 1-4 is mixed, and is added and gasification
Product A mass ratioes are 1:The deionized water of 1-3, and 1:0.01-0.05 zinc chloride, then under the protection of nitrogen, in 80-120
Constant temperature 1.0-1.5 hours at DEG C, filter, and obtain final product benzoic acid insoluble solids and the saline solution of imidazoles containing p-methylbenzoic acid, then will
P-methylbenzoic acid imidazoles saline solution is acidified, i.e., pH value is 1.0-2.0, obtains final product p-methylbenzoic acid precipitate；Described
Imidazoles or derivatives thereof is imidazoles, methylimidazole or diethyl tetramethyl imidazoles.
The separation of step 3, gasification product B：
It is 1 according to mol ratio by gasification product B and hydroxide：1 ratio is mixed, and described hydroxide is hydrogen-oxygen
Change calcium, barium hydroxide, Copper hydrate or cobalt hydroxide；And add deionized water quality ratio：1:10-20, and at 60-100 DEG C
Constant temperature 1.0-1.5 hours, filter, and the insoluble solids of phthalic acid saline solution and M-phthalic acid salt are obtained final product, then by them
It is acidified respectively, i.e., pH value is 0.5-3.0, you can separate out phthalic acid and M-phthalic acid.
50 grams of PTA residues are taken, 10 grams of activated alumina auxiliary agents are added（The quality of sample：The quality of aluminium oxide is about 1：
0.4）, then under nitrogen protection, it is heated to 150 degree with the heating rate of about 15 DEG C/min and collects gasification product A（Gross mass
For 32.5 grams）；When the quality of the gasification product for obtaining keeps constant, continuation is heated to the heating rate of about 15 DEG C/min
220-230 DEG C and collect gasification product B（Gross mass is 5.3 grams）, when the quality of the gasification product for obtaining keeps constant, continue
290-300 DEG C is heated to certain heating rate and collect gasification product C（Gross mass is 10.8 grams）, until the gasification for obtaining
The quality of product keeps constant, and stopping is heated and cooled down.
(1) gasification product A（Benzoic acid and p-methylbenzoic acid mixture）Separation
A () takes 20 grams of gasification product A and mixes with 21 grams of imidazoles, the deionized water and 0.4 gram of zinc chloride of 30 milliliters of addition,
Then under the protection of nitrogen, in 100 DEG C or so lower constant temperature 1.0-1.5 hours, filter, obtain final product benzoic acid insoluble solids and containing right
Ar-Toluic acid imidazoles saline solution, filters, and benzoic acid is carried out into recrystallization, obtains 15.2 grams of benzoic acid.Simultaneously also to methylbenzene
Formic acid imidazoles saline solution is acidified（PH value is about 1.0-2.0）, obtain final product 3.6 grams of p-methylbenzoic acid precipitates.
B () takes 20 grams of gasification product A and mixes with 32 grams of methylimidazoles, add 30 milliliters deionized water and 0.4 gram
Zinc chloride, then under the protection of nitrogen, in 100 DEG C or so lower constant temperature 1.0-1.5 hours, filters, and obtains final product benzoic acid insoluble solid
Body and the saline solution of imidazoles containing p-methylbenzoic acid, filter, and benzoic acid is carried out into recrystallization, obtain 15.5 grams of benzoic acid.Simultaneously
P-methylbenzoic acid imidazoles saline solution is acidified（PH value is about 1.0-2.0）, obtain final product 3.4 grams of p-methylbenzoic acid precipitates.
C () gas takes 20 grams of gasification product A and mixes with 43 grams of diethyl tetramethyl imidazoles, add 30 milliliters of deionized water
And 0.4 gram of zinc chloride, then under the protection of nitrogen, in 100 DEG C or so lower constant temperature 1.0-1.5 hours, filter, obtain final product benzoic acid
Insoluble solids and the saline solution of imidazoles containing p-methylbenzoic acid, filter, and benzoic acid is carried out into recrystallization, obtain 15.1 grams of benzoic acid.
Simultaneously also p-methylbenzoic acid imidazoles saline solution is acidified（PH value is about 1.0-2.0）, obtain final product 3.1 grams of p-methylbenzoic acid analysis
Go out thing.
(2) gasification product B（Phthalic acid and isophthalic acid mixtures）Separation
A 5.0 grams of gasification product B and 3.6 grams of barium hydroxide are 1 according to mol ratio by ()：1 ratio is mixed, and is added
About 50 milliliters of deionized water, and in 90 DEG C or so lower constant temperature 1.0-1.5 hours, filter, obtain final product the solution of phthalate
And the insoluble solids of M-phthalic acid salt, then they are acidified respectively（PH value is about 1.0）, you can separate out 3.2 grams of adjacent benzene two
Formic acid and 1.3 grams of M-phthalic acids.
B 5.0 grams of gasification product B and 2.2 grams of calcium hydroxide are 1 according to mol ratio by ()：1 ratio is mixed, and is added
About 50 milliliters of deionized water, and in 90 DEG C or so lower constant temperature 1.0-1.5 hours, filter, obtain final product the solution of phthalate
And the insoluble solids of M-phthalic acid salt, then they are acidified respectively（PH value is about 1.0）, you can separate out 3.3 grams of adjacent benzene two
Formic acid and 1.1 grams of M-phthalic acids.
5.0 grams of gasification product B and 2.8 grams of Copper hydrates are 1 according to mol ratio by (DEG C)：1 ratio is mixed, and is added
About 50 milliliters of deionized water, and in 90 DEG C or so lower constant temperature 1.0-1.5 hours, filter, obtain final product the solution of phthalate
And the insoluble solids of M-phthalic acid salt, then they are acidified respectively（PH value is about 1.0）, you can separate out 3.0 grams of adjacent benzene two
Formic acid and 1.1 grams of M-phthalic acids.
As can be seen here, the present invention is that position based on the substituent group on phenyl ring is different, so as to cause its with some metals from
Son reaction and the also different principle of dissolubility of compound that generates realize the separation of phthalic acid and M-phthalic acid；Profit
The method for generating class ionic liquid with p-methylbenzoic acid and imdazole derivatives realize benzoic acid and p-methylbenzoic acid point
From.It is thus achieved that efficiently separating the by-product in residue, it is to avoid cause secondary pollution.
The above, is only the embodiment of the present invention, and not the technical scope of the present invention is imposed any restrictions, therefore every
According to any trickle amendment, equivalent variations and modification that the technical spirit of the present invention is made to above example, this is still fallen within
In the range of inventive technique scheme.
Claims (2)
1., using the recovery method of material in a kind of p-phthalic acid industrial residu, its step includes：
Step 1, PTA residues are taken, it is 1 to add with PTA mass of residue ratio：0.4 activated alumina auxiliary agent, then protects in nitrogen
Under, it is heated to 150 DEG C and collects gasification product A, i.e. benzoic acid and p-methylbenzoic acid mixture；When the gasification product for obtaining
When quality keeps constant, continue to be heated to 220-230 DEG C and collect gasification product B, i.e. phthalic acid to mix with M-phthalic acid
Compound；When the quality of the gasification product for obtaining keeps constant, continue to be heated to 290-300 DEG C and collect gasification product C, i.e., it is right
Phthalic acid, until the quality of the gasification product for obtaining keeps constant, stopping is heated and cooled down；
The separation of step 2, gasification product A：
It is 1 that gasification product A and imidazoles or derivatives thereof are taken according to mass ratio:The ratio of 1-4 is mixed, and is added and gasification product
A mass ratioes are 1:The deionized water of 1-3, and 1:0.01-0.05 zinc chloride, then under the protection of nitrogen, at 80-120 DEG C
Constant temperature 1.0-1.5 hours, filter, and obtain final product benzoic acid insoluble solids and the solution containing p-methylbenzoic acid imidazole salts, then will contain
The solution of p-methylbenzoic acid imidazole salts is acidified, i.e., pH value is 1.0-2.0, obtains final product p-methylbenzoic acid precipitate；It is described
Imidazoles or derivatives thereof is imidazoles, methylimidazole or diethyl tetramethyl imidazoles；
The separation of step 3, gasification product B：
It is 1 according to mol ratio by gasification product B and hydroxide：1 ratio is mixed, and adds deionized water quality ratio：1:
10-20, and the constant temperature 1.0-1.5 hours at 60-100 DEG C, filter, and obtain final product the solution and M-phthalic acid salt of phthalate
Insoluble solids, then they are acidified respectively, i.e., pH value is 0.5-3.0, you can separate out phthalic acid and M-phthalic acid.
2. using the recovery method of material in p-phthalic acid industrial residu as claimed in claim 1, it is characterised in that：Institute
The hydroxide for stating step 3 is calcium hydroxide, barium hydroxide, Copper hydrate or cobalt hydroxide.
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| CN105237390B true CN105237390B (en) | 2017-04-12 |
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| US7285677B1 (en) * | 2006-11-13 | 2007-10-23 | Mechema Chemicals International Corp. | System and method for recovering CTA residues and purifying/regenerating catalyst |
| US9205388B2 (en) * | 2007-06-27 | 2015-12-08 | H R D Corporation | High shear system and method for the production of acids |
| CN102786412B (en) * | 2012-09-03 | 2014-09-03 | 绍兴汉青环保科技有限公司 | Extraction method for extracting benzoic acid, p-toluic acid, terephthalic acid and isophthalic acid from pure terephthalic acid (PTA) oxidation residues |
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