CN101121655A - Technique for purifying crude terephthalic acid - Google Patents
Technique for purifying crude terephthalic acid Download PDFInfo
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- CN101121655A CN101121655A CNA2007100706185A CN200710070618A CN101121655A CN 101121655 A CN101121655 A CN 101121655A CN A2007100706185 A CNA2007100706185 A CN A2007100706185A CN 200710070618 A CN200710070618 A CN 200710070618A CN 101121655 A CN101121655 A CN 101121655A
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- terephthalic acid
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Abstract
The invention is a purification process of the crude terephthalic acid. The method is: first, the crude terephthalic acid and water recycled from the dyeing wastewater are put into the dissolving container in order according to the ratio of 3 to 10; then the mixture uniformly is stired and heated up; uniformly the ammonia or ammonium bicarbonate are add with the concentration of 18 to 27 percent and the pH value above 8; after the temperature rises to about 60 to 95 Celsius system, the mixture is kept for 20 to 50 minutes so that the terephthalic acid can completely react and produce the terephthalic ammonium; secondly, while the mixture is hot, the terephthalic ammonium solution is filtered to remove the tiny insoluble solid particles; thirdly, the filtered solution is cooled to be below 10 Celsius system and the terephthalic ammonium crystal is crystallized; the white needle-shaped terephthalic ammonium crystal can be got after the filtration; the soluble impurities are separated; fourthly, the terephthalic ammonium crystal is put into the vacuum drying decomposition container; when the temperature is between 120 and 180 Celsius system for 2 to 6 hours, dehydrate and the terephthalic ammonium is decomposed to be terephthalic acid and ammonia; the purity of the acquired terephthalic acid is above 98 percent. The ammonia can be dissolved for use after absorption.
Description
Technical field
What the present invention relates to is a kind of purifying process that proposes at the crude terephthalic acid of the high impurity multicomponent of the water ratio that reclaims in printing and dyeing enterprise alkali decrement waste water complexity, and the purifying that terephthalic acid that it reclaims for polyethylene terephthalate (PET) alkaline hydrolysis that will give up and p xylene oxidation are produced the terephthalic acid that reclaims in the terephthalic acid wastewater is also suitable fully.
Background technology
The alkali decrement be textile printing and dyeing enterprises to polyester piece good at high temperature to terylene macromole ester linkage hydrolyzing, corrosion, impel fibrous tissue lax, alleviate fabric weight, thereby make fabric have a kind of novel process of silky touch.But alkali decrement process has produced organic waste lye that a large amount of high densitys contain phenyl ring, and COD is up to 6000-15000, and its main component has para-phthalic sodium, ethylene glycol etc., is difficult to handle, and becomes one of primary pollution source of enterprise.This part sewage is more difficult, if the terephthalic acid in the waste liquid is reclaimed, not only can reduce pollution load (COD) significantly, and its terephthalic acid also can be used as important Organic Chemicals and is able to recycling.More domestic enterprise implements the terephthalic acid recovery measure, COD is significantly reduced, but each enterprise's dyeing and printing process difference, alkali decrement waste water component complexity, pre-treatment and acid out process unit imperfection, recovery slightly to dioctyl phthalate particle diameter little (being generally 5-10um) filtration difficulty, water ratio big (more than 50%), impurity height (reaching more than 15% in siccative) is difficult to directly utilize as industrial chemicals, and having wasted resource influences environment again.
Chinese patent CN680261A discloses a kind of on October 12nd, 2005 " the crude terephthalic acid method of purification ", but existing ball milling becomes the 1-5um particle to make filtration difficulty, it is many to filter back water ratio high residue soluble impurity, and energy consumption for drying is big, and non-water soluble impurity is difficult to defectives such as removal again.
Summary of the invention
The objective of the invention is to overcome the deficiency of above-mentioned existence, and provide a kind of according to terephthaldehyde's acid ammonium salt solvability and crystallinity principle, impurity is removed in separation reaches more than 98% the purity of terephthalic acid, can be used as important chemical material, be used for the manufacturing of softening agent and coating resin, realize the purifying process of the crude terephthalic acid of recycling.
1), with the crude terephthalic acid and the water that reclaim in the dyeing waste water the objective of the invention is to finish by following technical solution: it is:, press 3-10 solid water ratio, add dissolution vessel successively, stirring all then, spoon begins to heat up, and all spoon adding concentration is 18-27% ammoniacal liquor or bicarbonate of ammonia, pH value is warming up to about 60--95 ℃ and is incubated 20-50 minute more than 8, makes the terephthalic acid complete reaction generate the terephthalic acid ammonium; 2), terephthaldehyde's acid ammonium solution of the above-mentioned formation of filtered while hot is removed the insoluble solid finely ground particles; 3), filtrate is cooled to below 10 ℃, terephthalic acid ammonium crystal is separated out, after the filtration white needles terephthalic acid ammonium crystal, soluble impurity is separated; 4), with terephthalic acid ammonium crystal, put into the vacuum-drying splitter, 120-180 ℃ of scope, 2-6 hour, dewater and make the terephthalic acid ammonium resolve into terephthalic acid and ammonia, gained terephthalic acid purity reaches more than 98%.
When equal spoon adding concentration of the present invention is 18-27% ammoniacal liquor or bicarbonate of ammonia, also be added with a kind of decolouring absorption impurity in activated carbon or the carclazyte sorbent material, the consumption of sorbent material is the 2-4% of crude terephthalic acid siccative; The ammonia water that thermolysis is emitted absorbs into ammoniacal liquor, can return the crude terephthalic acid dissolving and use.
Described with the crude terephthalic acid and the water that reclaim in the dyeing waste water, than 5, add dissolution vessel by solid water successively, also adding concentration is 22% ammoniacal liquor or bicarbonate of ammonia, pH value is warming up to about 90 ℃ and is incubated 30 minutes more than 8, makes the terephthalic acid complete reaction generate the terephthalic acid ammonium; With terephthalic acid ammonium crystal, the temperature of putting into the vacuum-drying splitter is 130-160 ℃ of scope, 3-5 hour, dewaters and makes the terephthalic acid ammonium resolve into terephthalic acid and ammonia.
The present invention is directed to the feature of the wet crude terephthalic acid of dyeing waste water recovery, according to terephthaldehyde's acid ammonium salt solvability and crystallinity principle, remove insoluble and water-soluble impurity simultaneously, improve crystal grain and be beneficial to filter operation, improve the purity drop cost, the purity of terephthalic acid is reached more than 98%,, be used for the manufacturing of softening agent and coating resin as important chemical material.Purification media can be recycled, and realizes the optimization utilization of resource, has good benefits in environment and economic benefit.
Description of drawings
Fig. 1 is a crude terephthalic acid purifying process process schematic block diagram of the present invention.
Embodiment
1), with the crude terephthalic acid and the water that reclaim in the dyeing waste water the present invention will be described in detail below in conjunction with drawings and Examples: purifying process of the present invention is:, press 3-10 solid water ratio, add dissolution vessel successively, stirring all then, spoon begins to heat up, and all spoon adding concentration is 18-27% ammoniacal liquor or bicarbonate of ammonia, pH value is warming up to about 60--95 ℃ and is incubated 20-50 minute more than 8, makes the terephthalic acid complete reaction generate terephthaldehyde's acid ammonium solution; At dissolved simultaneously, according to the application product requirement, can select sorbent materials such as activated carbon or carclazyte, to the crude terephthalic acid decolouring with remove trace impurity, the consumption of sorbent material is the 2-4% of crude terephthalic acid siccative, and their regeneration backs are reusable; 2), remove the insoluble solid finely ground particles, promptly insoluble solid phase impurity with terephthaldehyde's acid ammonium solution of the above-mentioned formation of filtration such as vacuum, whizzer or board and frame machine while hot; 3), filtrate is cooled to below 10 ℃, terephthalic acid ammonium crystal is separated out, after the filtration white needles terephthalic acid ammonium crystal, soluble impurity is separated; 4), with terephthalic acid ammonium crystal, put into the vacuum-drying splitter, 120-180 ℃ of scope, 2-6 hour, after dehydrating, make the terephthalic acid ammonium resolve into terephthalic acid and ammonia, gained terephthalic acid purity reaches more than 98%, can be used as to produce softening agent dioctyl terephthalate (DOTP) and coating resin raw materials for production; 5), with the ammonia water of emitting absorb ammoniacal liquor, can return crude terephthalic acid dissolving and use, realized the recycle of purified feed stock ammoniacal liquor.
Embodiment 1
Get the wet crude terephthalic acid (water ratio 50% that acid out reclaims in certain printing and dyeing enterprise alkali decrement waste water, butt meter terephthaldehyde acid content 84%) 100g, water 200ml, activated carbon 2g adds in the there-necked flask of band stirring arm successively, stir into equal spoon water slurry, progressively heat up, and evenly add 25% ammoniacal liquor 60ml, PH is 8.2, progressively be warming up to 90 ℃, be incubated 30 minutes; With hot solution vacuum filtration in Bu Shi leaks, adularescent insolubles particle on the filter paper; Filtrate is cooled to 5 ℃ with frozen water, and terephthalic acid ammonium crystal is separated out, and uses the B vacuum filtration; Filter cake terephthalic acid ammonium is put into there-necked flask, vacuumize down and be heated to 150 ℃ of insulations 3 hours, dehydrate and resolve into: terephthalic acid and ammonia, get terephthalic acid 39g, purity is 98.52%.Decompose the ammonia water of emitting and in absorption bottle, reclaim ammoniacal liquor, return dissolver and recycle.
Embodiment 2.
Get the wet crude terephthalic acid (water ratio 50% that acid out reclaims in certain printing and dyeing enterprise alkali decrement waste water, butt meter terephthaldehyde acid content 84%) 100g, water 330ml adds in the there-necked flask of band stirring arm successively, stirs into equal spoon water slurry, progressively heat up, and evenly adding bicarbonate of ammonia 80g (for preventing the CO2 foam, reinforced wanting slowly of initial stage), PH is 8.2, be warming up to 90 ℃, be incubated 30 minutes; With hot solution vacuum filtration in Bu Shi leaks, adularescent insolubles particle grain on the filter paper; Filtrate is cooled to 5 ℃ with frozen water, and terephthalic acid ammonium crystal is separated out, and uses the B vacuum filtration; Filter cake terephthalic acid ammonium is put into there-necked flask, vacuumize down and be heated to 150 ℃ of insulations 3 hours, dehydrate and resolve into: terephthalic acid and ammonia, get terephthalic acid 40g, purity is 98.22%.Decompose the ammonia water of emitting and in absorption bottle, reclaim ammoniacal liquor, return dissolving and use.
Claims (3)
1. the purifying process of a crude terephthalic acid, 1), with the crude terephthalic acid and the water that reclaim in the dyeing waste water it is:, press 3-10 solid water ratio, add dissolution vessel successively, stirs equal spoon then and begin to heat up, and all spoon adding concentration is 18-27% ammoniacal liquor or bicarbonate of ammonia that pH value is more than 8, be warming up to about 60--95 ℃ and be incubated 20-50 minute, make the terephthalic acid complete reaction generate the terephthalic acid ammonium; 2), terephthaldehyde's acid ammonium solution of the above-mentioned formation of filtered while hot is removed the insoluble solid finely ground particles; 3), filtrate is cooled to below 10 ℃, terephthalic acid ammonium crystal is separated out, after the filtration white needles terephthalic acid ammonium crystal, soluble impurity is separated; 4), with terephthalic acid ammonium crystal, put into the vacuum-drying splitter, 120-180 ℃ of scope, 2-6 hour, dewater and make the terephthalic acid ammonium resolve into terephthalic acid and ammonia, gained terephthalic acid purity reaches more than 98%.
2. the purifying process of crude terephthalic acid according to claim 1, when it is characterized in that described equal spoon adding concentration is 18-27% ammoniacal liquor or bicarbonate of ammonia, also be added with a kind of decolouring absorption impurity in activated carbon or the carclazyte sorbent material, the consumption of sorbent material is the 2-4% of crude terephthalic acid siccative; The ammonia water that thermolysis is emitted absorbs into ammoniacal liquor, can return the crude terephthalic acid dissolving and use.
3. the purifying process of crude terephthalic acid according to claim 1, it is characterized in that described with the crude terephthalic acid and the water that reclaim in the dyeing waste water, press solid water than 5, add dissolution vessel successively, also adding concentration is 22% ammoniacal liquor or bicarbonate of ammonia, pH value is warming up to about 90 ℃ and is incubated 30 minutes more than 8, makes the terephthalic acid complete reaction generate the terephthalic acid ammonium; With terephthalic acid ammonium crystal, the temperature of putting into the vacuum-drying splitter is 130-160 ℃ of scope, 3-5 hour, dewaters and makes the terephthalic acid ammonium resolve into terephthalic acid and ammonia.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNA2007100706185A CN101121655A (en) | 2007-08-30 | 2007-08-30 | Technique for purifying crude terephthalic acid |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNA2007100706185A CN101121655A (en) | 2007-08-30 | 2007-08-30 | Technique for purifying crude terephthalic acid |
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| CN101121655A true CN101121655A (en) | 2008-02-13 |
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| CNA2007100706185A Pending CN101121655A (en) | 2007-08-30 | 2007-08-30 | Technique for purifying crude terephthalic acid |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101503353B (en) * | 2009-03-05 | 2012-05-09 | 浙江大学 | Technique for purifying crude terephthalic acid from alkali deweighting wastewater |
| CN103922926A (en) * | 2014-04-17 | 2014-07-16 | 绍兴县远程树脂科技有限公司 | Process for purifying residual solid waste generated after alkali peeling wastewater treatment |
| CN106588638A (en) * | 2016-11-28 | 2017-04-26 | 钱胜文 | Method of purifying pure terephthalic acid (PTA) by means of white mud after treatment of textile alkali dissolution waste water and crude terephthalic acid after degradation of waste Dacron silk cloth |
| CN106966892A (en) * | 2017-04-01 | 2017-07-21 | 来安县万博丰环保科技有限公司 | A kind of purifying process of crude terephthalic acid |
| CN107774329A (en) * | 2016-08-29 | 2018-03-09 | 中国石油化工股份有限公司 | A kind of metal-organic framework materials and preparation method thereof |
-
2007
- 2007-08-30 CN CNA2007100706185A patent/CN101121655A/en active Pending
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101503353B (en) * | 2009-03-05 | 2012-05-09 | 浙江大学 | Technique for purifying crude terephthalic acid from alkali deweighting wastewater |
| CN103922926A (en) * | 2014-04-17 | 2014-07-16 | 绍兴县远程树脂科技有限公司 | Process for purifying residual solid waste generated after alkali peeling wastewater treatment |
| CN107774329A (en) * | 2016-08-29 | 2018-03-09 | 中国石油化工股份有限公司 | A kind of metal-organic framework materials and preparation method thereof |
| CN106588638A (en) * | 2016-11-28 | 2017-04-26 | 钱胜文 | Method of purifying pure terephthalic acid (PTA) by means of white mud after treatment of textile alkali dissolution waste water and crude terephthalic acid after degradation of waste Dacron silk cloth |
| CN106966892A (en) * | 2017-04-01 | 2017-07-21 | 来安县万博丰环保科技有限公司 | A kind of purifying process of crude terephthalic acid |
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