CN1307109C - Method for recovering aromatic carboxylic acid in waste water - Google Patents
Method for recovering aromatic carboxylic acid in waste water Download PDFInfo
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- CN1307109C CN1307109C CNB2005100411512A CN200510041151A CN1307109C CN 1307109 C CN1307109 C CN 1307109C CN B2005100411512 A CNB2005100411512 A CN B2005100411512A CN 200510041151 A CN200510041151 A CN 200510041151A CN 1307109 C CN1307109 C CN 1307109C
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Abstract
The present invention relates to a method for recycling aromatic carboxylic acid and a cobalt-manganese catalyst from industrial waste water for preparing terephthalic acid. The waste water is obtained after the solid-liquid separation of refining terephthalic acid is carried out; the waste water is led into a return pipeline of an original acetic acid dewatering tower in the process of preparing crude terephthalic acid through a pipeline, and the waste water as tower top reflux liquid flows into the tower and participates in rectification in the tower. When the acetic acid is dewatered in the rectification tower, the aromatic carboxylic acid and the cobalt-manganese catalyst in the waste water are diverted into an acetic acid solution in a tower still and are drawn from the tower still with the acetic acid, and then the aromatic carboxylic acid and cobalt-manganese catalyst return to an oxidation reactor and are recycled as reaction raw materials. The method makes use of the original acetic acid dewatering tower in the process of preparing the crude terephthalic acid and does not need to change the inner design parameters and the rectification operation parameters of the original acetic acid dewatering tower, so that the method has the advantages of no need of additional investment, practicable and simple process, high recovery rate, and low treatment cost of the waste water. In addition, the method can additionally recycle the acetic acid to reduce the consumption of the acetic acid.
Description
Technical field
The present invention relates to from the trade effluent of producing terephthalic acid, reclaim the method for aromatic carboxylic acid.
Background technology
Terephthalic acid is the main production raw material of polyester industrial, industrial is raw material with the p-Xylol, adopt the oxide purification explained hereafter, be that the raw material p-Xylol is dissolved in the acetic acid, under the katalysis of cobalt manganese bromine, become crude terephthalic acid by molecular oxygen oxidation, the water that oxidation generates is extracted out from reactive system with the form of aqueous acetic acid, feeds acetic acid dehydrating tower rectifying and dewatering Separation and Recovery acetic acid.Acetic acid dehydrating tower adopts tray column or packing tower.The further hydrofining of crude terephthalic acid remove wherein contain to carboxyl benzaldehyde and other impurity (about 1500～3000ppm), also containing the little acetic acid cobalt-manganese catalyst simultaneously makes it be dissolved in water under High Temperature High Pressure, under the palladium-carbon catalyst effect, wherein the carboxyl benzaldehyde hydrogenation is changed into the p-methylbenzoic acid of easily removing, through progressively decrease temperature and pressure crystallization of multistage, wherein most of terephthalic acid is separated out with crystalline form under 140～160 ℃.The terephthalic acid of separating, through further washing, solid-liquid separation, operations such as drying obtain pure terephthalic acid's product.Also contain aromatic carboxylic acid such as a large amount of terephthalic acids, p-methylbenzoic acid in the aqueous solution that the high temperature solid-liquid separation obtains, the general operations such as flash distillation, cooling that adopt, this aqueous solution is cooled to about 50 ℃, wherein most of terephthalic acid and part p-methylbenzoic acid are separated out with the solid form crystallization, isolated solid is dissolved in the oxidation solvent acetic acid, turns back in the p xylene oxidation reactor feed.And also contain a spot of aromatic carboxylic acid in the isolated liquid, wherein the content of terephthalic acid is about 0.05%～0.5%, cobalt manganese total amount is about 0-0.01%, because its concentration is low, it is uneconomical to adopt conventional method to reclaim, and therefore now directly waste water is sent to treatment unit for waste water in the industrial production and handles.Its consequence is to cause the waste of resource on the one hand, has also increased the cost of wastewater treatment on the other hand.As this part aromatic carboxylic acid is recycled, not only can be recovered to useful aromatic carboxylic acid, reduce the consumption of reaction raw materials p-Xylol, can also reduce the expense of wastewater treatment simultaneously.
The production technology of terephthalic acid constantly develops at present, direction develops towards throughput maximization, Production Flow Chart simplification, material consumption energy consumption be low etc., propose as CN1038409, adopt mobile band filter to carry out the solid-liquid separation of crude terephthalic acid and acetum, mode with the multistage washing is removed the acetic acid on crude terephthalic acid surface, this terephthalic acid directly and the water mixing, facility investment height, drying plant that operation energy consumption is high have been omitted in hydrofining under High Temperature High Pressure.Compare with drying process, acetate concentration in the terephthalic acid of this technology gained is higher relatively, about 2000ppm, this acetic acid major part remains in the aqueous solution of high temperature solid-liquid separation, is sent to treatment unit for waste water with the waste water after the cooling solid-liquid separation and carries out wastewater treatment.As not recycled, certainly will cause the increase of acetic acid unit consumption, also cause the increase of wastewater treatment expense simultaneously.
Summary of the invention
The purpose of this invention is to provide a kind of method that reclaims aromatic carboxylic acid from the waste water of the final solid-liquid separation of purified terephthalic, it need not to increase facility investment and processing cost, reclaims aromatic carboxylic acid and cobalt-manganese catalyst easily, reduces the expense of wastewater treatment.
The inventive method is with the waste water of the final solid-liquid separation of production purified terephthalic (calling the PTA refined wastewater in the following text), be incorporated into by pipeline in the reflux pipeline of acetic acid dehydrating tower, go into tower as trim the top of column liquid, participate in rectifying in the tower, the phlegma that trim the top of column liquid measure insufficient section is discharged with cat head replenishes; When rectifying tower carried out the acetic acid dehydration operation, the aromatic carboxylic acid in the waste water was transferred in the acetum of tower still, together extracted out to reclaim the Returning oxidation reactor from the tower still with acetic acid and served as reaction raw materials.Flow control circuit is housed in the pipeline, and links to each other, preferentially adopt refined wastewater, when the refined wastewater amount is not enough, can introduce overhead condensation water by original reflux pipeline as phegma with flow control circuit in the original water reflux pipeline.When refined wastewater is excessive, be introduced directly into treatment unit for waste water by bypass.When rectifying tower carries out the acetic acid dehydration operation, also reclaim the aromatic carboxylic acid in the PTA refined wastewater, mainly be terephthalic acid and p-methylbenzoic acid, reclaim the aromatic carboxylic acid obtain and cobalt-manganese catalyst together in the charging of Returning oxidation reactor, participate in reaction as the raw material of reaction.
In sum, the present invention utilizes the original acetic acid dehydrating tower in the crude terephthalic acid production process, employing is incorporated into the method for the cat head of acetic acid dehydrating tower as phegma with the PTA refined wastewater, make it participate in rectifying in the tower, thereby aromatic carboxylic acid (terephthalic acid, p-methylbenzoic acid) and cobalt-manganese catalyst in the waste water are transferred in the acetum of tower still, and tower bottoms reclaims in the Returning oxidation reactor and serves as reaction raw materials.If contain acetic acid in the PTA refined wastewater, then also can partly transfer in the tower still and be recovered.Adopt the inventive method, almost can all reclaim aromatic carboxylic acid and cobalt-manganese catalyst (rate of recovery reaches 99.9%) in the waste water, and can reclaim the residual acetic acid of part in the waste water simultaneously.This removal process needn't change original acetic acid dehydrating tower indoor design parameter and distillation operation parameter, need not extra investment, the technology simple possible, aromatic carboxylic acid and cobalt-manganese catalyst rate of recovery height, reduce the expense of wastewater treatment, and can additionally reclaim acetic acid, reduce acetic acid consumption.
Description of drawings
The present invention reclaims aromatic carboxylic acid general flow chart in the waste water.
Among the figure, the B-1-reflux pump, D-1-lime set return tank, T-1-dehydration tower, the E-1-overhead condenser, E-2-tower still reboiler, F-1, F-2-flow control circuit, 1-liquid phase feeding pipeline, 2-gas-phase feed pipeline, 3-tower bottoms pipeline, 4-are from the PTA refined wastewater of refined unit, and 5-is as the unnecessary lime set of waste discharge.
Aqueous acetic acid from oxidation system enters dehydration tower T-1 by liquid phase feeding pipeline 1, enters among the dehydration tower D-2 by gas-phase feed pipeline 2 from the gaseous phase materials of the acetic acid water of reactive system.Wherein the charging of gas-liquid phase can be the multiply charging, advances the different positions at tower respectively.The tower bottoms product is discharged by pipeline 3, turns back to oxidation reactor, or is used for other purposes.E-2 is a tower still reboiler, overhead vapours condensation in overhead condenser E-1, and lime set enters lime set return tank D-1.From the PTA refined wastewater 4 of refined unit,, join in the dehydration tower by the trim the top of column pipeline by flow control circuit F-1.After lime set in the lime set jar is pressurizeed by reflux pump B-1, according to the needs of trim the top of column liquid measure, by flow control circuit F-2, carry out replenishing of trim the top of column liquid, unnecessary lime set 5 is sent to waste water unit, carries out wastewater treatment
Embodiment
Embodiment 1
Adopt the conventional rectification tower to carry out industrial implementation, dehydration tower T-1 has 90 blocks of column plates directly through 3.2m in the tower, and tower still reboiler E-2 adopts the hydrocone type reboiler, and cat head is provided with atmospheric condenser E-1.Cat head working pressure 110kpa, the liquid phase feeding 1 of tower water tower T-1 comprise from the oxidation reactor condenser, from high-pressure absorber with from these three bursts of feed liquids of normal pressure washing tower; Gas-phase feed 2 comprises from the flash distillation of second crystallizer with from these two strands of steam of mother liquid evaporation recovery unit.The cat head lime set of dehydration tower is all discharged.The feed composition of dehydration tower becomes with group of products to see Table 1 and 2 respectively in this example.Aromatic carboxylic acid terephthalic acid, p-methylbenzoic acid and cobalt-manganese catalyst in the PTA refined wastewater all exists in the acetum of tower still, turns back to oxidation reactor with acetic acid and serves as reaction raw materials.
The feed composition of table 1 dehydration tower (flow rate unit K g/h)
The product of table 2 dehydration tower is formed (flow rate unit K g/hr)
| Composition | Tower still product | Cat head waste water |
| P-Xylol | 9.6 | |
| Acetic acid | 43994 | 1 |
| Water | 2034 | 68104 |
| P-methylbenzoic acid | 116 | |
| Terephthalic acid | 45.6 | |
| Ritalin | 0.4 | 692 |
| Cobaltous diacetate | 1.4 | |
| Manganese acetate | 1.4 |
Embodiment 2
This example contains in PTA waste water the acetic acid of 70kg/hr flow rate, and other condition is identical with example 1.Feed composition becomes with group of products to see Table 3 and 4 respectively.In the table 4, the amount of acetic acid promptly illustrates when containing acetic acid in the PTA waste water than increasing 15kg/hr in the table 2 in the tower still product, when reclaiming terephthalic acid and p-methylbenzoic acid, can also reclaim part acetic acid in the waste water, calculate as can be known, the acetic acid yield in the PTA waste water is more than 20%.
The charging group of table 3 dehydration tower (flow rate unit K g/hr)
| Stream burst title | From the charging of oxidation reactor condenser | From the high-pressure absorber charging | Charging from the normal pressure washing tower | Flash-off steam from second crystallizer | Reclaim unitary steam from mother liquor | The PTA refined wastewater |
| P-Xylol | 4.8 | 4.8 | ||||
| Acetic acid | 11047 | 1723 | 1120 | 10144 | 19961 | 70 |
| Water | 5179 | 1615 | 4932 | 1794 | 5812 | 50806 |
| P-methylbenzoic acid | 116.2 | |||||
| Terephthalic acid | 45.6 | |||||
| Ritalin | 90 | 15.6 | 408 | 87.6 | 91.2 |
The product of table 4 dehydration tower is formed (flow rate unit K g/hr)
| Stream burst title | Tower still product | Cat head waste water |
| P-Xylol | 9.6 | |
| Acetic acid | 44009 | 55 |
| Water | 2034 | 68104 |
| P-methylbenzoic acid | 116 | |
| Terephthalic acid | 45.6 | |
| Ritalin | 0.4 | 692 |
Claims (2)
1. method that reclaims aromatic carboxylic acid in the waste water, this waste water is from the water after the final solid-liquid separation of purified terephthalic, it is characterized in that being incorporated into this waste water in the reflux pipeline of original acetic acid dehydrating tower in the crude terephthalic acid production process by pipeline, go into tower as trim the top of column liquid, participate in rectifying in the tower, when rectifying tower carries out the acetic acid dehydration operation, aromatic carboxylic acid in the waste water and cobalt-manganese catalyst are transferred in the acetum of tower still, together extract out to reclaim the Returning oxidation reactor from the tower still with acetic acid and serve as reaction raw materials.
2. a kind of method that reclaims aromatic carboxylic acid in the waste water according to claim 1 is characterized in that the phlegma that trim the top of column liquid measure insufficient section is discharged with cat head replenishes.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2005100411512A CN1307109C (en) | 2005-07-22 | 2005-07-22 | Method for recovering aromatic carboxylic acid in waste water |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2005100411512A CN1307109C (en) | 2005-07-22 | 2005-07-22 | Method for recovering aromatic carboxylic acid in waste water |
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| Publication Number | Publication Date |
|---|---|
| CN1749175A CN1749175A (en) | 2006-03-22 |
| CN1307109C true CN1307109C (en) | 2007-03-28 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB2005100411512A Active CN1307109C (en) | 2005-07-22 | 2005-07-22 | Method for recovering aromatic carboxylic acid in waste water |
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Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102451573B (en) * | 2010-11-03 | 2014-12-03 | 中国石油化工股份有限公司 | Acetic acid dehydrating tower rectifying method |
| CN104447296B (en) * | 2013-09-18 | 2016-06-08 | 中国石油化工股份有限公司 | A kind of reclaim the method for aromatic in purified terephthalic acid wastewater |
| CN105001073B (en) * | 2015-07-02 | 2017-06-20 | 中国石油天然气集团公司 | Low energy consumption material consumption, the PTA production methods and system of few waste discharge |
| CN111606800A (en) * | 2020-06-09 | 2020-09-01 | 恒力石化（大连）有限公司 | Device for recovering acetic acid from waste water |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1176228A (en) * | 1996-09-12 | 1998-03-18 | 中国石油化工总公司抚顺石油化工研究院 | Processing method of waste water from refined p-benzene dicarboxylic acid production |
| CN1226550A (en) * | 1998-02-16 | 1999-08-25 | 中国石化辽阳石油化纤公司 | Process for recovering cobalt and manganese catalysts from production of terephthalic acid |
| CN1623930A (en) * | 2004-11-19 | 2005-06-08 | 清华大学 | Process for treating waste water of producing refined terephthalic acid |
-
2005
- 2005-07-22 CN CNB2005100411512A patent/CN1307109C/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1176228A (en) * | 1996-09-12 | 1998-03-18 | 中国石油化工总公司抚顺石油化工研究院 | Processing method of waste water from refined p-benzene dicarboxylic acid production |
| CN1226550A (en) * | 1998-02-16 | 1999-08-25 | 中国石化辽阳石油化纤公司 | Process for recovering cobalt and manganese catalysts from production of terephthalic acid |
| CN1623930A (en) * | 2004-11-19 | 2005-06-08 | 清华大学 | Process for treating waste water of producing refined terephthalic acid |
Non-Patent Citations (1)
| Title |
|---|
| 对苯二甲酸废水的处理技术 官宝红，水处理技术，第28卷第3期 2002 * |
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| CN1749175A (en) | 2006-03-22 |
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Effective date of registration: 20160206 Address after: 211900 Yizheng Changjiang Road, Jiangsu, China, No. 1, No. Patentee after: CHINA SINOPEC YIZHENG CHEMICAL FIBER CO., LTD. Address before: 211000 No. 1 Changjiang West Road, Xu Town, Jiangsu City, Yizheng Province Patentee before: Yizheng Chemical Fiber Co., Ltd., China Petrochemical Group Corp. |