CN101544429B - Extraction-hyperfiltration-reverse osmosis combined method for treating PTA refined wastewater - Google Patents
Extraction-hyperfiltration-reverse osmosis combined method for treating PTA refined wastewater Download PDFInfo
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Abstract
The invention relates to an extraction-hyperfiltration-reverse osmosis combined method for treating PTA refined wastewater. The method comprises the following steps: firstly, adopting paraxylene to extract PTA refined wastewater; returning an extraction phase to the preparation working procedure of the PTA; and enabling the extraction phase after the hyperfiltration-reverse osmosis treatment to reach a recycle standard by water and returning concentrated water back to the paraxylene extraction step or the preparation working procedure of the PTA. The invention overcomes the defect of exhaust waste of the prior PTA refined wastewater, recycles most PT acid and PTA in the wastewater, removes most metal ions and organic impurities, achieves the recycle aim, also solves the problem of easy blocking of a reverse osmosis film, has the advantages of lower investment and energy consumption, high wastewater recycle rate, and the like, not only recycles usable resources, but also lessens environmental pollution, integrates the advantages of various treatment technologies and realizes the zero emission of the technological process.
Description
Technical field
The invention belongs to field of waste water treatment, be specifically related to a kind of treatment process of purified terephthalic acid wastewater.
Background technology
Pure terephthalic acid (PTA) production process can be divided oxidation unit and hydrofining unit two portions.With p-Xylol (PX) is raw material, changes into crude terephthalic acid through atmospheric oxygen under catalyst action, is crude product through crystallization, filtration, drying successively again; Crude terephthalic acid is the PTA finished product through crystallization, centrifugation, drying through hydrogenation and removing impurity again.
Pure terephthalic acid (PTA) is indispensable starting material during terylene is produced, the waste water that the PTA treating process produces contains p-methylbenzoic acid (PT acid), pure terephthalic acid (PTA), metal ion and organic impurity, if directly discharging can cause environmental pollution, and can cause the waste of resource.The treatment technology of PTA refined wastewater mainly contains materialization treatment process, biochemical treatment process and materialization-biochemistry combination treatment method 3 classes, but there is the problem that investment and energy consumption are big, the waste water reclamation rate is low in existing method.
Summary of the invention
The objective of the invention is to overcome the shortcoming of original PTA refined wastewater discharging waste, adopt the extraction-hyperfiltration-reverse osmosis isolation technique, most of PT acid and PTA in the waste water that a kind of PTA of removing treating process produces are provided, further remove metal ions such as Mn, Co in the waste water, Fe again, reach the method for PTA refined wastewater reuse purpose.
Purpose of the present invention can reach by following measure:
A kind of method of extraction-hyperfiltration-reverse osmosis combined treatment PTA refined wastewater, adopt p-Xylol extraction purified terephthalic acid wastewater earlier, extraction phase turns back in pure terephthalic acid's the preparation section, after extracting phase process ultrafiltration and the reverse-osmosis treated, permeate water reaches reuse standard, and condensed water turns back in the extraction step of p-Xylol or turns back in pure terephthalic acid's the preparation section.
In the extraction step, the mass ratio of p-Xylol and purified terephthalic acid wastewater is 1: 5～10, and extraction temperature is 35～50 ℃, and extraction progression is 3～5 grades.In the extracting phase after the extraction, the content of p-methylbenzoic acid is not more than 200ppm, further requires to be, the PT acid in the extracting phase is that 50～200ppm (mass ratio, down with) and PTA can enter the ultrafiltration reverse osmosis system when being 50～100ppm.
Ultrafiltration and reverse-osmosis treated step can separately be carried out, and also can carry out in the ultrafiltration reverse osmosis unit.The combination of ultrafiltration and reverse osmosis not only can be held back the superfine solid particulate, the metal ion in the water can also be removed, and recovery PT acid wherein, reduce discharge of wastewater.
The material of ultra-filtration membrane is polysulfones, polyethersulfone, modified pvc membrane or polyvinylidene difluoride (PVDF) etc.The temperature of ultrafiltration is 35～45 ℃, and ultrafiltration pressure is 0.1～0.4MPa.The reverse osmosis membrane material is aromatic polyamide-based reverse osmosis membrane or cellulosic acetates reverse osmosis membrane, and the temperature of reverse osmosis step is 35～45 ℃, and reverse osmosis pressure is lower than 1.0MPa, is preferably 0.8～1.0MPa, and water production rate is at 80m
3More than/the h.Present method has solved the easy blocking problem of reverse osmosis membrane owing to removed most of PT acid and PTA before entering ultrafiltration-reverse osmosis.
In the permeate water (being penetrating fluid) after the ultrafiltration reverse-osmosis treated, each concentration of metal ions all less than 10ppm (Co＜10ppm particularly, Mn＜10ppm), p-methylbenzoic acid concentration is less than 50ppm; The permeate water reuse is to pure terephthalic acid's preparation section.
PTA refined wastewater described in the present invention is meant with PX to be in the process of raw material production PTA, and the waste water that refined unit produces comprises crystalline mother solution, washes and the contained waste water of other steps in refined unit.Not only contain PT acid and PTA in this waste water, also contain metal ion (as Co, Mn etc.) and organic impurity, these waste water are if directly discharging can cause environmental pollution.Through the processing of present method, turn back to the PX oxidation system as raw material after the extraction phase extraction PT acid, after extracting phase entered membrane separation assemblies, the water concentration of metal ions and the PT acid concentration that see through reached the reuse requirement, returned refining workshop section or other workshop sections; Condensed water contains higher PT acid and metal ion, the rectifying tower instead of part phegma of delivering to the PTA reactive system as reflux with or be back to other workshop sections, condensed water is returned reactive system, can not only efficient recovery PT acid and metal ion, but also can reduce PTA rectifying tower cat head acetic acid content, reduce the acetic acid loss.Through above-mentioned processing, the PTA refined wastewater can be fully used, and each component has obtained being close to completely and utilized again.
Extraction temperature of the present invention is not a normal temperature in general sense, can reach better effect of extracting under specific temperature and ratio.Through experiment discovery repeatedly, the preferred extraction temperature of the present invention is 35～50 ℃, and PX is 1: 5～10 with the preferred mass ratio of waste water.This result can be confirmed from table 1 and table 2.
Carry out the result of the single-stage extraction test of different PX and wastewater volume ratio under table 1 representative temperature
As can be seen from the above table, under uniform temp, the content of PT acid in water layer, the increase of waste water usage ratio is risen during with extraction; Under the PX condition identical with the waste water ratio, the content of PT acid in water layer increases with the rising of temperature.
The PX content that extracts back extracting phase (water) is analyzed with the content of extraction phase (PX mutually) water, and the result is as shown in table 2.
Table 2 water PX and oil phase water content measurement result
Can find out that from table 2 data after the extraction, PX has a spot of water mutually.The general solubleness of water in PX is very low, may be to contain some PT acid among the PX to have played solublization after extracting, thereby the content of water in PX is slightly increased.The PX content of aqueous phase adopts the method for using gas chromatographic analysis after the extraction again, and the interpretation of result fluctuation is bigger, may be due to the analytical error.But as can be seen, the content of PX is also very low.
Can find out that from above extraction experiments result refined wastewater is after extracting with PX, water content still can be low to moderate 500ppm after the extraction phase extraction PT acid, can turn back to the PX oxidation system; The PT acid content declines to a great extent in the extracting phase, and PX content very low (50ppm is following) does not influence the follow-up system reuse.Extracting phase waste water after the extraction is after ultrafiltration-reverse-osmosis treated, and the water concentration of metal ions and the PT acid concentration that see through reach the reuse requirement, returns refining workshop section.Condensed water contains higher PT acid and metal ion, delivers to a cover T-403 tower instead of part phegma as backflow.Wherein PT acid and metal ion be from the discharge of tower still, Returning reacting system and being reclaimed.Like this can not only efficient recovery PT acid and metal ion, but also can reduce T-403 column overhead acetic acid content, reduce the acetic acid loss.
The PTA refined wastewater also can tentatively filter earlier before extracting or carrying out ultrafiltration, removed the macrobead suspended solid in the waste water.Fig. 1 is a kind of general flow chart, and refined wastewater is sent into ultra-filtration equipment then through extraction, the superfine solid particulate is held back, seen through liquid and through reverse osmosis isolation the metal ion in the water is removed again, and recovery PT acid wherein, reduce discharge of wastewater, the water outlet after reverse osmosis can be back to refining making beating.
In conjunction with Fig. 1, a kind of detailed process of the present invention is: PTA waste water enters through the top of flow control valve from extraction tower, and PX passing ratio variable valve enters from the bottom of extraction tower, and its flow is about 1/5～1/10 of waste water.In extraction tower, after waste water and PX carry out continuous countercurrent extraction PT acid, extraction phase (moisture content＜500ppm) after the extraction cat head is discharged, turn back to oxidation system; (PX content＜50ppm) be sent to the ultrafiltration reverse osmosis unit after discharging at the bottom of the extraction tower, the concentration of metal ions of permeate water and PT acid concentration all reach reuse and require (Co＜10ppm, Mn＜10ppm, PT acid＜50ppm), return refining workshop section extracting phase.Condensed water contains higher PT acid and metal ion, delivers to rectifying tower instead of part phegma as refluxing or turning back to extraction tower.
The present invention has overcome the shortcoming of original PTA refined wastewater discharging waste, has reclaimed most of PT acid and the PTA in the waste water, has removed most of metal ion and organic impurity, reaches the purpose of reuse.The present invention has also solved the easy blocking problem of reverse osmosis membrane, have the investment and energy consumption is lower, waste water reclamation rate advantages of higher.The present invention had both reclaimed useful resources, can reduce the pollution to environment again.The present invention combines the advantage of various treatment process, realizes the zero release of this technological process, is an outstanding integrated technique.
Description of drawings
Fig. 1 is a kind of simple process flow diagram of the present invention.
Embodiment
Embodiment 1
PTA waste water enters through the top of flow control valve from extraction tower, and PX passing ratio variable valve enters extraction tower from the bottom of extraction tower.In extraction tower, after waste water and PX carried out continuous countercurrent extraction PT acid, extraction phase turned back to oxidation system after the extraction cat head is discharged; Extracting phase is sent to ultrafiltration reverse osmosis unit (material of ultra-filtration membrane is a polysulfones) after discharging at the bottom of by extraction tower, after the concentration of metal ions of permeate water and PT acid concentration all reach reuse and require, returns refining workshop section.Condensed water contains higher PT acid and metal ion, delivers to rectifying tower instead of part phegma as refluxing or turning back to extraction tower.
Wherein, the service temperature of extraction tower is 45 ℃, the charging of extraction tower (kilogram/hour) count by weight: stream burst 1:100 part contains the waste water of PT acid 638ppm, the stream strand pure p-Xylol of 2:10.82 part.Discharging from extraction tower after extraction step is finished is: stream burst 3:10.85 part contains the extraction liquid of PT acid 5000ppm, and stream burst 4:99.97 part contains the raffinate of PT acid 96ppm, and raffinate enters the subsequent ultrafiltration reverse osmosis system.The percentage extraction of PTA and PT acid is about 85.0%.
The service temperature of ultrafiltration reverse osmosis system is 40 ℃, and ultrafiltration pressure is 0.25MPa, and reverse osmosis pressure is 1MPa.Discharging after the ultrafiltration reverse-osmosis treated is: the permeate water of stream burst 5:90 part (PTA 10ppm, PT acid 42ppm, Co 2ppm, Mn 1ppm), stream burst 6:9.97 part condensed water (PTA 92ppm, PT acid 583ppm, Co 483ppm, Mn 392ppm).Each component recovery is about 90.0%.
Embodiment 2
Step is with embodiment 1, and wherein the operating parameters of each step is as follows:
45 ℃ of the service temperatures of extraction tower, the charging of extraction tower (kilogram/hour) count by weight: stream burst 1:100 part contains the waste water of PT acid 588ppm, the stream strand pure p-Xylol of 2:12.99 part.Discharging from extraction tower after extraction step is finished is: stream burst 3:13.02 part contains the extraction liquid of PT acid 4000ppm, and stream burst 4:99.97 part contains the raffinate of PT acid 67ppm, and raffinate enters the subsequent ultrafiltration reverse osmosis system.The percentage extraction of PTA and PT acid is 88.6%.
The service temperature of ultrafiltration reverse osmosis system is 40 ℃, and ultrafiltration pressure is 0.20MPa, and reverse osmosis pressure is 0.95MPa.Discharging after the ultrafiltration reverse-osmosis treated is: the permeate water of stream burst 5:90 part (PTA9ppm, PT acid 40ppm, Co 3ppm, Mn 2ppm), stream burst 6:9.97 part condensed water (PTA88ppm, PT acid 311ppm, Co 474ppm, Mn 383ppm).Each component recovery is about 90.0%.
Claims (5)
1. the method for an extraction-hyperfiltration-reverse osmosis combined treatment PTA refined wastewater, it is characterized in that adopting earlier p-Xylol extraction purified terephthalic acid wastewater, extraction phase turns back in pure terephthalic acid's the preparation section, after extracting phase process ultrafiltration and the reverse-osmosis treated, permeate water reaches reuse standard, and condensed water turns back in the extraction step of p-Xylol or turns back in pure terephthalic acid's the preparation section; Wherein in extraction step, the mass ratio of p-Xylol and purified terephthalic acid wastewater is 1: 5～10; The temperature of described p-Xylol extraction purified terephthalic acid wastewater is 35～50 ℃; In the described extracting phase, the content of p-methylbenzoic acid is not more than 200ppm; The material of described ultra-filtration membrane is polysulfones, polyethersulfone, modified pvc membrane or polyvinylidene difluoride (PVDF).
2. method according to claim 1, the temperature that it is characterized in that ultrafiltration or reverse osmosis step is 35～45 ℃.
3. method according to claim 1 and 2 is characterized in that ultrafiltration pressure is 0.1～0.4MPa.
4. method according to claim 1 and 2 is characterized in that reverse osmosis pressure is 0.8～1.0MPa.
5. method according to claim 1 is characterized in that in the described permeate water that each concentration of metal ions is all less than 10ppm, and p-methylbenzoic acid concentration is less than 50ppm; The permeate water reuse is to pure terephthalic acid's preparation section.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| WO2014189786A1 (en) * | 2013-05-20 | 2014-11-27 | Invista Technologies S.A R.L. | Pure plant waste water purification and recycle |
Families Citing this family (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101941901B (en) * | 2010-08-16 | 2013-04-17 | 福州大学 | Method for recycling mother solid in PTA-refining wastewater |
| CN102139970B (en) * | 2011-01-17 | 2013-06-05 | 浙江大学 | Recycling method for pure terephthalic acid industrial wastewater |
| CN102874955A (en) * | 2012-10-31 | 2013-01-16 | 南京工业大学 | Combined process for treating terephthalic acid refining wastewater |
| CN105037131B (en) * | 2015-06-17 | 2018-04-13 | 福州大学 | A kind of PTA waste water reclaimings recycle new process |
| CN111348795A (en) * | 2020-03-26 | 2020-06-30 | 福州大学 | Electrodialysis-based PTA refining wastewater resource recycling device and method |
| CN112520931A (en) * | 2021-01-25 | 2021-03-19 | 天津市汇筑恒升科技有限公司 | Purification method and device for PTA (purified terephthalic acid) refining mother liquor |
| CN114906964B (en) * | 2021-02-09 | 2023-07-21 | 大连波美科技有限公司 | PTA wastewater treatment system and application method |
| CN116282692B (en) * | 2023-03-08 | 2024-05-14 | 三达膜环境技术股份有限公司 | Recycling treatment method of bromine-containing wastewater of tail gas washing tower in production of refined terephthalic acid |
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| CN1039784A (en) * | 1989-06-20 | 1990-02-21 | 北京市环境保护科学研究所 | Pure terephthalic acid (PTA) Wastewater Treatment |
| CN1315295A (en) * | 2000-03-31 | 2001-10-03 | 郝彤 | Process for treating waste water generated in production of refined terephthalic acid |
| CN1765760A (en) * | 2004-10-29 | 2006-05-03 | 中国石油化工股份有限公司 | Terephthalic acid production waste water disposal method |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1039784A (en) * | 1989-06-20 | 1990-02-21 | 北京市环境保护科学研究所 | Pure terephthalic acid (PTA) Wastewater Treatment |
| CN1315295A (en) * | 2000-03-31 | 2001-10-03 | 郝彤 | Process for treating waste water generated in production of refined terephthalic acid |
| CN1765760A (en) * | 2004-10-29 | 2006-05-03 | 中国石油化工股份有限公司 | Terephthalic acid production waste water disposal method |
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| JP特开2006-272051A 2006.10.12 |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| WO2014189786A1 (en) * | 2013-05-20 | 2014-11-27 | Invista Technologies S.A R.L. | Pure plant waste water purification and recycle |
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Effective date of registration: 20160205 Address after: 211900 Yizheng Changjiang Road, Jiangsu, China, No. 1, No. Patentee after: CHINA SINOPEC YIZHENG CHEMICAL FIBER CO., LTD. Address before: 211900 No. 1 Changjiang West Road, Xu Town, Jiangsu City, Yizheng Province Patentee before: Yizheng Chemical Fiber Co., Ltd., China Petrochemical Group Corp. |