CN102139970B - Recycling method for pure terephthalic acid industrial wastewater - Google Patents
Recycling method for pure terephthalic acid industrial wastewater Download PDFInfo
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Abstract
The invention relates to the technical field of chemical engineering mass-transfer and separation and discloses a recycling method for pure terephthalic acid industrial wastewater, which comprises the following steps: firstly, solid organic aromatic carboxylic acid in the pure terephthalic acid industrial wastewater is removed through micro-filtration, and the solid organic aromatic carboxylic acid returns to an oxidation unit; filtered wastewater and extractant p-xylene (PX) are respectively delivered to a membrane extraction component by a pump so as to keep water phase pressure slightly higher than PX extraction phase; the PX extraction phase which undergoes membrane extraction is delivered to the oxidization unit to be used as PX raw material of oxidation reaction; after metal ions of water phase which undergoes membrane extraction are absorbed and recycled by resin, water phase can return to a refining unit to be used as refined raw material water; in order to prevent other impurities from accumulating in a system, part of pure terephthalic acid industrial wastewater needs to be extracted and sent into a wastewater treatment unit. The recycling method can substantially reduce wastewater emission, realize regeneration and utilization of water resources, also can recycle aromatic carboxylic acid, reduce raw material consumption of the process and have the advantages of high efficiency, lower investment and the like.
Description
Technical field
The present invention relates to chemical mass transfer separation technology field, related in particular to a kind of recoverying and utilizing method of water from refined p-benzene dicarboxylic acid production.
Background technology
Pure terephthalic acid (PTA) is a kind of important polyester (PET) raw materials for production, mainly adopts the production of p-Xylol (PX) air liquid phase catalytic oxidation.At first crude terephthalic acid (CTA) product of being produced by the PX oxidation, CTA is dissolved in the water under 250～300 ℃, through processes such as palladium carbon (Pd/C) catalytic hydrofinishing, multistage crystallization, solid-liquid separation, obtain pure terephthalic acid (PTA) product.Be solvent owing to adopting water in the PTA treating process, can produce the waste water that contains in a large number aromatic carboxylic acid, wastewater treatment is the difficult problem that a PTA technological process is needed solution badly always.
At present, the activated sludge biochemical method is the main method that the PTA refined wastewater is processed, and utilizes the metabolism of various microorganisms in active sludge to remove aromatic carboxylic acid pollutent in waste water, and industrial implementation is mainly two sections activated sludge processes of aerobic/anaerobic at present.But due to the biochemical metabolism poor-performing of aromatic carboxylic acid, the processing efficiency of activated sludge process is lower.Therefore, inevitably there are the shortcomings such as processing efficiency is low, floor space is large, energy consumption is high, excess sludge production is large in present PTA treatment unit for waste water.
Up to now, a large amount of improvement biochemical process that also patent report arranged.CN200410091131 has proposed the bio-reactor that a kind of aerobic/anaerobic active sludge that adopts porous-flexible carrier to build coexists, and can effectively reduce the sewage treatment unit floor space; CN200810020993 has proposed a kind of method of secondary membrane reactor biochemical treatment PTA waste water; CN200610097902, CN200610041561 and CN200810243708 etc. have also proposed the PTA wastewater biochemical facture that multiple employing chemical oxidation is strengthened, although these methods have improved the efficient of wastewater treatment, but consume the chemical such as a large amount of hydrogen peroxide, sodium chlorate, and the chemical that adds can be to the water generates secondary pollution.
Adopting liquid-liquid extraction method treatment PTA refined wastewater is also a pretty good selection, and Mitsui Chemicals, Inc. has proposed a kind of employing p-Xylol (PX) extraction process and reclaimed fragrant organic carboxyl acid in the PTA refined wastewater in patent CN200610001441.Standing demix by common decanting vessel, the PX of emulsification can not be fully by aqueous phase separation, thereby it is remaining to have a certain amount of PX in water, returns as hydrofining water if contain the water of PX, thereby not only can affect the quality product that hydrogenation reaction affects PTA, also can increase PX raw material consumption simultaneously.Therefore, in extraction process, inevitably introduce extraction agent in the incomplete water that is separated due to liquid-liquid two and pollute, also can affect the recycling of water.
In recent years, the membrane separation technique development has the related film isolation technique and is applied to the patent that the PTA refined wastewater is processed rapidly.CN00105478 has proposed a kind of PTA refined wastewater treatment process that adopts microfiltration membrane and resin absorption combination, but the aromatic carboxylic acid component in the method efficient recovery waste water; CN200410086297 has proposed a kind of method of wastewater treatment that adopts ultrafiltration, reverse osmosis and ion-exchange combination, and the method can effectively realize 70% reuse of waste water, has reduced discharge of wastewater; CN200810242729 has also proposed similar membrane separation PTA refined wastewater method with CN200810103270 etc.Because the aromatic carboxylic acids such as the p-methylbenzoic acid in the PTA refined wastewater, terephthalic acid generally are in state of saturation, in the membrane sepn process, the aromatic carboxylic acid fouling that causes for the concentration polarization that prevents the membrane interface aromatic carboxylic acid, the PTA refined wastewater prevented the fouling of aromatic carboxylic acid on membrane module by adding alkali (as sodium hydroxide or sodium carbonate) before entering membrane module.Make adding of sodium ion the recycling of water bring new pollutent owing to having, need to increase relevant heat exchange, cleaning and ion exchange system.Therefore, the membrane separation system of existing PTA refined wastewater is more complicated, and investment and running cost are also very high.
In sum, all there is certain limitation in above method.The biochemical process processing efficiency is low, and floor space is large, has wasted a large amount of water resourcess; Although membrane separation process reusable edible water, investment and the too high economic benefit of running cost are low.Therefore, be necessary to improve existing PTA refined wastewater treatment process, develop a kind of more efficient, cheap, simple PTA refined wastewater recoverying and utilizing method.
Summary of the invention
The present invention is directed in prior art processing efficiency low, floor space is large, waste a large amount of water resourcess, investment and running cost are too high, the shortcoming that economic benefit is low, provide a kind of reusable edible water, the recoverying and utilizing method of the water from refined p-benzene dicarboxylic acid production that highly-efficient treatment, cost are cheap, simple to operate.
In order to solve the problems of the technologies described above, the present invention is solved by following technical proposals:
A kind of recoverying and utilizing method of water from refined p-benzene dicarboxylic acid production comprises the following steps:
Step a: remove SOLID ORGANIC aromatic carboxylic acid in water from refined p-benzene dicarboxylic acid production by micro-filtration, the solid aromatic carboxylic acid that leaches returns to oxidation unit;
Step b: water from refined p-benzene dicarboxylic acid production and p-Xylol by pump delivery to the membrane extraction unit, water and oil phase are respectively by porous organic membrane both sides in membrane module, keep containing the waste water phase pressure of aromatic carboxylic acid a little more than the p-Xylol extraction phase, waste water contacts in membrane module with the p-Xylol two-phase, mass transfer, and the most of aromatic carboxylic acid in extraction wastewater is taken out of by the p-Xylol extraction agent;
Step c: the p-Xylol extraction phase that is enriched with aromatic carboxylic acid after membrane extraction is transported to oxidation unit, as the p-Xylol raw material of oxidizing reaction;
Steps d: return to refined unit as refining raw water after reclaiming metal ion through the water after membrane extraction through resin absorption;
Step e: extract the part water from refined p-benzene dicarboxylic acid production and remove treatment unit for waste water;
Described water from refined p-benzene dicarboxylic acid production derives from terephthalic acid hydrofining unit.
As preferably, in described step b, waste water and p-Xylol two-phase adopt adverse current, and stream or the complete mixing flow mode contacts, mass transfer in membrane module.
As preferably, the film that in described step b, the membrane extraction unit adopts is microporous membrane.
As preferably, described film is any in polypropylene, polysulfones, polyvinylidene difluoride (PVDF), organosilicon macromolecule film.
As preferably, the membrane module in described step b is any in hollow-fibre membrane, plate type membrane assembly.
As preferably, described aromatic carboxylic acid comprises p-methylbenzoic acid, phenylformic acid, terephthalic acid, m-phthalic acid, phthalic acid and benzenetricarboxylic acid.
As preferably, the metal ion in the steps d in described steps d comprises cobalt, manganese, nickel, iron, sodium.
As preferably, add organic compounds containing nitrogen to do extraction promotor in described p-Xylol extraction phase, extraction promotor can be selected from amine, guanidine class nitrogenous compound, and it is 5-1000ppm that extraction promotor is added concentration.In the p-Xylol extraction phase, can by adding organic compounds containing nitrogen facilitated extraction process, improve extraction efficiency.The nitrogenous compounds such as amine, guanidine class can effectively promote the p xylene oxidation process, and the catalytic promoter that can be used as p-Xylol atmospheric oxidation process adds in reactor.Therefore the effect that has simultaneously the facilitated extraction process due to this compounds when considering that interpolation amine and guanidine compound are made the p xylene oxidation catalytic promoter, also can be considered to come facilitated extraction efficient in p-Xylol by joining.
As preferably, the resin in described steps d is macroporous resin or ion exchange resin.
As preferably, extract 5～30wt% that the waste water that removes treatment unit for waste water accounts for total wastewater flow rate in described step e.
Refined wastewater chief component in typical case PTA technique sees Table shown in one.
Table one. the refined wastewater chief component in typical PTA technique
The present invention has significant technique effect owing to having adopted above technical scheme:
The present invention not only can realize the recycle of the PTA refined wastewater more than 80%, significantly reduces waste discharge; Reclaim simultaneously p-methylbenzoic acid and terephthalic acid in waste water, reduce the raw material consumption of PTA production process; The method has also that efficient is high, energy consumption is low, investment and the advantage such as operation and maintenance cost is low.
Description of drawings
Fig. 1 is the process flow sheet that membrane extraction of the present invention is recycled the PTA refined wastewater.
Fig. 2 is the experiment flow figure of membrane extraction treatment PTA refined wastewater of the present invention.
Embodiment
Below in conjunction with accompanying drawing 1 to Fig. 2 and embodiment, the present invention is described in further detail:
Embodiment 1
A kind of recoverying and utilizing method of water from refined p-benzene dicarboxylic acid production comprises the following steps:
Step a: remove SOLID ORGANIC aromatic carboxylic acid in water from refined p-benzene dicarboxylic acid production by micro-filtration, the solid aromatic carboxylic acid that leaches returns to oxidation unit;
Step b: water from refined p-benzene dicarboxylic acid production and p-Xylol by pump delivery to the membrane extraction unit, water and oil phase are respectively by porous organic membrane both sides in membrane module, keep containing the waste water phase pressure of aromatic carboxylic acid a little more than the p-Xylol extraction phase, waste water and p-Xylol two-phase adopt adverse current, and stream or the complete mixing flow mode contacts, mass transfer in membrane module, the most of aromatic carboxylic acid in extraction wastewater is taken out of by the p-Xylol extraction agent;
Step c: the p-Xylol extraction phase that is enriched with aromatic carboxylic acid after membrane extraction is transported to oxidation unit, as the p-Xylol raw material of oxidizing reaction;
Steps d: through returning to refined unit as refining raw water after the process macroporous resin of the water after membrane extraction or ion exchange resin absorption recovery metal ion;
Step e: extract the part water from refined p-benzene dicarboxylic acid production and remove treatment unit for waste water;
Described water from refined p-benzene dicarboxylic acid production derives from terephthalic acid hydrofining unit.
The film that the membrane extraction unit adopts is microporous membrane, and film is polypropylene, polysulfones, polyvinylidene difluoride (PVDF) or organosilicon macromolecule film.
Aromatic carboxylic acid comprises p-methylbenzoic acid, phenylformic acid, terephthalic acid, m-phthalic acid, phthalic acid and benzenetricarboxylic acid.
Metal ion comprises cobalt, manganese, nickel, iron, sodium.
Add organic compounds containing nitrogen to do extraction promotor in the p-Xylol extraction phase, extraction promotor can be selected from amine, guanidine class nitrogenous compound, and it is 5-1000ppm that extraction promotor is added concentration.
Extraction goes the waste water for the treatment of unit for waste water to account for 5～30wt% of total wastewater flow rate.
Because the purification of terephthalic acid waste water composition of different process differs greatly, the waste water that the present embodiment adopts is taken from a certain typical PTA factory.Need to filter under 40 ℃ of conditions before carrying out the membrane extraction experiment to remove solid, after filtering, the chief component of waste water sees Table shown in two.In waste water, organic aromatic carboxylic acid content adopts high performance liquid chromatography (HPLC) analysis, adopt Agilent1100 liquid chromatography liquid chromatograph, be furnished with DAD detector and quaternary pump, chromatographic column is the C18 post, and moving phase is the ternary gradient elution of water, methyl alcohol and acetonitrile; Acetic acid content in water adopts capillary gas chromatography (GC) analysis.The membrane module that the present embodiment adopts is polypropylene (PP) hollow-fibre membrane, comprises that altogether 400 PP hollow-fibre membranes form, and the external diameter of tubular fibre is 0.48mm, thickness 0.05mm, and length is 200mm, internal diameter is 0.40mm.Membrane module shell internal diameter is 25mm, and length is 250mm.
In experimentation, after filtering, waste water, membrane module and p-Xylol extraction liquid all are placed in 40 ℃ of waters bath with thermostatic control.At first deionized water is full of in the hollow-fibre membrane of membrane module, p-Xylol is full of the membrane module shell; Open waste water pump, adjust the recycle-water outlet valve, the maintenance gauge pressure is 0.03MPa, and adjustment discharge is 2L/h; Open the p-Xylol recycle pump, adjusting and keeping the p-Xylol circular flow is 4L/h, and p-Xylol is 4L, and wastewater flow rate is 20L.Keep p-Xylol extraction phase and water to flow with the adverse current form in membrane module, after carrying out moving continuously in 4 hours, get the membrane extraction assembly and go out saliva and carry out high performance liquid chromatography and capillary gas chromatography, analytical results sees Table shown in two.
Embodiment 2
A kind of recoverying and utilizing method of water from refined p-benzene dicarboxylic acid production adopts refined wastewater in the same manner as in Example 1 to carry out common liquid-liquid extraction experiment.Get the p-Xylol (PX) of 300ml waste water and 100ml in the separating funnel of 500ml, strenuous vibration mixes, and in 40 ℃ of waters bath with thermostatic control standing 24 hours, take off that layer water carries out HPLC and GC analyzes, the analytical results contrast is shown in table two.
Embodiment 3
A kind of recoverying and utilizing method of water from refined p-benzene dicarboxylic acid production adopts refined wastewater in the same manner as in Example 1 to carry out similar membrane extraction experiment.Keep all operations condition identical with embodiment 1, different is to contain the 2000ppm p-methylbenzoic acid in p-Xylol (PX) extraction phase that adopts.Carry out 4 hours continuously after operation, get the membrane extraction assembly and go out that saliva carries out HPLC and GC analyzes, the analytical results contrast is shown in table two.
Embodiment 4
A kind of recoverying and utilizing method of water from refined p-benzene dicarboxylic acid production adopts refined wastewater in the same manner as in Example 1 to carry out similar membrane extraction experiment.Keep all operations condition identical with embodiment 1, different is to contain the 100ppm vulkacit D in p-Xylol (PX) extraction phase that adopts.Carry out 4 hours continuously after operation, get the membrane extraction assembly and go out that saliva carries out HPLC and GC analyzes, the analytical results contrast is shown in table two.
Table two. membrane extraction is processed the waste water result relatively
By table two result as can be known, but adopt organic carboxyl acid in hollow-fibre membrane PX abstraction technique high efficiente callback waste water, reach the target of water circulation use.Because p-Xylol in extraction process inevitably can be dissolved in water, so also can bring the p-Xylol of (20ppm) on a small quantity in recycle-water into, because p-Xylol is very low, not hinder the water circuit utilization.On the other hand, by table two result as can be known, common p-Xylol extraction also can effectively reduce the organic carboxyl acid content in recycle-water; But, can cause the p-Xylol emulsification of a part due to the existence of aromatic carboxylic acid in waste water, although standing 24 hours, still can be up to 210ppm with the p-Xylol concentration in entry.This shows, if adopt common p-Xylol extraction, the efficient that is separated due to liquid-liquid two is very low, and in water, p-Xylol brings that to consume be a difficult problem into.And adopt the membrane extraction technology just can effectively solve effective separation problem of extraction agent PX and water.
Comparative example 1 and 3 results show, even p-Xylol contains the p-methylbenzoic acid up to 2000ppm in mutually, concentration affects for the organic carboxyl acid in recycle-water is also little, and this is also to be determined by the efficient extraction efficiency of p-Xylol to organic aromatic carboxylic acid.
Comparative example 1 and 4 results show, in embodiment 4, the concentration of the aromatic carboxylic acid of recycle-water generally will be lower than embodiment 1.This has illustrated the recovery of extraction that can effectively improve aromatic carboxylic acid that adds of vulkacit D, its reason is, vulkacit D can be combined with aromatic carboxylic acid as a kind of organic bases, can accelerate the p-Xylol mass transfer process of a side mutually, more is conducive to the transmission of extraction phase in opposite directions of aqueous phase organic acid.
Embodiment 5
A kind of recoverying and utilizing method of water from refined p-benzene dicarboxylic acid production adopts refined wastewater in the same manner as in Example 1 to carry out similar membrane extraction experiment.Just adopting the p-Xylol circular flow at the present embodiment is 2L/h, carries out 4 hours continuously after operation, gets the membrane extraction assembly and goes out that saliva carries out HPLC and GC analyzes, and the analytical results contrast is shown in table three.
A kind of recoverying and utilizing method of water from refined p-benzene dicarboxylic acid production, in the present embodiment recycle-water, PT concentration is 236ppm, the PT acid concentration of comparing 145ppm in embodiment 1 has increased a lot.This shows that also low p-Xylol cycle rate is unfavorable for Membrane Extraction, and its reason is can have influence on the mass transfer of organic phase film one side in membrane extraction due to too low p-Xylol cycle rate.
Embodiment 6
A kind of recoverying and utilizing method of water from refined p-benzene dicarboxylic acid production adopts refined wastewater in the same manner as in Example 1 to carry out similar membrane extraction experiment.Just adopting the PX circular flow at the present embodiment is 6L/h, carries out 4 hours continuously after operation, gets the membrane extraction assembly and goes out that saliva carries out HPLC and GC analyzes, and the analytical results contrast is shown in table three.
Comparing embodiment 1,5 and 6 results improve the PX cycle rate and can increase membrane extraction efficient as can be known, are increased to certain amplitude but work as cycle rate, and are less on the impact of extraction efficiency.
Embodiment 7
A kind of recoverying and utilizing method of water from refined p-benzene dicarboxylic acid production adopts refined wastewater in the same manner as in Example 1 to carry out similar membrane extraction experiment.The water outlet gauge pressure that just adopts at the present embodiment is 0.05MPa, carries out 4 hours continuously after operation, gets the membrane extraction assembly and goes out that saliva carries out HPLC and GC analyzes, and the analytical results contrast is shown in table three.
Embodiment 8
A kind of recoverying and utilizing method of water from refined p-benzene dicarboxylic acid production adopts refined wastewater in the same manner as in Example 1 to carry out similar membrane extraction experiment.The water outlet gauge pressure that just adopts at the present embodiment is 0.001MPa, carries out 4 hours continuously after operation, gets the membrane extraction assembly and goes out that saliva carries out HPLC and GC analyzes, and the analytical results contrast is shown in table three.
Comparative example 1,7 and 8 results keep certain intermembranous two phase pressures extremely important as can be known.As shown in embodiment 6 results, if intermembranous hypotony, in the water band entry that part PX extraction agent can flow in hollow-fibre membrane, the PX concentration in recycle-water can be very high, and the loss meeting of PX extraction phase is larger; If intermembranous hypertonia, thereby the phase contact area that can reduce the PX extraction phase of spe membrane water one side and water reduces membrane extraction efficient.
Table three. membrane extraction is processed the waste water result relatively
In a word, the above is only preferred embodiment of the present invention, and all equalizations of doing according to the present patent application the scope of the claims change and modify, and all should belong to the covering scope of patent of the present invention.
Claims (10)
1. the recoverying and utilizing method of a water from refined p-benzene dicarboxylic acid production, is characterized in that, comprises the following steps:
Step a: remove SOLID ORGANIC aromatic carboxylic acid in water from refined p-benzene dicarboxylic acid production by micro-filtration, the solid aromatic carboxylic acid that leaches returns to oxidation unit;
Step b: water from refined p-benzene dicarboxylic acid production and p-Xylol by pump delivery to the membrane extraction unit, water and oil phase are respectively by porous organic membrane both sides in membrane module, keep containing the waste water phase pressure of aromatic carboxylic acid a little more than the p-Xylol extraction phase, waste water contacts in membrane module with the p-Xylol two-phase, mass transfer, and the most of aromatic carboxylic acid in extraction wastewater is taken out of by the p-Xylol extraction agent;
Step c: the p-Xylol extraction phase that is enriched with aromatic carboxylic acid after membrane extraction is transported to oxidation unit, as the p-Xylol raw material of oxidizing reaction;
Steps d: return to refined unit as refining raw water after reclaiming metal ion through the water after membrane extraction through resin absorption;
Step e: extract the part water from refined p-benzene dicarboxylic acid production and remove treatment unit for waste water;
Described water from refined p-benzene dicarboxylic acid production derives from terephthalic acid hydrofining unit.
2. the recoverying and utilizing method of a kind of water from refined p-benzene dicarboxylic acid production according to claim 1 is characterized in that: in described step b, waste water and p-Xylol two-phase adopt adverse current, and stream or the complete mixing flow mode contacts, mass transfer in membrane module.
3. the recoverying and utilizing method of a kind of water from refined p-benzene dicarboxylic acid production according to claim 1, it is characterized in that: the film that in described step b, the membrane extraction unit adopts is microporous membrane.
4. the recoverying and utilizing method of a kind of water from refined p-benzene dicarboxylic acid production according to claim 3 is characterized in that: described film is any in polypropylene, polysulfones, polyvinylidene difluoride (PVDF), organosilicon macromolecule film.
5. the recoverying and utilizing method of a kind of water from refined p-benzene dicarboxylic acid production according to claim 1 is characterized in that: the membrane module in described step b is any in hollow-fibre membrane, plate type membrane assembly.
6. the recoverying and utilizing method of a kind of water from refined p-benzene dicarboxylic acid production according to claim 1, it is characterized in that: described aromatic carboxylic acid comprises p-methylbenzoic acid, phenylformic acid, terephthalic acid, m-phthalic acid, phthalic acid and trimellitic acid.
7. the recoverying and utilizing method of a kind of water from refined p-benzene dicarboxylic acid production according to claim 1, it is characterized in that: the metal ion in described steps d comprises cobalt, manganese, nickel, iron, sodium.
8. the recoverying and utilizing method of a kind of water from refined p-benzene dicarboxylic acid production according to claim 1, it is characterized in that: add organic compounds containing nitrogen to do extraction promotor in described p-Xylol extraction phase, extraction promotor can be selected from amine, guanidine class nitrogenous compound, and it is 5-1000ppm that extraction promotor is added concentration.
9. the recoverying and utilizing method of a kind of water from refined p-benzene dicarboxylic acid production according to claim 1, it is characterized in that: the resin in described steps d is ion exchange resin.
10. the recoverying and utilizing method of a kind of water from refined p-benzene dicarboxylic acid production according to claim 1, is characterized in that: extract 5～30wt% that the waste water that removes treatment unit for waste water accounts for total wastewater flow rate in described step e.
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| ES2896359T3 (en) | 2012-01-18 | 2022-02-24 | Purac Biochem Bv | Extraction of carboxylic acids from a dilute aqueous stream |
| 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 |
| CN102874955A (en) * | 2012-10-31 | 2013-01-16 | 南京工业大学 | Combined process for treatment of PTA (pure terephthalic acid) refined waste water |
| CN103387298B (en) * | 2013-06-18 | 2014-09-10 | 浙江逸盛石化有限公司 | Recycling apparatus and process for metal ions in terephthalic acid mother liquor |
| CN105585212B (en) * | 2015-12-24 | 2018-02-09 | 南京科技职业学院 | A kind of PTA produces waste water method for reusing synthesized |
| CN108002659A (en) * | 2017-12-25 | 2018-05-08 | 浙江华强环境科技有限公司 | A kind of new waste water treatment process |
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| CN1315295A (en) * | 2000-03-31 | 2001-10-03 | 郝彤 | Process for treating waste water generated in production of refined terephthalic acid |
| CN101333053A (en) * | 2008-08-05 | 2008-12-31 | 中国石化扬子石油化工有限公司 | Processing method for waste water in production process of fine terephthalic acid |
| CN101544429A (en) * | 2009-04-23 | 2009-09-30 | 中国石化仪征化纤股份有限公司 | Extraction-hyperfiltration-reverse osmosis combined method for treating PTA refined wastewater |
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| CN1315295A (en) * | 2000-03-31 | 2001-10-03 | 郝彤 | Process for treating waste water generated in production of refined terephthalic acid |
| CN101333053A (en) * | 2008-08-05 | 2008-12-31 | 中国石化扬子石油化工有限公司 | Processing method for waste water in production process of fine terephthalic acid |
| CN101544429A (en) * | 2009-04-23 | 2009-09-30 | 中国石化仪征化纤股份有限公司 | Extraction-hyperfiltration-reverse osmosis combined method for treating PTA refined wastewater |
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