CN101058467B - Method for treating waste water generated in production of refined terephthalic acid - Google Patents
Method for treating waste water generated in production of refined terephthalic acid Download PDFInfo
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- CN101058467B CN101058467B CN2006100762354A CN200610076235A CN101058467B CN 101058467 B CN101058467 B CN 101058467B CN 2006100762354 A CN2006100762354 A CN 2006100762354A CN 200610076235 A CN200610076235 A CN 200610076235A CN 101058467 B CN101058467 B CN 101058467B
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Abstract
The invention discloses a disposing method of manufacturing waste water of fined terephthalic acid, which comprises the following steps: contacting the waste water and complex extractant; making the CODCr in the waste water not less than 2500ml/L through contacting the manufacturing waste water of fined terephthalic acid and complex extractant; recycling the manufacturing waste water as the technical water; realizing the water circulation; possessing good disposing effect and simple technique with wide applying scale for water quality.
Description
Technical field
The invention relates to a kind of method of Industrial Wastewater Treatment, especially about a kind of treatment process of pure terephthalic acid's factory effluent.
Background technology
Pure terephthalic acid (PTA) is a kind of important chemical material, be widely used in the production aspect of various synthetic resins, polyster fibre, plastics film, softening agent and coating, and estimate in following 10 years, trevira, engineering plastics, powder coated resin will become a new consumption growth point in Chinese market, and their raw material all comes from the pure terephthalic acid.
The main production process of terephthalic acid is: in acetic aid medium, make catalyzer with Cobaltous diacetate, manganese acetate, raw material p-Xylol (PX) catalyzed oxidation is made the thick product of terephthalic acid (CTA), therefore by product p-methylbenzoic acid (P-TA) among the CTA and carboxyl benzaldehyde (4-CBA) had a strong impact on the form and aspect of esterification, polycondensation and the polyester product of polyester must manage to remove.
U.S. Amoco company in 1964 and Engelhard company have successfully developed on palladium carbon catalyst by the hydrofining method of terephthalic acid, this method comprises CTA product and process water (de-salted water) is mixed into slurry, through heat up, pressurization makes CTA water-soluble fully, will among the CTA carboxyl benzaldehyde intermediate product hydrogenating reduction be become p-methylbenzoic acid more soluble in water under 280 ℃, the reaction conditions of 7-8 MPa.Because the solubleness of p-methylbenzoic acid in water is big (100 ℃ the time in 100 gram water more than the solubleness of terephthalic acid, p-methylbenzoic acid is all dissolvings almost, and terephthalic acid only dissolves 0.034 gram), in 150 ℃ of hot water,, separate out the PTA crystal by after the step-down flash distillation step by step of the placed in-line crystallizer of 4-5 level, the cooling.Contain the crystalline slurry and filter with Pressure Centrifuges, filter cake enters making beating jar again, pulls an oar with novel process water (de-salted water) again, then after filtration, drying, makes the pure terephthalic acid.Pure terephthalic acid's purity can reach the requirement (as content＜25 mg/litre of impurity to carboxyl benzaldehyde, p-methylbenzoic acid＜150 mg/litre) of fibre-grade, but trevira is produced in the spent glycol direct esterification.
Waste water in the PTA production process mainly comes from refined unit.The terephthalic acid hydrofining reaction is just carried out under the catalysis of special-purpose catalyst-palladium charcoal (Pd/C) catalyzer, it is a kind of the palladium crystallite to be evenly distributed on special porous charcoal supported catalyst, cost an arm and a leg, to produce 22.5 ten thousand tons of PTA devices per year is example, design catalyst filling amount is 15 tons, be worth 5,280,000 yuan, estimate 1 year usage period, generally only use some months but have, catalyzer just loses activity because of various reasons, at present the work-ing life of the best PTA device of state's inner catalyst service condition less than 1 year still.
The reason that causes catalyst deactivation is a lot, wherein may be comprised by the reason that process water brings:
1. the SO in the water
4 2-Can under this reaction conditions, be reduced to S
2-, form Pd with metallic palladium
4S makes the catalyzer permanent deactivation;
2. the silicon of trace and metallic palladium reaction in the water makes catalyst deactivation;
3. metal ions such as the chromium of trace, iron, cobalt, manganese, calcium, magnesium, zinc can form insoluble terephthalate with PTA on the one hand and be adsorbed on the metallic surface in the water, and are blocking microporous, make catalyst deactivation, can be adsorbed by the Pd/C catalyzer on the other hand, afterwards by H
2Be reduced into low valence metal ion or big crystal grain metal covers catalyst surface, make catalyst deactivation;
4. the macromolecule organic in the water may cover catalyst surface, causes catalyst deactivation.
In PTA main flow production technology, the production technique of refined unit need use a large amount of de-salted waters as producing solvent, and the unit consumption of de-salted water is general all at 3-4 ton/ton PTA.A production equipment of producing 22.5 ten thousand tons of PTA per year, the annual de-salted water total amount that consumes is all more than 900,000 tons, add the water resources consumption of producing in de-salted water and the sewage treatment process, then the consumption of such device water is genuine water and sewage discharge rich and influential family considerably beyond 1,000,000 tons.From the water treatment expense: produce about 9,000,000 yuan of the working cost of 900,000 tons of de-salted waters, handle about 7,000,000 yuan of 900,000 tons of waste water working costs being produced, make the cost of water treatment of producing PTA per ton reach 71 yuan.
In the PTA production process, per hour the de-salted water that passes through the Pd/C beds is up to the 120-150 ton, if water quality is not up to standard, the detrimental impurity in the water is with continuous and the effect of catalyst activity component, destroy activity of such catalysts, finally may become the major cause of catalyst deactivation.Therefore, PTA produces high to the process water water quality requirement, concrete water quality requirement such as following table 1.
Table 1 PTA production technique water water-quality guideline
The sewage of PTA production process discharging is more unmanageable a kind of organic chemical industry sewage, water pollutant is mainly organism and metal ion, wherein removing terephthalic acid is main organic beyond the region of objective existence, the p-Xylol, phenylformic acid, tolyl acid, phthalic acid, ritalin and other organism that also have suitable concentration, the chemical oxygen demand (COD of this sewage
Cr) value is generally the 3000-6000 mg/litre, and rangeability is very big.Because above-mentioned benzene series thing Stability Analysis of Structures is than difficult for biological degradation, big with the ordinary method intractability.Owing to also contain metal ions such as cobalt, manganese, calcium, magnesium in the water, total metal contents in soil, specific conductivity are all higher simultaneously, therefore are difficult to recycling.
Because of fine terephthalic acid production to the water quality requirement height, the waste water quality complexity, the reuse difficulty is big, to the report of PTA factory effluent direct reuse seldom, does the precedent that the technology water cycle is used after the same device no-trump wastewater treatment still both at home and abroad in the domestic and foreign literature.The waste water recycling that the pure terephthalic acid is produced only limits to waste water entered at present incorporates the recirculated water pipe network into after sewage work handles, and does recirculated water, make up water is used.
To the processing of PTA factory effluent, main at present active sludge treatment technology or the employing anaerobic UASB+active contact oxidation technology of adopting handled waste water, and processed waste water satisfies the qualified discharge requirement.
For example, CN 1039784A proposes a kind of PTA Wastewater Treatment by pre-treatment, anaerobic biological treatment, aerobe treatment combination, and complex disposal process, cycle are long.And the waste water after handling through aforesaid method is merely able to qualified discharge, can not be as cyclically utilizing.
CN 1033176A proposes a kind of with method of terephthalic acid in the molysite preliminary sedimentation service water, this method mainly is to adopt ferric sulfate or iron trichloride to make the terephthalic acid in the waste water become the terephthalic acid molysite deposition, add an amount of polyacrylamide simultaneously to improve precipitation threshold, remove precipitation by filtering then.The aromatic acid of this method in can only preliminary sedimentation waste water, and can not remove other organic impurity, and the iron ion (the heavy back of alkali) of having brought at least 5 mg/litre in the water after handling into is given in the adding of molysite.Therefore, the PTA waste water after handling with aforesaid method still can only the qualified discharge standard, can not cyclically utilizing.
CN 1289725A relates to a kind of method with the smart para Toluic Acid's waste water of complexometric extraction pre-treatment.This method comprises at normal temperatures, with in tributyl phosphate, trialkylphosphine oxide, the trialkylamine any one as complexing extractant, waste water is carried out multi-stage counter current extraction purify, make main component such as phenylformic acid and acetic acid enrichment in solvent phase in the waste water, the COD of processed waste water
CrValue is reduced to 1/6 of raw wastewater, and every index satisfies the requirement of biochemical processing process or other secondary method of edge treatment.But after handling with this method, even through behind six grades or the seven grades of cross current solvent extractions, the COD of waste water
CrValue is still about the 2000-4000 mg/litre, and the waste water after the processing equally can only the qualified discharge standard, thereby this is the preconditioning technique of phenylformic acid waste water.
US 4675108 proposes a kind of method of handling wash-down water in the crude terephthalic acid production process, and this method mainly adopts the method for filtration, cationic exchange and anionresin that waste water is handled.The method that adds ion-exchange with filtration is handled organic waste water, though certain feasibility is arranged in theory, but practical application intermediate ion exchange resin is extremely tight to water quality requirement, suspended substance in the water and organism can be deposited on resin surface, cause that exchange capacity reduces and resin property damages, therefore general ion exchange bed allows water inlet COD
CrValue is＜5 mg/litre, and the wash-down water of crude terephthalic acid production process contains a large amount of terephthalic acids, p-Xylol and other organic by-products, COD
CrValue can't directly be carried out ion-exchange up to the 3000-8000 mg/litre at all.
CN 1315295A proposes a kind of pure terephthalic acid's production wastewater treatment method, the method is characterized in that to adopt membrane sepn to separate the treatment technology that combines with resin absorption, makes the COD in the waste water after the processing
CrValue is reduced to about 150 mg/litre.But the water quality after handling still can't satisfy the requirement as the process water reuse.And membrane separation technique exists, and investment is high, working cost is high, operational conditions is harsh, pre-treatment requires high shortcoming to water quality; and the characteristics of PTA waste water are very easily strippings of PTA; often contain a large amount of white particles or throw out in the waste water, can't adopt membrane separation technique to handle as not adding pre-treatment.In addition, this patented method adopts acetic acid that resin is regenerated, and in fact because terephthalic acid is insoluble to acetic acid, therefore the organic acid substance wash-out of resin absorption also can can't be brought into a large amount of COD in the waste water of processing on the other hand with acetic acid on the one hand at all.Therefore, this technology can't satisfy the requirement of PTA device technique water reuse.
Summary of the invention
The objective of the invention is the shortcoming that can not satisfy the cyclically utilizing requirement after prior art is handled the PTA factory effluent in order to overcome, a kind of deep treatment method of pure terephthalic acid's factory effluent is provided, make the waste water after the processing realize the recycling of waste water as the process water cyclically utilizing.
The invention provides a kind of treatment process of pure terephthalic acid's factory effluent, this method comprises pure terephthalic acid's factory effluent is contacted with complexing extractant that the condition that pure terephthalic acid's factory effluent contacts with complexing extractant makes the COD of described waste water
CrBe not more than 2500 mg/litre, separate and remove after the organic phase, the gained water is contacted with ion-exchange material with sorbent material respectively.
The present invention has obtained the deep treatment method of pure terephthalic acid's factory effluent by complexometric extraction and adsorbents adsorb and ion-exchange techniques are combined.Every index with the PTA factory effluent after the method processing provided by the invention all satisfies the upward production of pure terephthalic acid shown in the table 1 to requirements in water quality, can realize pure terephthalic acid's factory effluent as the process water direct reuse, realize that process water truly recycles.And this method treatment effect is good, technology is simple, workable, wide to the water quality scope of application, working cost is lower (facility investment only need treatment process described in the CN 1315295A 1/3rd), and has also saved substantial contribution and the expense of handling fresh process water simultaneously.
Embodiment
Process water that can Recycling of the present invention is meant that every index all satisfies the water of going up pure terephthalic acid's production requirement shown in the table 1.
Complexometric extraction of the present invention is based on a kind of method of separating organic water solution that Lewis acid (or alkali) the property functional group of solute carries out with the Lewis alkali of complexing extractant (or acid) property functional group interaction.Owing to contain a large amount of aforesaid Lewis acidic impurities in the PTA factory effluent, therefore complexing extractant of the present invention can be the organism (being the Lewis basic cpd) that contains the various Lewis of having basic groups, for example can be in alkyl fatty amine, aromatic amine, trialkylphosphine oxide, the trialkylphosphate one or more.Described alkyl is preferably C
2-C
20Positive structure and in the isomery alkyl one or more, C more preferably
6-C
15Positive structure and in the isomery alkyl one or more.For example, the example of described alkyl fatty amine includes but not limited to triethylamine, Trimethylamine 99, diethylamine, trioctylamine, tridodecylamine, dimethylamine, quadrol, methylamine, ethamine, propylamine.The example of described aromatic amine includes but not limited to aniline, para-totuidine, N-methyl-p-nitroaniline.Described TRPO can be one or more in trimethylammonium oxygen phosphorus, triethyl oxygen phosphorus, tripropyl oxygen phosphorus, the tri-tert oxygen phosphorus.The example of described tricresyl phosphate alkane ester preferably includes but is not limited to trimethyl phosphite 99, triethyl phosphate, tributyl phosphate, tricresyl phosphate tertiary butyl ester, TNPP tri n pentyl phosphate, tridecyl phosphate.Complexing extractant of the present invention is preferably the mixing complexing extractant of above-mentioned complexing extractant, for example be preferably the mixed twine mixture of tricresyl phosphate alkane ester and trialkylamine, the mixed weight of tricresyl phosphate alkane ester and trialkylamine is preferably 1 than (association's collection than): 1-15, more preferably 1: 1-5.The inventor is surprised to find that, cooperate the mixing complexing extractant that forms according to aforementioned proportion by trioctylamine, tridodecylamine and tributyl phosphate, be particularly useful for the processing of pure terephthalic acid's factory effluent of the present invention, therefore, the mixing complexing extractant that the preferred described complexing extractant of the present invention is trioctylamine, tridodecylamine, tributyl phosphate, wherein, the weight ratio of trioctylamine and tridodecylamine is preferably 0.5-7: 1.
Preferably also contain thinner in the complexing extractant of the present invention, described thinner can be C
6-C
20Positive structure and isoparaffin, C
6-C
20Halogenated alkane, aromatic hydrocarbons, substituted arene in one or more, for example can be in hexanaphthene, kerosene, the toluene one or more.From environmental protection and bring COD the water into what consider that thinner of the present invention is preferably kerosene.Total amount with complexing extractant is a benchmark, and the content of thinner of the present invention is preferably 0-90 weight %, more preferably 40-70 weight %.
In order to increase the intermiscibility of complexing extractant and waste water, can also optionally contain solubility promoter in the complexing extractant of the present invention.For example, described solubility promoter can be C
2-C
20Positive structure and isomery Fatty Alcohol(C12-C14 and C12-C18), be preferably C
6-C
10Positive structure or in the isomery Fatty Alcohol(C12-C14 and C12-C18) one or more.Add-on to solubility promoter has no particular limits, as long as can make complexing extractant and pending effectively dissolving of waste water.Total amount with complexing extractant is a benchmark, and the content of solubility promoter of the present invention is preferably 0-90 weight %, more preferably 5-15 weight %.There is no particular limitation to the consumption of complexing extractant in the present invention, specifically decides on the concentration and the total amount that have Lewis acidic functionality impurity in the pending waste water.The relative content of complexing extractant is high more, and the effect of complexometric extraction is good relatively more, but cost is also high more; And the relative content of complexing extractant is low more, and the effect of complexometric extraction is poor relatively more, but cost is lower, and this complexing effect can remedy by complexometric extraction repeatedly.The cost of comprehensive complexing extractant, extraction time considers, for the PTA factory effluent of routine, the weight ratio of complexing extractant and pending waste water is 1: 1-20, more preferably 1: 1-6.The operational condition of complexometric extraction can be the complexometric extraction condition of this area routine, and for example, temperature can be that room temperature is to the interior arbitrary temp of system boiling temperature scope.
After above-mentioned complexometric extraction, the most of organic acidity impurity in the PTA factory effluent can be removed.Described complexometric extraction can only carry out once, also can repeat repeatedly, looks the content of impurity and to requirements in water quality and concrete the selection.The inventor finds, because the synergetic between phosphoric acid ester and trioctylamine and the tridodecylamine, the compound complexing extractant that uses above-mentioned phosphoric acid ester of the present invention and trioctylamine and tridodecylamine to form only needs 1 extraction, can make the COD of described waste water
CrBe not more than 1100 mg/litre, treatment effect is far superior to the report in CN 1289725A and the pertinent literature.The time of preferred complexometric extraction is 10-100 minute in the specific embodiment of the invention, and temperature is preferably 15-45 ℃.Complexing extractant after complexometric extraction is finished can be with recycling behind the alkali liquid regeneration.The alkali lye of complexing extractant of being used to regenerate can be NaOH, KOH, Na
2CO
3In one or more, the concentration of alkali lye for example can be 0.5-15 weight %, the add-on of alkali lye is preferably 1 with the ratio of complexing extractant add-on: 5-20.The regenerated temperature is preferably 50-80 ℃, and the time is 10-100 minute.Described complexometric extraction and regenerated concrete operations have been conventionally known to one of skill in the art, do not repeat them here.
Behind the complexometric extraction, isolate water that does not contain or contain small part organic acidity impurity and metal ion and the oil phase that has adsorbed a large amount of organic acidity impurity.Described water preferably is introduced in the adsorption unit to contact with sorbent material and adsorbs, and removing a small amount of organic impurity remaining in the waste water, and then contact the metal ion in the removal waste water with ion-exchange material.Described sorbent material is preferably one or more in macroporous resin, gac, the activated carbon fiber, more preferably activated carbon fiber.Described macroporous resin can be various absorption resins, for example can be that marque is one or more in the resin of DA-201, DM-301, NKA-2, XAD-4, CHA-11, CHA-101, XAD7HP.Described gac can be the various gacs that are conventionally used as sorbent material.Described activated carbon fiber can be various activated carbon fiber, is preferably in viscose-based active carbon fiber, polypropylene cyanogen activated carbon fiber, asphalt based active carbon fiber and the phenolic resin based activated carbon fiber that specific surface is not less than 1000 meters squared per gram one or more.The inventor is surprised to find that, effect when activated carbon fiber is used for PTA production wastewater treatment technology of the present invention obviously is better than macroporous resin and the conventional acticarbon adsorption effect to organic acidity impurity, therefore, the more preferably described sorbent material of the present invention is above-mentioned activated carbon fiber, and more preferably the specific surface of activated carbon fiber is the 1000-2500 meters squared per gram.
Described waste water can be realized by waste water behind the complexometric extraction and sorbent material are mixed the mode that contacts in container with contacting of sorbent material, also can realize by the mode of adsorption column.The consumption that it will be appreciated by persons skilled in the art that sorbent material is big more, and is good more to the treatment effect of waste water, but cost is also high more.Comprehensive cost and effect of extracting consider that the waste water behind the preferred complexometric extraction of the present invention and the weight ratio of sorbent material are 5-1500: 1, and 50-1000 more preferably: 1.When adopting the mode of mixing contact in container, the temperature of mixing contact is preferably 15-50 ℃, and the time is preferably 10-300 minute.Comprehensive production cost considers, preferably at room temperature, mix contact 20-60 minute under agitation condition.Described adsorption column mode can be adsorbed by the mode that goes out on advancing below the waste water behind the complexometric extraction is passed in the adsorption column, sorbent material and the ratio of the add-on of waste water are looked the different in kind of the capacity of adsorption unit and sorbent material and are different, the blade diameter length ratio of preferred adsorption column is 1: 3-10, waste water is preferably≤10BV/ hour by the flow velocity of adsorption column, under the preferable case, the described adsorption operations of water and sorbent material carries out at 15-50 ℃, more preferably at room temperature carries out.The sorbent material that adsorbs after saturated can carry out counter-current regeneration, regenerated liquid consumption≤12BV with for example 1-2 weight %NaOH aqueous solution.Absorption and regenerated specific operation process have been conventionally known to one of skill in the art, do not repeat them here.
After above-mentioned complexometric extraction and adsorption treatment, the organic impurity content in the waste water reaches the standard that can recycle, as long as the impurity metal ion of removing in the waste water is that the PTA of being used for capable of circulation has produced.The present invention adopts the method for ion-exchange to remove metal ion in the waste water.The method of described ion-exchange preferably realizes by making to contact with ion-exchange material through the water after complexometric extraction and the adsorbents adsorb.Described ion-exchange material is preferably ion exchange resin, and described ion exchange resin can be the storng-acid cation exchange resin that can remove metal ions such as chromium, iron, cobalt, manganese, calcium, magnesium, zinc known to a person of ordinary skill in the art.Described storng-acid cation exchange resin for example can be selected from that marque is 001 * 7, among 001 * 7FC, the 001 * 7MB one or more.The consumption that it will be appreciated by persons skilled in the art that Zeo-karb is big more, and is good more to the treatment effect of waste water, but cost is also high more.Comprehensive cost and effect of extracting consider that the preferred described Zeo-karb of the present invention is preferably 1 with the ratio of the add-on of water: 5-1500, more preferably 1: 50-1000.The mode of described ion-exchange can be the mode that stirs contact of mixing in container, also can be the form of ion exchange column.When adopting the mode of mixing contact in container, the temperature of mixing contact is preferably 15-50 ℃, and the time is preferably 10-200 minute.Comprehensive production cost considers, preferably at room temperature, mix contact 20-60 minute under agitation condition.The described form of crossing ion exchange column is preferably and makes to advance below the water mode adverse current process that outes is the mode of the ion exchange column of stationary phase with ion exchange resin.The blade diameter length ratio of ion exchange column is 1: 3-10, and the temperature that described water contacts with ion exchange resin is preferably room temperature to 50 ℃, and the flow velocity of water is preferably≤15BV/h.
For the waste water of directly discharging with Pressure Centrifuges, method of wastewater treatment provided by the invention preferably also comprises the filtration step that waste water is removed by filter insoluble solid impurities.Described filtration can adopt conventional various filter types to carry out.
With the PTA factory effluent is example, and method of the present invention specifically can realize as follows:
1. will produce the waste water that Pressure Centrifuges is discharged the refining step from PTA at first filters with strainer;
2. the waste water after filtering enters the complexometric extraction device and carries out complexometric extraction, makes organic substance enrichments in solvent phase such as acetic acid in the waste water, aromatic acid, isolates water;
3. the waste water after extraction enters resin or carbon fiber adsorption and catalytic combustion tripping device, thoroughly removes residual organic;
4. thoroughly remove organic waste water through extraction, absorption and enter ion exchange unit, remove metal ion, handle the back water sample and introduce refining step again as the recycled process water.
Among the present invention, the alkali dope after the alkali dope after the complexometric extraction regeneration, macroporous adsorbent resin and the activated carbon fiber regeneration contains the terephthalic acid of high density, and further acid is heavy, reclaims terephthalic acid, thus the resource utilization of realization waste water.
The following examples will the invention will be further described.Use COD among the embodiment
CrThe value representation chemical oxygen demand, its value is according to GB11914-89 COD
CrRapid determination instrument (the logical enviromental protection instrument company limited of Chengde China produces) is measured; Sulfide content is with SO
4 2-Meter is measured with the ion chromatography of GB/T14642-93; The silicide spectrophotometry of GB/T16633-1996.
Embodiment 1
Present embodiment is used to illustrate PTA production wastewater treatment reuse method provided by the invention.
The waste water (shown in the table 2 composed as follows of waste water) of getting the TA refining stage of 2000 gram solids removed by filtration impurity join in 5000 milliliters the separating funnel, the mixing complexing extractant that will contain 100 gram trioctylamines, 200 gram n-Octanols and 300 gram kerosene then joins in the separating funnel, cover bottle stopper, under the room temperature, vibration is 30 minutes in shaking table, makes two-phase reach extraction equilibrium, leaves standstill then, take out water, carry out COD
CrPH-value determination pH.Measurement result is as shown in table 3 below.
It is in 2.3 centimetres the glass adsorption column that the macroporous adsorbent resin (DM301) that weighing 20 gram is done is packed into diameter, loading height is 11.0 centimetres, go out mode on advancing below the waste water and flow into adsorption column, flow velocity is 5 ml/min, and collection 1000 restrains effluent liquid and measures the COD of effluent liquid
CrValue.Measurement result is as shown in table 3 below.
The storng-acid cation exchange resin (001 * 7 type) that weighing 4.5 grams are done, place 1000 milliliters of Erlenmeyer flasks, add the water sample after 500 milliliters of above-mentioned complexometric extractions and the resin absorption, put into shaking bath vibration 5 hours, separation resin and water carry out COD to water sample
CrThe mensuration of value, metal content and specific conductivity.The results are shown in Table shown in 3.
Embodiment 2
Present embodiment is used to illustrate PTA production wastewater treatment reuse method provided by the invention.
Getting 2000 grams forms in the separating funnel that the waste water identical with embodiment 1 joins 5000 milliliters, the complexing extractant that will contain 200 gram tributyl phosphates and 200 gram kerosene then joins in the separating funnel, cover bottle stopper, under 40 ℃, vibration is 10 minutes in shaking table, makes two-phase reach extraction equilibrium, leaves standstill then, take out water, carry out COD
CrPH-value determination pH.Measurement result is as shown in table 3 below.
The macroporous adsorbent resin (NKA-2) that weighing 10 grams are done places 1000 milliliters of Erlenmeyer flasks, and the water sample behind the above-mentioned complexometric extraction of adding 2000 grams is put into shaking table vibration 3 hours with Erlenmeyer flask, and separation resin and water carry out COD to water sample
CrPH-value determination pH.Measurement result is as shown in table 3 below.
It is in 2.3 centimetres the glass adsorption column that the storng-acid cation exchange resin (001 * 7 type) that weighing 20 gram is done is packed into diameter, loading height is 11.0 centimetres, go out mode on advancing below the waste water and flow into adsorption column, flow velocity is 5 ml/min, and collection 2000 restrains effluent liquid and measures the COD of effluent liquid
CrValue, metal content and specific conductivity.The results are shown in Table shown in 3.
Embodiment 3
Present embodiment is used to illustrate PTA production wastewater treatment reuse method provided by the invention.
According to the method for embodiment 1 2000 gram PTA factory effluents are carried out Treatment for Reuse, different is, complexing extractant is 50 gram trioctylamines, 50 gram tridodecylamines, 300 gram kerosene and 100 gram isooctyl alcohol, and the amount of Zeo-karb is 4.0 grams.Experimental result is shown in table 3 or table 4.
Embodiment 4
Present embodiment is used to illustrate PTA production wastewater treatment reuse method provided by the invention.
Method according to embodiment 3 is carried out Treatment for Reuse to 2000 gram PTA factory effluents, and different is that complexing extractant is 50 gram tridodecylamines, 150 gram tributyl phosphates, 270 gram kerosene and 30 n-Octanols.Experimental result is as shown in table 4.
Embodiment 5
Present embodiment is used to illustrate PTA production wastewater treatment reuse method provided by the invention.
Method according to embodiment 3 is carried out Treatment for Reuse to 2000 gram PTA factory effluents, and different is that complexing extractant is 50 gram trioctylamines, 150 gram tributyl phosphates, 270 gram kerosene and 30 n-Octanols.Experimental result is as shown in table 4.
Embodiment 6
Present embodiment is used to illustrate PTA production wastewater treatment reuse method provided by the invention.
Method according to embodiment 3 is carried out Treatment for Reuse to 2000 gram PTA factory effluents, and different is that complexing extractant is 30 gram tributyl phosphates, 60 gram trioctylamines and 10 gram tridodecylamines, 300 gram kerosene.Experimental result is shown in table 3 or table 4.
Embodiment 7
Present embodiment is used to illustrate PTA production wastewater treatment reuse method provided by the invention.
Method according to embodiment 3 is carried out Treatment for Reuse to 2000 gram PTA factory effluents, and different is that complexing extractant is 10 gram tributyl phosphates, 50 gram trioctylamines and 40 gram tridodecylamines.Experimental result is as shown in table 4.
Embodiment 8
Present embodiment is used to illustrate PTA production wastewater treatment reuse method provided by the invention.
Method according to embodiment 3 is carried out Treatment for Reuse to 2000 gram PTA factory effluents, and different is that complexing extractant is 20 gram tributyl phosphates, 60 gram trioctylamines and 20 gram tridodecylamines.Experimental result is as shown in table 4.
Comparative Examples 1
This Comparative Examples is used to illustrate the method for prior art treatment PTA factory effluent.
Method according to embodiment 1 is handled 2000 gram PTA factory effluents, and different is that the complexometric extraction step is used the membrane sepn treatment step replacement described in the CN 1315295A instead, and selected microfiltration membrane is a stainless steel membrane, 0.1 micron in aperture.Experimental result such as table 3.
Table 2 raw material waste water composition
| The compound title | Content |
| Terephthalic acid (mg/litre) | 1150 |
| P-methylbenzoic acid (mg/litre) | 1700 |
| Phenylformic acid (mg/litre) | 50 |
| Acetic acid (mg/litre) | 1200 |
| P-Hydroxybenzaldehyde (mg/litre) | 30 |
| Cobalt (mg/litre) | 9.8 |
| Manganese (mg/litre) | 5.2 |
| The pH value | 3.6 |
| Total metal (mg/litre) | 26.3 |
| COD value (mg/litre) | 3256.8 |
| Specific conductivity (μ s/cm) | 230 |
Table 3 wastewater treatment result
*These data are the data behind the membrane sepn, rather than the data behind the complexometric extraction.
Table 4 wastewater treatment result
From the result of last table 3, table 4 as can be seen, after with method provided by the invention the PTA factory effluent being handled, every index of the water after gained is handled meets the requirement of process water fully, can cyclically utilizing.And, the mixture that uses trioctylamine, tridodecylamine and tributyl phosphate obviously is better than the complexometric extraction effect of other complexing extractant as the complexometric extraction effect of complexing extractant, and the adsorption effect of activated carbon fiber is obviously owing to the macroporous resin absorption effect.
Claims (12)
1. the treatment process of pure terephthalic acid's factory effluent, this method comprises pure terephthalic acid's factory effluent is contacted with complexing extractant, the condition that pure terephthalic acid's factory effluent contacts with complexing extractant makes the chemical oxygen demand of described waste water be not more than 2500 mg/litre, separate and remove after the organic phase, the gained water is contacted with ion-exchange material with sorbent material respectively, described complexing extractant contains the Lewis basic cpd, described Lewis basic cpd is the mixture of trialkyl aliphatic amide and trialkylphosphate, the weight ratio of trialkyl aliphatic amide and trialkylphosphate is 1-15: 1, and described alkyl is C
2-C
20Positive structure and in the isomery alkyl one or more.
2. method according to claim 1, wherein, the condition that described pure terephthalic acid's factory effluent contacts with complexing extractant comprises that the temperature of contact is a room temperature to 50 ℃, and the time is 10-100 minute, and the weight ratio of described complexing extractant and waste water is not less than 0.05.
3. method according to claim 2, wherein, the weight ratio of described complexing extractant and waste water is 0.05-1.
4. method according to claim 1, wherein, described trialkyl aliphatic amide is trioctylamine and/or tridodecylamine, described trialkylphosphate is a tributyl phosphate.
5. method according to claim 4, wherein, described trialkyl aliphatic amide is the mixture of trioctylamine and tridodecylamine, the weight ratio of trioctylamine and tridodecylamine is 0.5-7.
6. method according to claim 1, wherein, described complexing extractant also contains the thinner of 0-90 weight %, and described thinner is selected from C
6-C
20Positive structure and in the isoparaffin, halogenated alkane, aromatic hydrocarbons, substituted arene one or more.
7. method according to claim 1, wherein, described water contacts with sorbent material for elder generation with the order that sorbent material contacts with ion-exchange material respectively, and then contacts with ion-exchange material.
8. according to claim 1 or 7 described methods, wherein, described sorbent material is one or more in macroporous resin and the gac, and described ion-exchange material is a Zeo-karb.
9. method according to claim 8, wherein, described sorbent material be specific surface be not less than 1000 the gram/square metre activated carbon fiber.
10. method according to claim 9, wherein, the specific surface of described activated carbon fiber be 1000-2500 gram/square metre.
11. according to claim 1 or 7 described methods, wherein, the weight ratio of described water and sorbent material is 50-1000: 1, the weight ratio of described water and ion-exchange material is 50-1000: 1.
12. according to claim 1 or 7 described methods, wherein, the temperature that described water contacts with sorbent material is a room temperature to 50 ℃, the time is 20-300 minute; The temperature that contacts with ion-exchange material is a room temperature to 50 ℃, and the time is 20-300 minute.
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| CN102295380A (en) * | 2011-08-19 | 2011-12-28 | 杭州江南科学研究院有限公司 | Processing and recovering method of aromatic nitro-compound wastewater |
| CN102910761B (en) * | 2012-11-06 | 2015-03-11 | 绍兴汉青环保科技有限公司 | Extraction method for reducing emission of chemical oxygen demand (COD) in pure terephthalic acid (PTA) wastewater |
| CN103693772B (en) * | 2013-01-11 | 2015-09-02 | 绍兴汉青环保科技有限公司 | PTA refined wastewater Resource comprehensive utilization method |
| CN106477770B (en) * | 2016-10-26 | 2019-11-08 | 浙江奇彩环境科技股份有限公司 | The processing method of N- (1- ethyl propyl) -3,4- dimethylaniline production waste water |
| CN107935092A (en) * | 2017-11-06 | 2018-04-20 | 广东省资源综合利用研究所 | A kind of method of hydroximic acid production waste water reclaiming |
| CN108439520A (en) * | 2018-03-13 | 2018-08-24 | 青岛凤凰东翔印染有限公司 | A method of it reducing batik with Complexation Extraction Technique and produces Aniline content |
| CN111747601B (en) * | 2019-03-26 | 2022-03-29 | 中蓝连海设计研究院有限公司 | Treatment method of PTA-containing wastewater RO concentrated water |
| CN110372116A (en) * | 2019-08-09 | 2019-10-25 | 大连凯信石化科技有限公司 | A method of acetic acid in recycling PTA oxidation unit waste water |
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