CN104003555A - Method of pretreating dyeing and finishing wastewater - Google Patents
Method of pretreating dyeing and finishing wastewater Download PDFInfo
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- CN104003555A CN104003555A CN201410255469.XA CN201410255469A CN104003555A CN 104003555 A CN104003555 A CN 104003555A CN 201410255469 A CN201410255469 A CN 201410255469A CN 104003555 A CN104003555 A CN 104003555A
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Abstract
The invention belongs to a method of pretreating dyeing and finishing wastewater. The method comprises the steps of wastewater collection, primary precipitation, primary acid precipitation and secondary acid precipitation, wherein the primary acid precipitation comprises the steps of adding concentrated sulfuric acid in dirt removal alkali-minimization wastewater, carrying out neutral reaction under the condition of mixing, stopping adding the concentrated sulfuric acid when a pH value is 3-4, then precipitating out a great deal of phthalic acid in a reaction tank, removing the phthalic acid, and then carrying out vacuum centrifugal filtration, drying, purifying and recycling. With the adoption of the method, the dyeing and finishing wastewater generated in a part of procedures in the printing and dyeing process is pretreated by virtue of a physicochemical method, organic matters in the dyeing and finishing wastewater are removed, a part of organic matters, particularly the phthalic acid in the alkali-minimization wastewater is separated and recovered, and the wastewater discharged in the procedures is mixed and regulated finally, so that the wastewater can reach the requirement of subsequent biochemical deep treatment and has the advantages of high resource recovery utilization rate and good energy-saving and environmental protection effects.
Description
Technical field
The invention belongs to a kind of method of pre-treatment dyeing and finishing wastewater.
Background technology
The dyeing and finishing wastewater of textile printing and dyeing industry discharge is one of major polluting sources in China's industrial system.According to State Environmental Protection Administration statistics, the dyeing and finishing wastewater total amount of dyeing discharge is positioned at five of total flow controls of each industrial sector discharge of the whole nation, and its gross contamination emission (in COD) is positioned at the 6th of each industrial sector.
Dyeing and finishing wastewater is that a class contains a certain amount of organic wastewater that is difficult to degradable chemical, and complicated component, and change of water quality amplitude is large.Its Pollutant levels high (COD), colourity are dark and have certain toxicity, are one of unmanageable trade effluents.In recent years, along with the variation of market to dyeing and printing products demand, in dyeing and printing products, the output of many kinds, be pilot strengthens, and production unit discontinuous formula dyeing apparatus accounts for larger specific gravity.Due to the variation of range of product and the automatic control level of dyestuff and auxiliary agent dosage lower, its wastewater discharge and water concentration are all higher than continous way dyeing installation in the past, and different enterprises applies the chemical agents such as different production technologies, dyestuff and auxiliary agent, water-quality constituents is complicated, the waste water composition and the water yield that under the different operating modes of same enterprise, produce also change larger, this has increased wastewater treatment difficulty to built waste water treatment engineering, also traditional Pollution abatement qualified discharge technology has been proposed to new challenge.
The water quality of dyeing and finishing wastewater is with the difference of the kinds of fibers adopting and complete processing and different, and contaminant component is widely different.The pH value of general dyeing and finishing wastewater is between 6 to 10, and CODcr is between 400 to 1000mg/L, and colourity is 100 to 400 times, and SS is 100 to 200mg/L.But after the kinds of fibers and complete processing variation of dyeing and printing process and employing, will there is larger variation in waste water quality.For example, while containing the alkali decrement waste water producing in terylene artificial silk dyeing process in waste water, more than the CODcr of waste water will increase to 20000mg/L, BOD
5also more than increasing to 800mg/L, pH value reaches more than 13, and waste water quality adding and worsen with terylene artificial silk dyeing and finishing alkali decrement waste water.In the amount excess wastewater of the alkali decrement waste water adding, 20% of COD amount time, biochemical treatment will be difficult to adaptation.
The waste water situation of each operation of printing and dyeing discharge is generally:
(1) desized wastewater: the water yield is less, but Pollutant levels are high, wherein contain various slurries, slurry resolvent, fiber flock, starch alkali and various auxiliary agent.Waste water is alkalescence, and pH value is 12 left and right.Starching be take starch as main (as cotton) desized wastewater, its COD, BOD
5be worth all very high, good biodegradability.Starching be take polyvinyl alcohol (PVA) and is main (as polyester-cotton blend warp thread) desized wastewater, and COD is high and BOD is low, and wastewater biodegradability is poor.
(2) boiled-off waste water: the water yield is large, Pollutant levels are high, wherein contains Mierocrystalline cellulose, tartaric acid, wax, grease, alkali, tensio-active agent, nitrogenous compound etc., and waste water is alkalescence, and water temperature is high, is brown.
(3) bleaching effluent: the water yield is large, but pollution is lighter, wherein contains remaining SYNTHETIC OPTICAL WHITNER, a small amount of acetic acid, oxalic acid, Sulfothiorine etc.
(4) mercerizing waste water: alkalinity is high, NaOH content is 3%～5%, and most printing and dyeing mills reclaim NaOH by evaporation concentration, so mercerizing waste water is generally seldom discharged, the waste water that is repeatedly used final discharge through technique is still strong basicity, and BOD, COD, SS are all higher.
(5) dyeing waste-water: the water yield is larger, water quality is different with the difference of dyestuff used, wherein, containing slurry, dyestuff, auxiliary agent, tensio-active agent etc., is generally strong basicity, and colourity is very high, and COD is compared with BOD
5much higher, biodegradability is poor.
(6) printing waste water: the water yield is larger, except the waste water of stamp process, also comprises soaping after stamp, washing waste water, and Pollutant levels are higher, wherein contain slurry, dyestuff, auxiliary agent etc., and BOD, COD are all higher.
(7) arrange waste water: the water yield is less, wherein contains fiber flock, resin, finish, slurry etc.
(8) alkali decrement waste water: be that terylene artificial silk alkali decrement operation produces, main containing terylene hydrolyzate terephthalic acid (PTA), ethylene glycol (EG) etc., wherein terephthaldehyde's acid content is up to 75%, not only pH value is high for alkali decrement waste water, and organic concentration is high, in the waste water of alkali decrement operation discharge, CODcr can reach 90000mg/L, and macromolecule organic and part dyestuff are difficult to be biodegradable, and this kind of waste water belongs to high concentration hard-degraded organic waste water.
From the composition of above-mentioned dyeing and finishing wastewater, be not difficult to find out, in dyeing and finishing wastewater, especially organic content is higher in alkali decrement waste water, alkalescence is larger, the dyeing and finishing wastewater combination treatment directly all process steps being produced, scale and the difficulty of waste water treatment have not only been strengthened, and be difficult to carry out biological chemistry advanced treatment, strengthened treatment cost, and the large amount of organic in water effectively do not recycled, easily produced secondary pollution.How solving an above-mentioned difficult problem, is problem in the urgent need to address.
Summary of the invention
The object of the invention is to design a kind of method of pre-treatment dyeing and finishing wastewater, the dyeing and finishing wastewater that dyeing process middle part operation break-down can be produced first carries out physicochemical method pre-treatment, remove organism wherein, phthalic acid in partial organic substances especially alkali decrement waste water is carried out to Separation and Recovery, finally make the waste water of these operation discharges mix adjusting, can reach the requirement of follow-up biological chemistry advanced treatment, there is resource recycling rate high, the advantage that effects of energy conservation and environmental protection is good.
For this reason, the present invention includes following steps:
Comprise the steps,
(1) wastewater collection, builds respectively alkali decrement waste water, dyeing and finishing wastewater collecting tank and wastewater equalization pond, and the alkali decrement waste water of generation and dyeing and finishing wastewater are collected respectively in alkali decrement waste water collecting tank and dyeing and finishing wastewater collecting tank;
(2) preliminary sedimentation carries out alkali decrement waste water preliminary sedimentation in alkali decrement waste water collecting tank, dyeing and finishing wastewater is carried out in dyeing and finishing wastewater collecting tank to preliminary sedimentation, and the throw out at the bottom of two ponds after precipitation is removed;
(3) acid outs, in scrubbing alkali decrement waste water, add the vitriol oil and under agitation carry out neutralization reaction, when pH value is 3～4, stopping acid adding, now in reaction tank, having a large amount of phthalic acids to separate out, phthalic acid is removed, through traditional vacuum filter, dry after, purify recycling;
(4) secondary acid out, the supernatant liquor of alkali decrement waste water after an acid out is mixed with dyeing and finishing wastewater, adding the vitriol oil to composite waste pH value is 3～4 o'clock, stop acid adding, add polyacrylamide flocculant coagulation, making the concentration in composite waste is 10～30ppm, after coagulum sedimentation again, with plate-and-frame filter press, by the waste water filtering after secondary acid out, filter mud and separately use it for anything else;
(5) mix and regulate, after supernatant liquor other waste water low with other chemical oxygen content, that concentration is little after secondary acid out is filtered mixes in wastewater equalization pond, regulate this pond mixing water pH after between 6～7, can enter into biological chemistry advanced treatment flow process, complete the pre-treatment in early stage of waste water.
The time of described preliminary sedimentation is at least 12 hours.Described polyacrylamide flocculant molecular-weight average is 3,000,000～1,200 ten thousand.Described polyacrylamide flocculant is cationic organic polymer coargulator.
Aforesaid method has reached object of the present invention.
Tool of the present invention has the following advantages:
The dyeing and finishing wastewater that the present invention can produce dyeing process middle part operation break-down first carries out physicochemical method pre-treatment, remove organism wherein, phthalic acid in partial organic substances especially alkali decrement waste water is carried out to Separation and Recovery, finally make the waste water of these operation discharges mix adjusting, can reach the requirement of follow-up biological chemistry advanced treatment, there is resource recycling rate high, the advantage that effects of energy conservation and environmental protection is good.
1, substep acid out, first, first carries out alkali decrement waste water and dyeing and finishing wastewater after preliminary sedimentation decontamination, then carries out substep acid out.Substep acid out is because only contain the ethylene glycol etc. of a large amount of para-phthalic sodiums and minute quantity in alkali decrement waste water.Therefore existing, alkali decrement waste water is carried out to acid out and obtain a large amount of phthalic acids and can collect and do industrial application, played the effect of changing waste into resources, bring economic benefit.Meanwhile, the phthalic acid particle forming after acid out is tiny, is difficult for coagulant precipitation, uses Plate Filtration very difficult.Therefore existing, alkali decrement waste water is done to acid out and process, do not add flocculation agent and directly carry out vacuum (centrifugal) filtration, both guaranteed the purity of phthalic acid, reduced again follow-up sludge treatment problem.In addition, distribution acid out has been saved the consumption of the vitriol oil and flocculation agent, reduces treatment cost.
2, acid-precipitation method with respect to active carbon adsorption, salting-out process, to subtract the method for analysing etc. simple to operate, is applicable to extensive processing.The expense of the vitriol oil is low, and colourless, can not increase the colourity of waste water, and acid out is effective.
3, polyacrylamide flocculant is macromolecule organic flocculating agent, experiment finds that absorption and coagulation effect is better than inorganic flocculating agent, secondly polyacrylamide flocculant all has good absorption and coagulation effect in acid and alkaline environment, in addition, polyacrylamide flocculant can make organic macromolecule and the chromophoric group in waste water assemble sedimentation, removes to a certain extent colourity and the chemical oxygen content of waste water.
4, some chemical oxygen content concentration are little, can not carry out pre-treatment by the high waste water of biochemical degree, reach and can biochemical standard mix and regulate in expection after other wastewater treatments, reduced the pre-treatment water yield, saved treatment cost.
In a word, the dyeing and finishing wastewater that the present invention can produce dyeing process middle part operation break-down first carries out physicochemical method pre-treatment, remove organism wherein, phthalic acid in partial organic substances especially alkali decrement waste water is carried out to Separation and Recovery, finally make the waste water of these operation discharges mix adjusting, make its requirement that has reached follow-up biological chemistry advanced treatment, there is resource recycling rate high, the advantage that effects of energy conservation and environmental protection is good.
Accompanying drawing explanation
Fig. 1 is pre-treatment dyeing and finishing wastewater process flow sheet of the present invention.
Fig. 2 is that the invention process is processed dyeing and finishing wastewater process flow sheet in Jiangsu Province dyeing and finishing company.
Embodiment
As shown in Figure 1, a kind of method of pre-treatment dyeing and finishing wastewater, comprises the steps:
(1) wastewater collection, builds respectively alkali decrement waste water, dyeing and finishing wastewater collecting tank and wastewater equalization pond, and the alkali decrement waste water of generation and dyeing and finishing wastewater are collected respectively in alkali decrement waste water collecting tank and dyeing and finishing wastewater collecting tank.
(2) preliminary sedimentation carries out alkali decrement waste water preliminary sedimentation in alkali decrement waste water collecting tank, dyeing and finishing wastewater is carried out in dyeing and finishing wastewater collecting tank to preliminary sedimentation, and the throw out at the bottom of two ponds after precipitation is removed.The time of described preliminary sedimentation is at least 12 hours, and two collecting tanks can adopt circulation intermediate processing to guarantee sedimentation time, and as adopted upper end, pond to establish into waste water, opposite side upper end corresponding to pond sets out the mouth of a river, can guarantee the time of the preliminary sedimentation of waste water.
(3) acid outs, in scrubbing alkali decrement waste water, add the vitriol oil and under agitation carry out neutralization reaction, when pH value is 3～4, stopping acid adding, now in reaction tank, having a large amount of phthalic acids to separate out, phthalic acid is removed, through traditional vacuum filter, dry after, purify recycling.
(4) secondary acid out, the supernatant liquor of alkali decrement waste water after an acid out is mixed with dyeing and finishing wastewater, adding the vitriol oil to composite waste pH value is 3～4 o'clock, stop acid adding, then add polyacrylamide flocculant coagulation, making the concentration in composite waste is 10～30ppm, after coagulum sedimentation, with plate-and-frame filter press, by the waste water filtering after secondary acid out, filter mud and separately use it for anything else, as being mixed and made into fire coal with coal dust.
(5) mix and regulate, after supernatant liquor other waste water low with other chemical oxygen content, that concentration is little after secondary acid out is filtered mixes in wastewater equalization pond, regulate this pond mixing water pH after between 6～7, can enter into biological chemistry advanced treatment flow process, complete the pre-treatment in early stage of waste water.
Described polyacrylamide flocculant molecular-weight average is 3,000,000～1,200 ten thousand.Described polyacrylamide flocculant is cationic organic polymer coargulator.
The present invention embodiment in process of production:
As shown in Figure 2, for the invention process is processed dyeing and finishing wastewater process flow sheet in Jiangsu Province dyeing and finishing company.
The large-scale manufacturing enterprise that Jiangsu Province dyeing and finishing company is that Yi Jiaji weaves cotton cloth, dyeing, coating are integrated.Due to need of production, every day all will be discharged a large amount of high densitys, difficult degradation organic basic waste water by this factory, processes direct discharge will cause serious water pollution problems if do not added.This factory's waste water water temperature is higher, poisonous in water, hardly degraded organic substance content is large, medicine dosage is held the difficulty that the reason such as improper has strengthened waste water treatment.
This factory each workshop waste water production under full production state is as shown in table 1.The waste water that this factory's production plant produces comprises refining wastewater, alkali decrement waste water, horizontal waste water and the overflow waste water of opening the door.Wherein alkali decrement waste water is mainly containing terylene hydrolyzate terephthalic acid (PTA), ethylene glycol (EG) etc., not only pH value can be up to more than 14, and organic concentration is high, macromolecule organic and part dyestuff are difficult to be biodegradable, and belong to high concentration hard-degraded organic waste water.Refining wastewater is that starching be take polyvinyl alcohol (PVA) as main (as polyester-cotton blend warp thread) desized wastewater, and chemical oxygen content (COD) is high and biochemical oxygen level (BOD) is low, and wastewater biodegradability is poor; In the horizontal waste water that opens the door, also contain on a small quantity with polyvinyl alcohol (PVA), (COD) is low compared with refining wastewater for chemical oxygen content, but owing to being printing and dyeing links, the chroma in waste water of generation is high, turbidity is large; The overflow waste water water yield is large, but chemical oxygen content (COD) is lower, below 1000mg/L.
Table 1 waste water production
Investigate the concrete generation situation of this factory's waste water, find that each workshop waste water differs greatly, water quality is seriously unstable, and due to each workshop discharge of wastewater channel and simple and crude of this factory, due to not separately, fixedly blowdown channel causes the unstable of got waste water quality.
Water quality and quantity situation in conjunction with this factory's dyeing and finishing wastewater, adopts pretreatment process of the present invention to waste water:
(1) wastewater collection, builds respectively alkali decrement waste water, dyeing and finishing wastewater collecting tank and wastewater equalization pond, and the alkali decrement waste water of generation and dyeing and finishing wastewater are collected respectively in alkali decrement waste water collecting tank and dyeing and finishing wastewater collecting tank.
(2) preliminary sedimentation carries out alkali decrement waste water preliminary sedimentation in alkali decrement waste water collecting tank, dyeing and finishing wastewater is carried out in dyeing and finishing wastewater collecting tank to preliminary sedimentation, and the throw out at the bottom of two ponds after precipitation is removed.
(3) one step acid outs: by alkali decrement waste water, add 98% the vitriol oil to pH between 3～4, carry out online pH control, and adopting mechanical stirring, a large amount of phthalic acids (PTA) are separated out, and after continuously centrifuged filtration, dry efflorescence, can obtain pure phthalic acid (PTA).Alkali decrement waste water with 800t/d calculates, and the phthalic acid of generation (PTA) can reach 5-6t/d, and through detecting, the phthalic acid of recovery (PTA) purity reaches the requirement that commercial recovery is used completely, makes enterprise produce huge economic benefit.
(4) two step acid outs: the supernatant liquor of processing after alkali decrement waste water is mixed at mixing pit with refining wastewater and the horizontal waste water that opens the door, because the alkalescence of refining wastewater and the horizontal waste water that opens the door is strong, the water yield is little, mainly contain phthalic acid (PTA) and two kinds of Persistent organic pollutants of polyvinyl alcohol (PVA), biodegradability is poor, and supernatant liquor is strongly-acid after alkali decrement waste water acidifying, the two mixing is carried out quadratic acid and is analysed, and has saved the consumption of the vitriol oil.To add in mixing pit 98% the vitriol oil to pH between 3～4, carry out online pH control, and adopt mechanical stirring, solid is separated out, add again cationic polyacrylamide (CPAM) flocculation agent coagulation, making its concentration in water is 10 to 30ppm, after coagulant precipitation, solid is filtered by plate-and-frame filter press, three's mixing water is pressed the treatment capacity of 1700t/d and is calculated, and the sludge quantity of generation, only less than 5t/d, has greatly reduced the treatment capacity of mud, reduce the generation of solid waste, saved treatment cost.After testing, now the chemical oxygen content in waste water (COD), in 2500mg/L left and right, greatly reduces chemical oxygen content (COD) concentration.
(5) mix and regulate: the supernatant liquor that two step acid outs are obtained is introduced in wastewater equalization pond and mixed with overflow waste water, the overflow waste water water yield is large, (COD) is low for chemical oxygen content, biodegradability is high, need not carry out pre-treatment in front, and mix with the supernatant liquor of two step acid outs, regulated pH, reduced the consumption of pH regulator medicament, utilize pH on-line monitoring, add pH adjusting agent to regulate pH to 6～7, after testing, now the COD in waste water, in 1500mg/L left and right, can carry out follow-up biological chemistry advanced treatment completely.
In a word, the dyeing and finishing wastewater that the present invention can produce dyeing process middle part operation break-down first carries out physicochemical method pre-treatment, remove organism wherein, phthalic acid in partial organic substances especially alkali decrement waste water is carried out to Separation and Recovery, finally make the waste water of these operation discharges mix adjusting, make its requirement that has reached follow-up biological chemistry advanced treatment, there is resource recycling rate high, the advantage that effects of energy conservation and environmental protection is good.
Claims (4)
1. a method for pre-treatment dyeing and finishing wastewater, is characterized in that: comprises the steps,
(1) wastewater collection, builds respectively alkali decrement waste water, dyeing and finishing wastewater collecting tank and wastewater equalization pond, and the alkali decrement waste water of generation and dyeing and finishing wastewater are collected respectively in alkali decrement waste water collecting tank and dyeing and finishing wastewater collecting tank;
(2) preliminary sedimentation carries out alkali decrement waste water preliminary sedimentation in alkali decrement waste water collecting tank, dyeing and finishing wastewater is carried out in dyeing and finishing wastewater collecting tank to preliminary sedimentation, and the throw out at the bottom of two ponds after precipitation is removed;
(3) acid outs, in scrubbing alkali decrement waste water, add the vitriol oil and under agitation carry out neutralization reaction, when pH value is 3～4, stopping acid adding, now in reaction tank, having a large amount of phthalic acids to separate out, phthalic acid is removed, through traditional vacuum filter, dry after, purify recycling;
(4) secondary acid out, the supernatant liquor of alkali decrement waste water after an acid out is mixed with dyeing and finishing wastewater, adding the vitriol oil to composite waste pH value is 3～4 o'clock, stop acid adding, add polyacrylamide flocculant coagulation, making the concentration in composite waste is 10～30ppm, after coagulum sedimentation again, with plate-and-frame filter press, by the waste water filtering after secondary acid out, filter mud and separately use it for anything else;
(5) mix and regulate, after supernatant liquor other waste water low with other chemical oxygen content, that concentration is little after secondary acid out is filtered mixes in wastewater equalization pond, regulate this pond mixing water pH after between 6～7, can enter into biological chemistry advanced treatment flow process, complete the pre-treatment in early stage of waste water.
2. by the method for a kind of pre-treatment dyeing and finishing wastewater claimed in claim 1, it is characterized in that: the time of described preliminary sedimentation is at least 12 hours.
3. by the method for a kind of pre-treatment dyeing and finishing wastewater claimed in claim 1, it is characterized in that: described polyacrylamide flocculant molecular-weight average is 3,000,000～1,200 ten thousand.
4. by the method for a kind of pre-treatment dyeing and finishing wastewater claimed in claim 1, it is characterized in that: described polyacrylamide flocculant is cationic organic polymer coargulator.
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Cited By (2)
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| CN109592853A (en) * | 2019-01-04 | 2019-04-09 | 厦门立思节能科技有限公司 | A kind of wastewater treatment method |
| CN115557636A (en) * | 2022-10-09 | 2023-01-03 | 湖北泰盛化工有限公司 | Treatment method of phenol-containing wastewater of 2, 4-drop condensation mother liquor |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103755081A (en) * | 2014-01-17 | 2014-04-30 | 杭州创享环境技术有限公司 | Method for reclaiming and recycling terephthalic acid and alkali by alkali peeling wastewater |
Non-Patent Citations (1)
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN109592853A (en) * | 2019-01-04 | 2019-04-09 | 厦门立思节能科技有限公司 | A kind of wastewater treatment method |
| CN115557636A (en) * | 2022-10-09 | 2023-01-03 | 湖北泰盛化工有限公司 | Treatment method of phenol-containing wastewater of 2, 4-drop condensation mother liquor |
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Application publication date: 20140827 |