CN107215998A - A kind of deep treatment method of waste water - Google Patents

A kind of deep treatment method of waste water Download PDF

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Publication number
CN107215998A
CN107215998A CN201610164377.XA CN201610164377A CN107215998A CN 107215998 A CN107215998 A CN 107215998A CN 201610164377 A CN201610164377 A CN 201610164377A CN 107215998 A CN107215998 A CN 107215998A
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water
treatment
nanofiltration
micro
filtration
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宁文娟
黄圣散
杨瑜芳
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Toray Advanced Materials Research Laboratories China Co Ltd
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Toray Advanced Materials Research Laboratories China Co Ltd
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    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F9/00Multistage treatment of water, waste water, or sewage
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00Treatment of water, waste water, or sewage
    • C02F1/28Treatment of water, waste water, or sewage by sorption
    • C02F1/281Treatment of water, waste water, or sewage by sorption using inorganic sorbents
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00Treatment of water, waste water, or sewage
    • C02F1/44Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis
    • C02F1/441Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis by reverse osmosis
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00Treatment of water, waste water, or sewage
    • C02F1/44Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis
    • C02F1/442Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis by nanofiltration
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00Treatment of water, waste water, or sewage
    • C02F1/44Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis
    • C02F1/444Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis by ultrafiltration or microfiltration
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00Treatment of water, waste water, or sewage
    • C02F1/52Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00Treatment of water, waste water, or sewage
    • C02F1/72Treatment of water, waste water, or sewage by oxidation
    • C02F1/78Treatment of water, waste water, or sewage by oxidation with ozone
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2103/00Nature of the water, waste water, sewage or sludge to be treated
    • C02F2103/30Nature of the water, waste water, sewage or sludge to be treated from the textile industry
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2301/00General aspects of water treatment
    • C02F2301/08Multistage treatments, e.g. repetition of the same process step under different conditions

Abstract

The invention belongs to sewage advanced treatment field, waste water obtains single treatment water after single treatment, single treatment water is after pretreatment unit, obtain producing water after film process again, part nanofiltration and/or reverse osmosis concentrated water and part micro-filtration and/or hyperfiltration reverse-rinsing discharge water are recycled to before pretreatment unit, then obtain after pretreatment unit, micro-filtration and/or ultrafiltration after-treatment water.After-treatment water in part improves water use efficiency with obtaining recycle-water after production hydration simultaneously in the case where not improving nanofiltration and the counter-infiltration rate of recovery.Not with production hydration and after-treatment water and non-loopback be hydrated and obtain it is secondary merge water, available for occasions such as landscape water and industrial cooling waters.The present invention takes full advantage of existing process, do not influence to improve the system rate of recovery in the case of film service life, reduce ton cost of water treatment, while it is recycling after processing nanofiltration or reverse osmosis concentrated water and micro-filtration or hyperfiltration reverse-rinsing is discharged water, charges for disposing pollutants are reduced, water utilization rate is improved.

Description

A kind of deep treatment method of waste water
Technical field
The invention belongs to field of waste water treatment, and in particular to a kind of use embrane method carries out Sewage advanced treatment Technology.
Background technology
The organic wastewater with difficult degradation thereby such as dyeing waste water are industrial wastewater discharge rich anies influential family, and intractability is larger.Dyestuff The base stock of production includes benzene series, naphthalene system, anthraquinone, aniline and diphenyl amine compound etc., and in life The material such as many and metal, salt is chelated during production. art, causes the intractable feature of waste water.At present The processing method of the organic wastewater with difficult degradation thereby such as dyeing waste water mainly includes biological treatment, oxidizing process (chemical oxygen Change, photocatalytic method, microwave cooperating method), absorption method, Coagulation Method and electrochemical process etc..In addition, film Technology is used as a kind of new isolation technics, because of its unique separation characteristic, the application in such waste water Also it is more and more extensive.Waste water etc. can be obtained after embrane method advanced treatment process again by biochemical, materializing strategy To the excellent production Water circulation of water quality in industrial production, the utilization rate of water resource is improved, China is alleviated The nervous situation of water resource.
In recent years, diversified dual-membrane process is got growing concern for, micro-filtration (MF)/milipore filter (UF) Combination with nanofiltration (NF)/reverse osmosis membrane (RO) is film combination the most frequently used in Sewage advanced treatment.But film skill Art still suffers from some problems, such as the concentrated water process problem of nanofiltration/reverse osmosis membrane in application process.Printing and dyeing Deng waste water nanofiltration/reverse osmosis concentrated water the characteristics of for content of organics is high and difficult for biological degradation, it is impossible to directly Discharge, is difficult to remove using traditional treatment method such as biochemical treatment or coagulating sedimentation.There is sewage collection The area of middle advanced treating factory, the nanofiltration/reverse osmosis concentrated water for being typically up to indirect discharge standard is discharged into sewage Concentrate and handled in advanced treating factory, certain sewage disposal expense is produced, if while nanofiltration/counter-infiltration Concentrated water is unable to reach indirect discharge standard and can not be then directly discharged into sewage concentration advanced treating factory, needs extra It is handled by concentrated water treatment facility.In the case where no sewage concentrates advanced treating factory, one As it is handled using adding the method such as evaporative crystallization, high energy consumption, processing cost is high.
Patent (CN 201010117987.7) refer to the part counter-infiltration after reverse-osmosis treated by waste water Concentrate recirculation to regulating reservoir passes through electric flocculation circular treatment again, improves the rate of recovery.But the known example is added The processing load of follow-up reverse osmosis membrane, at the same be not directed in patent on the basis of existing technology to ultrafiltration/ The processing method and the increase system time on the basis of reverse-osmosis treated burden is not increased of micro-filtration backwash discharge water The method of yield, and seen by embodiment data, the content of organics of outer row's reverse osmosis concentrated water is higher than direct , there is certain charges for disposing pollutants and environmental pollution in discharge standard.
Patent (CN 201410800474.4) refer to by the reverse osmosis concentrated water of dyeing waste water by electrodialysis, Softening, evaporation crystallization equipment are handled.But the reverse osmosis thick water treatment method high energy consumption of the known example, Processing cost is high.
Therefore it provides it is a kind of based on existing handling process cause nanofiltration and/or reverse osmosis concentrated water and micro-filtration with/ Or hyperfiltration reverse-rinsing discharge water reprocessing is utilized, and system is improved on the basis of reverse osmosis membrane pollution is not aggravated The deep treatment method for the rate of recovery of uniting, the popularization for waste water recycling advanced treatment process is significant.
The content of the invention
The technical problem to be solved in the present invention is:
The nanofiltration produced for waste water after Treatment for Reuse or reverse osmosis concentrated water and ultrafiltration or micro-filtration backwash discharge The problem of water can not reach discharge standard and low utilization rate is there is provided one kind on the basis of existing treatment technology Backflow reprocessing is carried out to it, so as to improve the Sewage Reuse System rate of recovery, processing cost, and root is reduced The further treatment technique of water utilization rate is at utmost improved according to reuse requirement.
The purpose of the present invention can be reached by following measures:
A kind of deep treatment method of waste water, waste water obtains single treatment water after single treatment, once Water is handled after pretreatment unit, then after micro-filtration and/or ultrafiltration, nanofiltration and/or reverse-osmosis treated Obtain producing water, part nanofiltration and/or reverse osmosis concentrated water and/or part micro-filtration and/or hyperfiltration reverse-rinsing discharge water time Deliver to before pretreatment unit, then after-treatment is obtained by pretreatment unit and micro-filtration and/or hyperfiltration treatment Water.
It is preferred that being back to the micro-filtration before pretreatment unit and/or hyperfiltration reverse-rinsing discharge water accounts for micro-filtration and/or super Filter 20-100%, further preferred 50%-100% that water total Water is discharged in backwash.When backflow ratio is improved When, the capacity of returns of micro-filtration and/or hyperfiltration reverse-rinsing discharge water also accordingly increases, but the load of pretreatment unit It can improve, therefore backflow ratio can be true according to requirement when single treatment water water quality and reuse to producing water water quality It is fixed, so as to farthest reduce processing cost.
It is preferred that being back to the nanofiltration before pretreatment unit and/or reverse osmosis concentrated water water accounts for nanofiltration and/or reverse osmosis The 20-100%, further preferred 50%-100% of saturating concentrated water total Water.When the ratio of backflow is improved, receive The capacity of returns of filter and/or reverse osmosis concentrated water also accordingly increases, but the load of pretreatment unit can also be improved, because This backflow ratio can determine according to comprehensive in terms of single treatment water water quality and the counter-infiltration rate of recovery and energy consumption, Farthest reduce processing cost.
The rate of recovery of nanofiltration or counter-infiltration is preferably 40-80%, specifically by nanofiltration or feed water by reverse osmosis water quality and Processing requirement is determined.When the rate of recovery of nanofiltration and/or counter-infiltration is improved, nanofiltration and/or counter-infiltration operation pressure Power also can accordingly increase, but be back to the nanofiltration before pretreatment unit and/or the meeting of reverse osmosis concentrated water water accordingly Reduce, the load of pretreatment unit can also be reduced.When the rate of recovery of nanofiltration and/or counter-infiltration is more than 80%, Nanofiltration and/or reverse osmosis concentrated water water can be reduced accordingly, and backflow water yield also can be reduced accordingly, pretreatment unit Load reduction, can according to producing water water quality require improve or reduction backflow water yield, so as to farthest carry High reusing rate and reuse cost.The rate of recovery of nanofiltration and/or counter-infiltration be less than 40% when, now nanofiltration and / or counter-infiltration energy consumption decline, concentrated water water increase, backflow water yield can according to production water require improve or reduce, So as to farthest improve reusing rate and reuse cost.
It is preferred that after-treatment water in part is back in production, can be used for obtaining recycle-water after production hydration simultaneously Cooling water, slurry, boiler feedwater or industry and the one or more in product water, so that The rate of recovery of whole system, reduction are improved in the case where not improving nanofiltration and/or the counter-infiltration system rate of recovery Ton cost of water treatment, improves water utilization rate.
Not with production hydration and another part after-treatment water and be not back to the nanofiltration before pretreatment unit and / or reverse osmosis concentrated water and micro-filtration and/or hyperfiltration reverse-rinsing discharge be hydrated and secondary merging water, available for landscape It is not high to sulfate and hardness requirement to the less demanding occasion of electrical conductivity, industrial cooling water etc. with water etc. Occasion, specifically by single treatment water water quality and micro-filtration or the rate of recovery of ultrafiltration, nanofiltration or counter-infiltration system It is determined that, most suitable application direction and occasion are determined according to after-treatment water water quality.
Be preferred for production hydration and part after-treatment water account for recycle-water ratio be 5-40%, enter one Preferred 10-15% is walked, is determined jointly by after-treatment water water quality, producing water water quality and recycle-water purposes, two In the case of secondary processing water and producing water water quality determination, recycle-water is different according to purposes, and ratio is with reuse standard And change, recycle-water water is farthest improved on the basis of standard is met.
It is preferred that single treatment contains the one or more in biochemical treatment, chemical treatment or physical treatment.It is raw The technology type for changing processing is not particularly limited, including the life of activated sludge process, anaerobic bio-treated, anoxic Thing processing, Aerobic biological process, hydrolysis acidification processing, oxidation ditch, biomembrance process, biofilter, life One or more in thing catalytic oxidation, biological fluidized bed, biological rotating disk or membrane bioreactor.Change The technology type for learning processing is not particularly limited, including coagulating treatment, adsorption treatment, neutralisation treatment, change Learn the one or more in precipitation process, redox processing or electrolysis processing.The technique of physical treatment Type is not particularly limited, including grid, screen cloth, precipitation process, membrane filtration, air supporting separation of solid and liquid, One or more in filter, multi-medium filtering or sand filtration.
It is preferred that pretreatment unit is the one or more in advanced oxidation or adsorbent equipment.Advanced oxidation is to produce With the characteristics of the raw hydroxyl radical free radical (OH) with Strong oxdiative ability, in HTHP, electricity, sound, light spoke According under the reaction conditions such as, catalyst, macromolecular hardly degraded organic substance is set to be oxidized to small molecule organic material, And physical absorption or chemisorbed performance of the adsorbent equipment using its solid absorbent, it can effectively go water removal In the small organic molecule that contains so that the organic pollution materials content effectively contained in reduction waste water, is protected Card micro-filtration and/or the operation steady in a long-term of ultrafiltration, nanofiltration and/or counter-infiltration, extension micro-filtration and/or ultrafiltration, Nanofiltration and/or the Chemical cleaning cycle of counter-infiltration, so as to extend membrane lifetime, reduce processing cost.Micro-filtration and / or ultrafiltration can then go water removal in suspension, particulate matter, algae, bacterium, fractionated viral and large scale Colloid etc., and various inorganic ions that nanofiltration and/or counter-infiltration can be in trap waters, colloidal substance and big Molecule solute, so as to obtain producing water, reaches reuse purpose.The nanofiltration of backflow and/or reverse osmosis concentrated water and micro- Filter and/or hyperfiltration reverse-rinsing discharge water are after advanced oxidation and/or adsorbent equipment processing, and Organic substance in water is dirty Contaminate content of material reduction, it is ensured that do not aggravate the organic of follow-up micro-filtration and/or ultrafiltration, nanofiltration and/or counter-infiltration Thing pollutes, so as to ensure the stable operation of micro-filtration and/or ultrafiltration, nanofiltration and/or counter-infiltration.
It is preferred that containing in single treatment water in slurry, finish, dyestuff, chemical assistant or surfactant One or more, the equal difficult for biological degradation of these materials, it is difficult to removed by biochemical treatment.It is reverse osmosis concentrated Such material in water is returned to before pretreatment unit, and the decomposition and absorption handled by advanced oxidation is filled The suction-operated to small-molecule substance is put, effectively the content of organics in reduction water.
It is preferred that the content of organics that single treatment water middle-molecular-weihydroxyethyl is more than 100,000 dalton is more than or equal to 10%, more preferably 10-30%, advanced oxidation processing can be played to greatest extent organic to macromolecular The decomposition of thing, it is senior when the content of organics that molecular weight is more than 100,000 dalton is less than 10% Oxidation processes effect reduce, and with molecular weight be more than 100,000 dalton content of organics increase when, Treatment effect is improved, therefore for the water of this preferred type, treatment method has excellent treatment effect.
It is preferred that it is BOD (biochemical oxygen demand (BOD)) in water that the B/C values of single treatment water, which are 0.1~0.3, B/C values, With COD (COD) ratio, the biodegradable degree of water is characterized, when B/C values are smaller, The water gets over difficult for biological degradation, difficult by conventional biochemical mode when single treatment water is difficult for biological degradation water To remove, and advanced oxidation has excellent treatment effect to difficult for biological degradation water, therefore for this preferred The water of type, treatment method has excellent treatment effect.
Advanced oxidation be processed as Fenton oxidation, photochemical oxidation, catalysis humidifying oxidation, electrochemical oxidation, Or the one or more in ozone oxidation, the refractory organic in waste water is handled, decomposed For small organic molecule or permineralization.
Adsorbent equipment is that resin adsorption, kieselguhr adsorption, cinder adsorption, zeolite adsorption or activated carbon are inhaled The one or more of attached middle school, are adsorbed by physical absorption or chemisorption to the organic matter in water Remove, especially there is good removal effect to small organic molecule.
The present invention to nanofiltration and/or reverse osmosis concentrated water and micro-filtration and/or surpasses on the basis of existing treatment technology Filter backwash discharge water is handled, and the waste water by this PROCESS FOR TREATMENT has following advantage:
1st, recycle-water water is farthest improved on the basis of recycle-water meets industrial water standard, together When after-treatment water after treatment can be used for other purposes, water utilization rate is improved, with certain Economy and environmental benefit;
2nd, on the basis of existing treatment technology, partial reflux cause nanofiltration or reverse osmosis concentrated water and ultrafiltration or Micro-filtration backwash water reaches reuse standard after treatment, can be applied to landscape water etc. and salt content is required not High occasion, while reducing processing cost to greatest extent;
3rd, do not aggravate to improve the system rate of recovery on the basis of counter-infiltration pollution, the use of reverse osmosis membrane is not influenceed Life-span.
Brief description of the drawings
Fig. 1 is the flow chart using the present invention.
Fig. 2 is the flow chart of the common process in contrast to the present invention.
Embodiment
The measure of hardness (calcium, magnesium) in embodiment uses the inductively coupled plasma of Japanese Shimadzu Corporation Body emission spectrometer (ICP), the measure of sulfate radical uses ion chromatograph (the model MIC of Wan Tong companies Type), TDS (total dissolved solid) measure uses the total dissolved solidss analyzer of Hash company of the U.S., COD measure clears up instrument (model DRB200), BOD survey using the COD of Hash company of the U.S. Fixed to use dilution inocalation method, molecular weight distribution uses the gel permeation chrommatograph of Japanese Shimadzu Corporation.
Embodiment 1
This test process water is 500m3/ d, certain waste water is obtained through Aerobic biological process and after coagulating kinetics To single treatment water, single treatment water COD is 50mg/L, and molecular weight is more than 100kDa (i.e. 100,000 Dalton) more than macromolecular content be that 12%, B/C values are that 0.2, TDS is 250mg/L, hardness is 60mg/L, sulfate radical is 45mg/L, and single treatment water is by ozone processing, activated carbon processing and ultrafiltration Ultrafiltration production water is obtained after processing, the ultrafiltration rate of recovery is 90%, ultrafiltration production water is obtained after reverse-osmosis treated Reverse osmosis produced water, the counter-infiltration rate of recovery is 80%, and salt rejection rate is 98%, and reverse osmosis concentrated water COD is 100mg/L, it is impossible to directly discharge.95% reverse osmosis concentrated water and the discharge water backflow of 100% hyperfiltration reverse-rinsing To ozone, then handled by ozone, obtain after-treatment water, portion after activated carbon processing and hyperfiltration treatment Processing water and reverse osmosis produced water obtain recycle-water after merging in two times, and after-treatment water accounts for recycle-water ratio 10%, recycle-water COD are less than 5mg/L, and TDS is 90mg/L, and hardness is 20mg/L, and sulfate radical is 15mg/L, reaches textile industry water supply standard.Other part after-treatment water with do not flow back it is reverse osmosis concentrated Water and hyperfiltration reverse-rinsing discharge are hydrated and obtain secondary merging water, and the COD of secondary merging water is 26mg/L, TDS For 780mg/L, hardness is 190mg/L, and sulfate radical is 143mg/L, is reached《Regeneration of urban sewage profit Use industry water standard》(GB/T19923-2005) water standard.The system rate of recovery of the technique is 80%.
Embodiment 2
This test process water is 500m3/ d, certain dyeing waste water obtains one after biochemical treatment and precipitation process Secondary processing water, single treatment water COD is 135mg/L, and molecular weight is more than more than 100kDa macromolecular Content is that 5%, B/C values are 400mg/L for 0.10, TDS, and hardness is 100mg/L, and sulfate radical is 70mg/L, single treatment water is handled by ozone, obtain ultrafiltration production water after activated carbon processing and hyperfiltration treatment, The ultrafiltration rate of recovery is 90%, and ultrafiltration production water obtains reverse osmosis produced water after reverse-osmosis treated, and counter-infiltration is returned Yield is 60%, and salt rejection rate is 99%, reverse osmosis concentrated water COD be 180mg/L, it is impossible to directly or Run in and put.100% reverse osmosis concentrated water and 90% hyperfiltration reverse-rinsing discharge water are back to before ozone, then are passed through After-treatment water is obtained after ozone processing, activated carbon processing and hyperfiltration treatment, after-treatment water is not with flowing back Reverse osmosis concentrated water and hyperfiltration reverse-rinsing discharge be hydrated and secondary merging water, the COD of secondary merging water For 78mg/L, TDS is 852mg/L, and hardness is 214mg/L, and sulfate radical is 150mg/L, is reached《City City's reuse of wastewater industry water standard》(GB/T19923-2005) the cooling direct current water supply standard in And standard of washing water.Reverse osmosis produced water is that the COD of recycle-water is 4mg/L, and TDS is 9mg/L, Hardness is less than 5mg/L, and sulfate radical is less than 5mg/L, reaches textile industry water supply standard.The technique is The rate of recovery of uniting is 54%.
Embodiment 3
This test process water is 500m3/ d, certain dyeing waste water obtains one after biochemical treatment and precipitation process Secondary processing water, single treatment water COD is 135mg/L, and molecular weight is more than more than 100kDa macromolecular Content is that 18%, B/C values are 400mg/L for 0.15, TDS, and hardness is 100mg/L, and sulfate radical is 70mg/L, single treatment water is handled by ozone, obtain ultrafiltration production water after activated carbon processing and hyperfiltration treatment, The ultrafiltration rate of recovery is 90%, and ultrafiltration production water obtains reverse osmosis produced water after reverse-osmosis treated, and counter-infiltration is returned Yield is 60%, and salt rejection rate is 99%, and reverse osmosis concentrated water COD is 130mg/L, it is impossible to directly discharged. 65% reverse osmosis concentrated water and 90% hyperfiltration reverse-rinsing discharge water are back to before ozone, then handled by ozone, Obtain after-treatment water after activated carbon processing and hyperfiltration treatment, after-treatment water with do not flow back it is reverse osmosis concentrated Water and hyperfiltration reverse-rinsing discharge are hydrated and obtain secondary merging water, and the COD of secondary merging water is 73mg/L, TDS is 710mg/L, and hardness is 178mg/L, and sulfate radical is 125mg/L, is reached《Municipal sewage is again Make profits and use industry water standard》(GB/T19923-2005) cooling direct current water supply standard and washing in are used Water quality standard.Reverse osmosis produced water is that the COD of recycle-water is 3mg/L, and TDS is 6mg/L, and hardness is less than 5mg/L, sulfate radical is less than 5mg/L, reaches textile industry water supply standard.The system rate of recovery of the technique For 54%.Compared with Example 2, although larger molecular organicses content is different in water inlet water, pre-treatment effect Fruit is different, but the reuse purpose reached after processing is identical with effect, while anti-in the handling process of the water The reuse ratio of infiltration concentrated water decreases, and reduces pre-treatment burden.
Embodiment 4
This test process water is 500m3/ d, certain dyeing waste water obtains one after biochemical treatment and precipitation process Secondary processing water, single treatment water COD is 135mg/L, and molecular weight is more than more than 100kDa macromolecular Content is that 18%, B/C values are 400mg/L for 0.15, TDS, and hardness is 100mg/L, and sulfate radical is 70mg/L, single treatment water is handled by ozone, obtain ultrafiltration production water after activated carbon processing and hyperfiltration treatment, The ultrafiltration rate of recovery is 90%, and ultrafiltration production water obtains reverse osmosis produced water after reverse-osmosis treated, and counter-infiltration is returned Yield is 60%, and salt rejection rate is 99%, and reverse osmosis concentrated water COD is 130mg/L, it is impossible to directly discharged. 65% reverse osmosis concentrated water and 90% hyperfiltration reverse-rinsing discharge water are back to before ozone, then handled by ozone, After-treatment water, part after-treatment water and reverse osmosis produced hydration are obtained after activated carbon processing and hyperfiltration treatment And after obtain recycle-water, after-treatment water accounts for the 15% of recycle-water ratio, and recycle-water COD is 9mg/L, TDS is 95mg/L, and hardness is 23mg/L, and sulfate radical is 16mg/L, reaches textile industry water supply standard. Other part after-treatment water and the reverse osmosis concentrated water not flowed back and hyperfiltration reverse-rinsing discharge are hydrated and obtain secondary close And water, the COD of secondary merging water is 78mg/L, and TDS is 740mg/L, and hardness is 185mg/L, Sulfate radical is 130mg/L, is reached《Urban sewage reutilization industry water standard》 (GB/T19923-2005) cooling direct current water supply standard and standard of washing water in.The system of the technique The rate of recovery is 64%, and 10% is improved in reuse water, you can the cost of reduction by 10%.
Embodiment 5
This test process water is 500m3/ d, certain dyeing waste water obtains one after biochemical treatment and precipitation process Secondary processing water, single treatment water COD is 135mg/L, and molecular weight is more than more than 100kDa macromolecular Content is that 18%, B/C values are 400mg/L for 0.15, TDS, and hardness is 100mg/L, and sulfate radical is 70mg/L, single treatment water is handled by ozone, obtain ultrafiltration production water after activated carbon processing and hyperfiltration treatment, The ultrafiltration rate of recovery is 90%, and ultrafiltration production water obtains reverse osmosis produced water after reverse-osmosis treated, and counter-infiltration is returned Yield is 60%, and salt rejection rate is 99%, and reverse osmosis concentrated water COD is 130mg/L, it is impossible to directly discharged. 100% reverse osmosis concentrated water and 90% hyperfiltration reverse-rinsing discharge water be back to before ozone, then by ozone at After-treatment water is obtained after reason, activated carbon processing and hyperfiltration treatment, part after-treatment water and reverse osmosis produced Recycle-water is obtained after being hydrated simultaneously, after-treatment water accounts for the 40% of recycle-water ratio, and recycle-water COD is 20mg/L, TDS are 350mg/L, and hardness is 87mg/L, and sulfate radical is 60mg/L, reaches dyer Industry water water standard.Other part after-treatment water and the reverse osmosis concentrated water and hyperfiltration reverse-rinsing that do not flow back are arranged Discharge water and merge to obtain secondary merging water, the COD of secondary merging water is 51mg/L, and TDS is 800mg/L, Hardness is 200mg/L, and sulfate radical is 140mg/L, is reached《Urban sewage reutilization industrial water water Matter》(GB/T19923-2005) water standard.The system rate of recovery of the technique is 90%.
Embodiment 6
This test process water is 500m3/ d, certain waste water obtains single treatment water after biochemical treatment, once It is 180mg/L to handle water COD, and the macromolecular content that molecular weight is more than more than 100kDa is 30%, B/C It is 210mg/L to be worth for 0.3, TDS, and hardness is 45mg/L, and sulfate radical is 30mg/L, single treatment water Handle by Fenton oxidation, obtain micro-filtration production water after kieselguhr adsorption processing and micro-filtration processing, micro-filtration is returned Yield is 90%, and micro-filtration production water obtains reverse osmosis produced water after reverse-osmosis treated, and the counter-infiltration rate of recovery is 60%, salt rejection rate is 98%, and reverse osmosis concentrated water COD is 175mg/L, it is impossible to directly or indirectly discharged, Need to be handled again just can directly or indirectly discharge.100% reverse osmosis concentrated water and 100% micro-filtration backwash Discharge water is back to Fenton oxidation before processing, then is handled by Fenton oxidation, at kieselguhr adsorption After-treatment water is obtained after reason and micro-filtration processing, part after-treatment water and reverse osmosis produced water are obtained after merging Recycle-water, after-treatment water accounts for the 20% of recycle-water ratio, and recycle-water COD is 15mg/L, and TDS is 95mg/L, hardness is 20mg/L, and sulfate radical is 13mg/L, reaches textile industry water water standard. Other part after-treatment water and the reverse osmosis concentrated water not flowed back and micro-filtration backwash discharge are hydrated and obtain secondary close And water, the COD of secondary merging water is 70mg/L, and TDS is 440mg/L, and hardness is 95mg/L, sulphur Acid group is 64mg/L, is reached《Urban sewage reutilization industry water standard》(GB/T19923-2005) Industrial washing with water water standard and cooling direct current water water standard.The system rate of recovery of the technique is 90%.The system rate of recovery of the technique is 68%.
Embodiment 7
This test process water is 500m3/ d, certain dyeing waste water is once located after biochemical and precipitation process Water is managed, single treatment water COD is 80mg/L, and molecular weight is more than more than 100kDa macromolecular content It is that 0.1, TDS is 1600mg/L for 15%, B/C values, hardness is 430mg/L, and sulfate radical is 320mg/L, Single treatment water is handled by Fenton oxidation, obtain ultrafiltration production after resin adsorption processing and hyperfiltration treatment Water, the ultrafiltration rate of recovery is 90%, and ultrafiltration production water obtains reverse osmosis produced water, reverse osmosis after reverse-osmosis treated The saturating rate of recovery is 65%, and salt rejection rate is 98%, and reverse osmosis concentrated water COD is 90mg/L, it is impossible to directly arranged Put.20% reverse osmosis concentrated water and 20% hyperfiltration reverse-rinsing discharge water are back to Fenton oxidation before processing, Handled again by Fenton oxidation, resin adsorption processing and hyperfiltration treatment after obtain after-treatment water, part After-treatment water and reverse osmosis produced water obtain recycle-water after merging, and after-treatment water accounts for recycle-water ratio 5%, recycle-water COD are less than 5mg/L, and TDS is 90mg/L, and hardness is 22mg/L, and sulfate radical is 18mg/L, reaches textile industry water water standard.Other part after-treatment water and the reverse osmosis not flowed back Saturating concentrated water and hyperfiltration reverse-rinsing discharge are hydrated and obtain secondary merging water, and the COD of secondary merging water is 67mg/L, TDS is 2600mg/L, and hardness is 780mg/L, and sulfate radical is 620mg/L, is reached《Municipal sewage is again Make profits and use water for scenic environment use water quality》(GB18921-2002) water standard.The system of the technique is reclaimed Rate is 62%.
Embodiment 8
This test process water is 500m3/ d, certain waste water obtains single treatment water after biochemical treatment, once It is 150mg/L to handle water COD, and the macromolecular content that molecular weight is more than more than 100kDa is 18%, B/C It is 2200mg/L to be worth for 0.18, TDS, and hardness is 580mg/L, and sulfate radical is 450mg/L, is once located Reason water is handled by ozone, obtain ultrafiltration production water after activated carbon processing and hyperfiltration treatment, and the ultrafiltration rate of recovery is 90%, ultrafiltration production water obtains reverse osmosis produced water after reverse-osmosis treated, and the counter-infiltration rate of recovery is 40%, Salt rejection rate is 98%, and reverse osmosis concentrated water COD is 120mg/L, it is impossible to directly discharged.70% counter-infiltration Concentrated water and 50% hyperfiltration reverse-rinsing discharge water be back to before ozone, then handled by ozone, activated carbon processing With obtain after-treatment water after hyperfiltration treatment, part after-treatment water and reverse osmosis produced water are returned after merging With water, after-treatment water accounts for the 10% of recycle-water ratio, and recycle-water COD is 8mg/L, and TDS is 340mg/L, hardness is 84mg/L, and sulfate radical is 65mg/L, reaches dyeing water quality standard for industries. Other part after-treatment water and the reverse osmosis concentrated water not flowed back and hyperfiltration reverse-rinsing discharge are hydrated and obtain secondary close And water, the COD of secondary merging water is 65mg/L, and TDS is 3100mg/L, and hardness is 810mg/L, Sulfate radical is 620mg/L, is reached《Urban sewage reutilization water for scenic environment use water quality》 (GB18921-2002) water standard.The system rate of recovery of the technique is 40%.
Embodiment 9
This test process water is 500m3/ d, certain dyeing waste water obtains one after biochemical treatment and precipitation process Secondary processing water, single treatment water COD is 135mg/L, and molecular weight is more than more than 100kDa macromolecular Content is that 18%, B/C values are 400mg/L for 0.15, TDS, and hardness is 100mg/L, and sulfate radical is 70mg/L, single treatment water is handled by ozone, obtain micro-filtration production water after activated carbon processing and micro-filtration processing, The micro-filtration rate of recovery is 90%, and micro-filtration production water obtains nanofiltration production water after nanofiltration is handled, and the nanofiltration rate of recovery is 60%, salt rejection rate is 90%, and nanofiltration concentrated water COD is 130mg/L, it is impossible to directly discharged.90% receives Filter concentrated water and 20% micro-filtration backwash discharge water are back to before ozone, then are handled by ozone, at activated carbon Manage and after-treatment water is obtained after micro-filtration processing, returned after part after-treatment water and nanofiltration production hydration simultaneously With water, after-treatment water accounts for the 10% of recycle-water ratio, and recycle-water COD is 10mg/L, and TDS is 135mg/L, hardness is 21mg/L, and sulfate radical is 15mg/L, reaches textile industry water supply standard.In addition After-treatment water in part is hydrated with the nanofiltration concentrated water not flowed back and micro-filtration backwash discharge and secondary must merge water, The secondary COD for merging water is 60mg/L, and TDS is 670mg/L, and hardness is 180mg/L, sulfuric acid Root is 125mg/L, is reached《Urban sewage reutilization industry water standard》(GB/T19923-2005) In cooling direct current water supply standard and standard of washing water.The system rate of recovery of the technique is 60%.
Embodiment 10
This test process water is 500m3/ d, certain waste water obtains single treatment water after biochemical treatment, once It is 210mg/L to handle water COD, and the macromolecular content that molecular weight is more than more than 100kDa is 30%, B/C It is 210mg/L to be worth for 0.3, TDS, and hardness is 45mg/L, and sulfate radical is 30mg/L, single treatment water Handle by Fenton oxidation, kieselguhr adsorption processing, obtain ultrafiltration production water after micro-filtration and hyperfiltration treatment, Micro-filtration and the rate of recovery of ultrafiltration are 90%, and ultrafiltration production water obtains nanofiltration production water after nanofiltration is handled, and receives It is 65% to filter the rate of recovery, and salt rejection rate is 90%, and reverse osmosis concentrated water COD is 190mg/L, it is impossible to directly With indirect discharge, need to be handled again just can directly or indirectly discharge.100% nanofiltration concentrated water, 40% Water is discharged in micro-filtration backwash and 40% hyperfiltration reverse-rinsing discharge water is back to Fenton oxidation before processing, then is passed through After-treatment water, portion are obtained after Fenton oxidation processing, kieselguhr adsorption processing, micro-filtration and hyperfiltration treatment Recycle-water is obtained after processing water and nanofiltration production hydration simultaneously in two times, after-treatment water accounts for recycle-water ratio 5%, recycle-water COD are 10mg/L, and TDS is 65mg/L, and hardness is 6mg/L, and sulfate radical is 4mg/L, Reach textile industry water water standard.Other part after-treatment water and the nanofiltration concentrated water, micro- not flowed back Filter backwash discharge water and hyperfiltration reverse-rinsing discharge is hydrated and obtains secondary merging water, the COD of secondary merging water is 70mg/L, TDS are 410mg/L, and hardness is 95mg/L, and sulfate radical is 64mg/L, is reached《City Reuse of wastewater industry water standard》(GB/T19923-2005) industrial washing water water standard With cooling direct current water water standard.The system rate of recovery of the technique is 55%.
Embodiment 11
This test process water is 500m3/ d, certain waste water obtains single treatment water after biochemical treatment, once It is 150mg/L to handle water COD, and the macromolecular content that molecular weight is more than more than 100kDa is 18%, B/C It is 2200mg/L to be worth for 0.18, TDS, and hardness is 580mg/L, and sulfate radical is 450mg/L, is once located Reason water is handled by ozone, obtain ultrafiltration production water after activated carbon processing and hyperfiltration treatment, and the ultrafiltration rate of recovery is 90%, ultrafiltration production water obtains reverse osmosis produced water after nanofiltration and reverse-osmosis treated, and nanofiltration and counter-infiltration are returned Yield is 60% and 80%, and it is 90% and 98% that salt rejection rate, which is respectively, and nanofiltration concentrated water COD is 140mg/L, Can not directly it discharge.100% nanofiltration concentrated water and 90% hyperfiltration reverse-rinsing discharge water are back to before ozone, then Handled by ozone, activated carbon processing and hyperfiltration treatment after obtain after-treatment water, part after-treatment water Recycle-water is obtained after merging with reverse osmosis produced water, after-treatment water accounts for the 5% of recycle-water ratio, recycle-water COD is less than 5mg/L, and TDS is 127mg/L, and hardness is 30mg/L, and sulfate radical is 24mg/L, is reached To dyeing water quality standard for industries.Other part after-treatment water and the nanofiltration concentrated water not flowed back, reverse osmosis Saturating concentrated water and hyperfiltration reverse-rinsing discharge are hydrated and obtain secondary merging water, and the COD of secondary merging water is 50mg/L, TDS are 2450mg/L, and hardness is 620mg/L, and sulfate radical is 480mg/L, is reached《City City's reuse of wastewater water for scenic environment use water quality》(GB18921-2002) water standard.The technique The system rate of recovery is 45%.
Comparative example 1
This test process water is 500m3/ d, certain dyeing waste water secondary clarifier effluent is obtained after coagulating kinetics Single treatment water, single treatment water COD is 50mg/L, and TDS is 250mg/L, and hardness is 60mg/L, Sulfate radical is 45mg/L, and single treatment water is handled by ozone, obtained after activated carbon processing and hyperfiltration treatment Water is produced in ultrafiltration, and the ultrafiltration rate of recovery is 90%, and ultrafiltration production water obtains reverse osmosis produced water after reverse-osmosis treated, The counter-infiltration rate of recovery is 80%, and salt rejection rate is 98%, and the system rate of recovery is 70%.
It is 70% that embodiment and comparative example 1, which are compared, and can be seen that the system rate of recovery of comparative example, Reverse osmosis concentrated water and hyperfiltration reverse-rinsing discharge water are directly discharged simultaneously, and reverse osmosis concentrated water COD is 100mg/L, Discharge standard is not reached, need to be handled into garden wastewater treatment field, and processing cost is 1.4 yuan/ton.And implement Reflow treatment and the method merged back into are used in example so that concentrated water COD after the processing not row of only reaching Standard is put, while cooling cycling use of water standard is reached, can reuse, the raising of the simultaneity factor rate of recovery, reduction The charges for disposing pollutants of whole system are used with and with water rate, with economy and environmental benefit, while reverse osmosis concentrated water After hyperfiltration reverse-rinsing discharge water reflow treatment, organic pollution content is remarkably decreased, into ultrafiltration and reverse osmosis Saturating Organic substance in water content is essentially identical with Organic substance in water content before not flowing back, do not aggravate ultrafiltration and The Organic Pollution of counter-infiltration, it is ensured that ultrafiltration and the operation steady in a long-term of reverse osmosis membrane.

Claims (11)

1. a kind of deep treatment method of waste water, waste water obtains single treatment water, one after single treatment Secondary processing water is after pretreatment unit, then by micro-filtration and/or ultrafiltration, nanofiltration and/or reverse-osmosis treated After obtain produce water, it is characterised in that:Part nanofiltration and/or reverse osmosis concentrated water and/or part micro-filtration and/or super Filter backwash discharge water be recycled to before pretreatment unit, then by pretreatment unit and micro-filtration and/or ultrafiltration at Reason obtains after-treatment water.
2. deep treatment method according to claim 1, it is characterised in that:It is recycled to pre-treatment list Micro-filtration and/or hyperfiltration reverse-rinsing discharge water before member account for micro-filtration and/or hyperfiltration reverse-rinsing discharges water total Water 20-100%.
3. deep treatment method according to claim 1, it is characterised in that:It is recycled to pre-treatment list Nanofiltration and/or reverse osmosis concentrated water water before member account for the 20-100% of nanofiltration and/or reverse osmosis concentrated water total Water.
4. deep treatment method according to claim 1, it is characterised in that:Nanofiltration or counter-infiltration The rate of recovery is 40-80%.
5. deep treatment method according to claim 1, it is characterised in that:The after-treatment water In part after-treatment water with production hydration and after obtain recycle-water.
6. deep treatment method according to claim 5, it is characterised in that:For being hydrated simultaneously with production Part after-treatment water account for recycle-water ratio be 5-40%.
7. according to deep treatment method according to any one of claims 1 to 6, it is characterised in that:One Secondary processing contains the one or more in biochemical treatment, chemical treatment or physical treatment.
8. according to deep treatment method according to any one of claims 1 to 6, it is characterised in that:Before Processing unit is the one or more in advanced oxidation or adsorbent equipment.
9. according to deep treatment method according to any one of claims 1 to 6, it is characterised in that:One Contain one kind in slurry, finish, dyestuff, chemical assistant or surfactant or many in secondary processing water Kind.
10. according to deep treatment method according to any one of claims 1 to 6, it is characterised in that:One The content of organics that secondary processing water middle-molecular-weihydroxyethyl is more than 100,000 dalton is 10-30%.
11. according to deep treatment method according to any one of claims 1 to 6, it is characterised in that:One The B/C values of secondary processing water are 0.1~0.3.
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