CN105540967A - Processing method for reducing and recycling organic waste water and processing system - Google Patents

Processing method for reducing and recycling organic waste water and processing system Download PDF

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Publication number
CN105540967A
CN105540967A CN201510906365.5A CN201510906365A CN105540967A CN 105540967 A CN105540967 A CN 105540967A CN 201510906365 A CN201510906365 A CN 201510906365A CN 105540967 A CN105540967 A CN 105540967A
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unit
water
reverse osmosis
treatment
nanofiltration
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CN105540967B (en
Inventor
李春启
梅长松
刘学武
岳培恒
段世慈
康善娇
牟伟腾
张文博
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Datang International Chemical Technology Research Institute Co Ltd
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Datang International Chemical Technology Research Institute 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
    • C02F1/02Treatment of water, waste water, or sewage by heating
    • C02F1/04Treatment of water, waste water, or sewage by heating by distillation or evaporation
    • 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
    • C02F1/24Treatment of water, waste water, or sewage by flotation
    • 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
    • C02F1/40Devices for separating or removing fatty or oily substances or similar floating material
    • 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
    • C02F1/52Treatment 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
    • C02F2101/00Nature of the contaminant
    • C02F2101/30Organic compounds
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F3/00Biological 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
    • C02F3/00Biological treatment of water, waste water, or sewage
    • C02F3/30Aerobic and anaerobic processes

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  • Life Sciences & Earth Sciences (AREA)
  • Hydrology & Water Resources (AREA)
  • Engineering & Computer Science (AREA)
  • Environmental & Geological Engineering (AREA)
  • Water Supply & Treatment (AREA)
  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Separation Using Semi-Permeable Membranes (AREA)

Abstract

The invention provides a processing method for reducing and recycling organic waste water. The method comprises steps: (1) pre-treating waste water to obtain pre-treated out-water; (2) treating the out-water obtained from the step (1) through solid-liquid separation; (3) nano-filtering the out-water obtained from step (2); (4) treating nano-filtered concentrated water obtained from the step (3) to obtain out-water subjected concentrated water nano-filtering, returning to the step (3) for mixing the out-water subjected to concentrated water nano-filtering with the out-water subjected to solid-liquid separation, and performing nano-filtering; (5) performing first reverse osmosis treatment on out-water obtained from the step (3) through nano-filtering; (6) performing second reverse osmosis treatment on concentrated water obtained from the step (5) through first reverse osmosis treatment; and (7) evaporating and crystallizing a concentrated liquid obtained from the step (6) through second reverse osmosis treatment in order to obtain crystallized salt and evaporated concentrated water. The invention further provides a processing system of the method. Through the method and system, waste water is truly reduced and recycled.

Description

A kind of organic waste water minimizing, recycling processing method and treatment system
Technical field
The present invention relates to technical field of waste water processing, relate to the treatment process of a kind of organic waste water minimizing, resource utilization particularly, and for implement the method organic waste water minimizing, recycling treatment system.
Background technology
At present, the emission standard of the industry such as Coal Chemical Industry, petrochemical complex, printing and dyeing is increasingly strict, and sewage minimizing, resource utilization become the inevitable choice of all industries and society gradually.In actual process, because being subject to processing the restriction of the factor such as technology and processing cost, the middle water that treating processes produces mainly is divided into two kinds: in the first, water is the filtration water outlet after biochemical treatment, this middle water can be subdivided into multi-medium filtering water outlet, micro-filtration water outlet and ultra-filtration water again, the difference of the difference of three mainly suspended substance and turbidity; In the second water be in the first water again through product water that reverse-osmosis treated obtains.In the first, water is because of residual more macromole hardly degraded organic substance, polyvalent ion, exist in actual use foam many, have the various problems such as peculiar smell, corrodibility and/or fouling tendency are strong, use range is very limited.In the second, water is reverse osmosis produced water, and its water quality is better, but processing cost is expensive, and reverse osmosis produces a large amount of concentrated organic waste water, and all kinds of Pollutant levels are higher, cannot discharge.
The many employings of concentrated organic waste water high salt membrane concentration technique " nanofiltration+reverse osmosis " of discharging for intermediate water reuse system reverse osmosis at present concentrates further, and the high organic concentrated solution of high salt that nanofiltration and reverse osmosis are discharged enters that vapo(u)rization system is concentrated, crystallization.Because in this concentrated solution, organism and salinity are very high, problems such as causing vapo(u)rization system to produce serious fouling, fly material, organic concentration is high in many, the crystal salt of foam, evaporation condensate COD is high, specific conductivity is high, has a strong impact on the operation of vapo(u)rization system.In addition, in actual motion, after reverse osmosis concentrated water enters the dense water system of high salt film, because organism and the further of salinity concentrate, fouling and etching problem are all more outstanding, have a strong impact on the safe and stable operation of system, the work-ing life of film shortens greatly, investment and running cost all very high.
Chinese patent CN201510189929 discloses a kind of printing and dyeing wastewater recovery and disposal method, this invention adopts equalizing tank, coagulative precipitation tank, composite aeration activated sludge reaction pond, hydrolysis acidification pool, contact-oxidation pool, second pond, membrane biological reaction pond and reverse osmosis reaction tank, recycles.Because the biodegradability of dyeing waste water is poor, still there is more solubilised state hardly degraded organic substance after biochemical treatment, and in actual procedure, ultra-filtration membrane is very low to the organic removal rate of solubilised state, almost nil; Although reverse osmosis has very high clearance to this part organism, but create a large amount of high saliferous and organic dense water in reverse osmosis concentrated compression process, the such waste water of obvious discharge does not meet environmental requirement, and the polyvalent ion in organism and water can cause serious fouling membrane, the operation of influential system.
Chinese patent CN201210057639 discloses a kind of system for recycling and treating coking wastewater and method, this technique comprises coagulation basin, inclined-plate clarifying basin, ultra-filtration equipment, ultrafiltration produce pond, first pump housing, the first strainer, the second strainer, second pump housing, nanofiltration device, nanofiltration product pond, the 3rd pump housing, the 3rd strainer, reverse osmosis unit and reverse osmosis produced pond, the dense water of its nanofiltration makes sintering processes, and its reverse osmosis concentrated water makes evaporation process.Although this technique proposes treatment process to the dense water of nanofiltration and reverse osmosis concentrated water, because the dense water yield of nanofiltration and the reverse osmosis concentrated water yield are all comparatively large, nanofiltration dense water organic concentration is low, calorific value is low, adopts sintering processes, and its processing costs is expensive; Although reverse osmosis concentrated water have passed through concentrated, saltiness is still lower, if adopt evaporation process, processing costs is high.
Summary of the invention
In order to overcome the problems referred to above of the prior art and defect, the invention provides a kind of stable, with low cost and the organic waste water minimizing that treatment effect is good, recycling processing method and treatment system thereof, thus achieving wastewater reduction, resource utilization.
The invention provides a kind of organic waste water minimizing, recycling processing method, the method comprises following steps sequentially:
(1) pre-treatment is carried out to organic waste water, obtain the water outlet after pre-treatment; Wherein, described pre-treatment is selected from pre-treatment and/or biochemical treatment and/or advanced treatment; Wherein, described pre-treatment is selected from one or more in coagulation, oil removal, air supporting, precipitation, filtration, stripping; Described advanced treatment be selected from coagulating sedimentation, absorption, advanced oxidation, biological filter process in one or more;
(2) solid-liquid separation process is carried out to the water outlet that step (1) obtains, obtain solid-liquid separation water outlet;
(3) nanofiltration process is carried out to the solid-liquid separation water outlet that step (2) obtains, obtain nanofiltration and produce water and the dense water of nanofiltration;
(4) carry out the dense water treatment of nanofiltration to the dense water of nanofiltration that step (3) obtains, obtain the water outlet of the dense water treatment of nanofiltration, the water outlet of the dense water treatment of nanofiltration is back to step (3) and mixes with solid-liquid separation water outlet, carries out nanofiltration process; Wherein, the dense water treatment of described nanofiltration is selected from one or more in biochemical optimization process, sofening treatment, MBR process;
(5) nanofiltration obtained step (3) is produced water and is carried out the first reverse-osmosis treated, obtains the first reverse osmosis produced water and the first reverse osmosis concentrated water; Preferably, the part that water is produced in nanofiltration step (3) obtained is drawn, and to carry out reuse/discharge, or is used as the former water of advanced purification system;
(6) the second reverse-osmosis treated is carried out to the first reverse osmosis concentrated water that step (5) obtains, obtain the second reverse osmosis produced water and the second reverse osmosis concentrated water;
(7) evaporative crystallization process is carried out to the second reverse osmosis concentrated water that step (6) obtains, obtain crystal salt and evaporation condensate.
According to method of the present invention, wherein, organic waste water includes but not limited to the industrial organic waste water that Coal Chemical Industry, petrochemical complex, pharmacy, printing and dyeing, food service industry are discharged and sanitary sewage.
According to method of the present invention, wherein, in described method steps (1), pre-treatment can remove organism, ammonia nitrogen, oil, nitric nitrogen, phosphoric acid salt, the suspended substance of the overwhelming majority in water.Described biochemical processing method includes but not limited to anaerobic treatment, acidication process, anaerobic treatment, aerobic treatment and combination thereof; Wherein anaerobic treatment comprises anaerobic filter process, upflow anaerobic sludge blanket process process, anaerobic fluidized bed process and combination thereof; Aerobic treatment comprise in contact-oxidation pool process, BAF process, activated sludge tank process one or more.Advanced treatment includes but not limited to coagulating sedimentation, absorption, advanced oxidation, biological filter process and combination thereof, and wherein advanced oxidation comprises ozone oxidation, Fenton (Fenton) oxidation, fenton-type reagent and combination thereof.
According to method of the present invention, wherein, in described method steps (2), the water outlet obtained by step (1) adopts precipitation, coagulating sedimentation, air supporting, filtration, membrane sepn and combination thereof to carry out solid-liquid separation, to remove suspended substance and the turbidity of the overwhelming majority in water.Preferably, membrane separating method comprises microfiltration membrane and is separated and/or Ultra filtration membrane, transports outward disposal after the solid reuse after solid-liquid separation or further dehydration.The concentration that solid-liquid separation produces the suspended substance of water is 0 ~ 100mg/L, is preferably 0 ~ 50mg/L; Turbidity is 0 ~ 100NTU, is preferably 0 ~ 50NTU.
According to method of the present invention, wherein, in described method steps (3), the dense water of nanofiltration that the solid-liquid separation product water obtain step (2) and step (4) return carries out nanofiltration process, so that most of organism, hardness, secondary and the polyvalent ion in water, partial solubility total solids (TDS) are separated and are concentrated.Wherein, nanofiltration process adopts nano filter membrance device to carry out; Preferably, cartridge filter is set before nanofiltration device; Nanofiltration membrane is sulfonated polyether sulfone film and/or polyamide composite film.It is 60 ~ 95% that Water Sproading rate is produced in nanofiltration, is preferably 70 ~ 90%; Ratio of desalinization 5 ~ 60%, is preferably 10 ~ 50%; Organic removal rate 30 ~ 100%, is preferably 50 ~ 90%; Divalence and polyvalent ion clearance 20 ~ 100%, be preferably 40 ~ 98%.
According to method of the present invention, wherein, in described method steps (4), the dense water treatment of nanofiltration is carried out to the dense water of nanofiltration that step (3) obtains, to remove most of organism, divalence and polyvalent ion in water and hardness.Preferably, biochemical optimization process comprises absorption, advanced oxidation, acidication, other changes one or more to improve in the method for biochemical sewage of Organic substance in water molecular structure and composition.More preferably, advanced oxidation comprises ozone oxidation, Fenton oxidation, fenton-type reagent and combination thereof.Sofening treatment comprise in lime soften for sewage, carbonate deposition, ion-exchange one or more; Further, lime soften for sewage is that white lime is softening and/or unslaked lime is softening; The carbonate used in carbonate deposition is sodium carbonate and/or sodium bicarbonate; Ion-exchange comprises cation bed ion-exchange, anion bed ion-exchange and mixed bed ion exchange in one or more.MBR process adopts micro-filtration MBR membrane bioreactor and/or ultrafiltration MBR membrane bioreactor to carry out.The organic removal rate 70 ~ 95% of the dense water treatment water outlet of nanofiltration, is preferably 80 ~ 90%; Hardness clearance is 80 ~ 95%, is preferably 85 ~ 90%.
According to method of the present invention, wherein, in described method steps (5), the first reverse-osmosis treated is carried out, to remove the total dissolved solid of the overwhelming majority and remaining organism to the nanofiltration product water that step (3) obtains.Preferably, the first reverse-osmosis treated adopts reverse osmosis membrane to carry out; Preferably, cartridge filter is set before reverse osmosis membrane.More preferably, reverse osmosis membrane is cellulose acetate membrane and/or polyamide composite film.
The rate of recovery of the first reverse osmosis produced water is 50 ~ 80%, is preferably 55 ~ 75%; Ratio of desalinization 80 ~ 99%, is preferably 90 ~ 98.5%; Organic removal rate 80 ~ 100%, is preferably 90 ~ 98%.
According to method of the present invention, wherein, in described method steps (6), the second reverse-osmosis treated is carried out to the first reverse osmosis concentrated water that step (5) obtains, to concentrate total dissolved solid and organism further, and produce less salt product water.Preferably, the second reverse-osmosis treated adopts reverse osmosis membrane apparatus to carry out; Preferably, cartridge filter is set before reverse osmosis membrane apparatus; More preferably, reverse osmosis membrane is pollution-resistant brackish water desalination film and/or pollution-resistant sea water desalination membrane.
The second reverse osmosis produced water rate of recovery is 40 ~ 75%, is preferably 50 ~ 70%; Ratio of desalinization 80 ~ 99%, is preferably 90 ~ 98.5%; Organic removal rate 80 ~ 100%, is preferably 90 ~ 98%.
According to method of the present invention, wherein, in described method steps (7), evaporative crystallization process is carried out to the second reverse osmosis concentrated water that step (6) obtains, to produce crystal salt, and reclaims phlegma.Preferably, one or more in evaporative crystallization process employing vaporizer, crystallizer, crystal salt separator carry out.More preferably, vaporizer is MVR vaporizer or multiple-effect evaporator; Crystallizer is evaporative crystallizer or cooling crystallizer; Crystal salt separator is whizzer.Crystal salt include but not limited in sodium-chlor, sodium sulfate, magnesium sulfate, SODIUMNITRATE one or more.
Specific conductivity 20 ~ 500 μ s/cm of phlegma, is preferably 30 ~ 200 μ s/cm; The concentration of total dissolved solid is 10 ~ 300mg/L, is preferably 20 ~ 100mg/L; The concentration of TOC (total organic carbon) is 1 ~ 50mg/L, is preferably 2 ~ 30mg/L; COD is 5 ~ 100mg/L, is preferably 10 ~ 50mg/L.
According to method of the present invention, wherein, the product water for the treatment of process of the present invention and treatment system comprises the solid-liquid separation water outlet obtained by the step of the inventive method (2), water, the first reverse osmosis produced water obtained by the step (5) of the inventive method, the second reverse osmosis produced water obtained by the step (6) of the inventive method, the evaporation condensate that obtained by the step (7) of the inventive method are produced in the nanofiltration obtained by the step (3) of the inventive method.These produce water can reuse/discharge, or is used as the former water of advanced purification system.
Present invention also offers a kind of for implementing the organic waste water minimizing of the inventive method, the treatment system of resource utilization, this treatment system comprises pretreatment unit that fluid is successively communicated with, solid-liquid separation unit, nano-filtration unit, is connected to the dense unit for treating water of nanofiltration, the first reverse osmosis units, the second reverse osmosis units and evaporative crystallization unit between the dense water water outlet of nano-filtration unit and solid-liquid separation unit water outlet.
Wherein, solid-liquid separation unit accepts the water outlet from pretreatment unit, and after carrying out solid-liquid separation process, nano-filtration unit is delivered in the solid-liquid separation water outlet obtained.
Nano-filtration unit accepts the solid-liquid separation water outlet from solid-liquid separation unit, after carrying out nanofiltration process, obtains nanofiltration and produces water and the dense water of nanofiltration, dense for nanofiltration water is delivered to the dense unit for treating water of nanofiltration.
The dense unit for treating water of nanofiltration accepts the dense water of nanofiltration from nano-filtration unit, after carrying out the dense water treatment of nanofiltration, obtains the water outlet of the dense unit for treating water of nanofiltration; After the water outlet of dense for nanofiltration unit for treating water being mixed with solid-liquid separation water outlet, send nano-filtration unit back to.
First reverse osmosis units accepts to produce water from the nanofiltration of nano-filtration unit, after carrying out the first reverse-osmosis treated, obtains the first reverse osmosis produced water and the first reverse osmosis concentrated water; First reverse osmosis concentrated water is delivered to the second reverse osmosis units.
Second reverse osmosis units accepts the first reverse osmosis concentrated water from the first reverse osmosis units, after carrying out the second reverse-osmosis treated, obtains the second reverse osmosis produced water and the second reverse osmosis concentrated water; Second reverse osmosis concentrated water is delivered to evaporative crystallization unit.
Evaporative crystallization unit accepts the second reverse osmosis concentrated water from the second reverse osmosis units, through evaporative crystallization, obtains crystal salt and evaporation condensate.
Preferably, in treatment system of the present invention, the product water of solid-liquid separation unit, nano-filtration unit, the first reverse osmosis units, the second reverse osmosis units and evaporative crystallization unit delivers to reuse/discharge, or delivers to advanced purification system and be used as former water.
Preferably, in treatment in accordance with the present invention system, pretreatment unit comprises pretreatment unit and/or biochemical treatment unit and/or advanced treatment unit.More preferably, pretreatment unit includes but not limited to one or more in coagulation, oil removal, air supporting, precipitation, filtration, stripping.Preferably, biochemical treatment unit includes but not limited to anaerobic treatment unit and/or acidication and/or anaerobic treatment unit and/or aerobic treatment unit; More preferably, anaerobic treatment unit includes but not limited to anaerobic filter, upflow anaerobic sludge blanket process, anaerobic fluidized bed and combination; Aerobic treatment unit include but not limited in contact-oxidation pool, BAF, activated sludge tank one or more.Preferably, advanced treatment unit includes but not limited to coagulating sedimentation unit, absorbing unit, advanced oxidation unit, biological filter and combination thereof; More preferably, advanced oxidation unit comprises ozone oxidation unit, Fenton oxidation unit, fenton-type reagent unit and combination thereof.
Preferably, in treatment in accordance with the present invention system, solid-liquid separation unit comprises precipitation unit, coagulating sedimentation unit, air flotation cell, filtering unit, film separation unit and combination thereof; More preferably, film separation unit comprises microfiltration membrane separating unit and/or Ultra filtration membrane unit.
Preferably, in treatment in accordance with the present invention system, nano-filtration unit is nano filter membrance device; More preferably, nano-filtration unit also comprises the cartridge filter before being arranged on nano filter membrance device.More preferably, nanofiltration membrane is sulfonated polyether sulfone film and/or polyamide composite film.
Preferably, in treatment in accordance with the present invention system, the dense unit for treating water of nanofiltration comprises biochemical and optimizes unit and/or pliable cell and/or MBR unit.More preferably, biochemical optimize unit comprise absorbing unit, advanced oxidation unit, acidication unit or other change one or more to improve in the processing unit of biochemical sewage of Organic substance in water molecular structure and composition.Again preferably, advanced oxidation unit comprises ozone oxidation unit, Fenton oxidation unit, fenton-type reagent unit and combination thereof.Preferably, pliable cell is lime soften for sewage unit, carbonate deposition unit, ion-exchange unit and combination thereof; More preferably, lime soften for sewage unit is white lime pliable cell and/or unslaked lime pliable cell; Carbonate deposition unit comprises sodium carbonate and/or sodium bicarbonate precipitation unit; Ion-exchange unit is cation bed ion-exchange unit, anion bed ion-exchange unit, mixed bed ion crosspoint and combination thereof.More preferably, MBR unit is micro-filtration MBR membrane biological reaction unit and/or ultrafiltration MBR membrane biological reaction unit.
Preferably, in treatment in accordance with the present invention system, the first reverse osmosis units is reverse osmosis membrane apparatus; More preferably, the first reverse osmosis units also comprises the cartridge filter be arranged on before the first reverse osmosis unit.More preferably, the reverse osmosis membrane in the first reverse osmosis units is cellulose acetate membrane and/or polyamide composite film.
Preferably, in treatment in accordance with the present invention system, the second reverse osmosis units is reverse osmosis membrane apparatus; More preferably, the second reverse osmosis units also comprises the cartridge filter be arranged on before anti-second reverse osmosis units.More preferably, the reverse osmosis membrane in the second reverse osmosis units is pollution-resistant brackish water desalination film and/or pollution-resistant sea water desalination membrane.
Preferably, in treatment in accordance with the present invention system, evaporative crystallization unit comprises vaporizer, crystallizer, crystal salt separator.More preferably, vaporizer is MVR vaporizer or multiple-effect evaporator; Crystallizer comprises evaporative crystallizer, cooling crystallizer; Crystal salt separator is whizzer.
Solid-liquid separation from processing unit produces water, water, the first reverse osmosis produced water, the second reverse osmosis produced water, evaporation condensate are produced in nanofiltration, qualified discharge or require carry out reasonable reuse or be used as the former water of advanced purification system according to by water spot water water quality, the water yield.
Treatment process of the present invention and treatment system have but are not limited to following beneficial effect:
1. adopt nanofiltration as the pre-treating technology of reverse osmosis, retain and remove nanofiltration and produce most organism and divalence and polyvalent ion, hardness in water, reduce the risk of the first reverse osmosis units and follow-up second reverse osmosis units fouling and pollution, the rate of recovery of reverse osmosis units can be improved, extend the work-ing life of reverse osmosis units, ensure the safe and stable operation of reverse osmosis units, and reduce the intractability of follow-up strong brine, processing load and facility investment and working cost.
2. adopt the dense water of nanofiltration dense unit for treating water process nanofiltration, the product water of the dense unit for treating water of nanofiltration gets back to the treatment process that nano-filtration unit carries out reprocessing, achieves treatment system of the present invention and produces without the dense water of nanofiltration, improve the rate of recovery of system water.
3. adopt nanofiltration dense unit for treating water process nanofiltration dense water not only can remove the remaining hardly degraded organic substance of the overwhelming majority in water, and the most divalence can removed in water and polyvalent ion, reduce nanofiltration by the risk of Organic pollutants and fouling.
4. the present invention adopts nanofiltration to produce water as middle water, and it produces water quality and is significantly better than solid-liquid separation unit product water quality, and its cost of water treatment per ton is significantly lower than reverse osmosis produced water.Nanofiltration produces water as middle water, time particularly as the recirculating cooling water system moisturizing that water loss is large, have solid-liquid separation unit and the incomparable advantage of reverse osmosis produced water, not only its processing cost is low, and its organism, hardness content are very low, be conducive to the safe and stable operation of circulating water system.
5. treatment process of the present invention and treatment system adopt the second reverse-osmosis treated to concentrate further the first reverse osmosis concentrated water, reclaim the second reverse osmosis produced water, adopt evaporative crystallization unit to the second reverse osmosis concentrated water condensing crystal, extract crystal salt, and reclaim evaporation condensate, really realize the zero release of waste water.
6. the present invention passes through organic waste water process in various degree, and carries out reuse by quality and purposes, really achieves the minimizing of sewage, resource utilization, energy-saving and cost-reducing object.
Accompanying drawing explanation
Below, describe embodiment of the present invention in detail by reference to the accompanying drawings, wherein:
Fig. 1 shows the process flow diagram of an embodiment of organic waste water minimizing of the present invention, recycling processing method;
Fig. 2 shows the schematic diagram of an embodiment of organic waste water minimizing of the present invention, recycling treatment system;
Fig. 3 shows the organic waste water minimizing of the present invention for crushed coal pressure gasifying wastewater treatment, the schematic diagram of recycling treatment system;
Fig. 4 shows the organic waste water minimizing of the present invention for crushed coal pressure gasifying wastewater treatment, the detail drawing of recycling treatment system;
Fig. 5 shows the organic waste water minimizing of the present invention for petroleum asphaltene process, the schematic diagram of recycling treatment system;
Fig. 6 shows the organic waste water minimizing of the present invention for petroleum asphaltene process, the detail drawing of recycling treatment system;
Fig. 7 shows the organic waste water minimizing of the present invention for treatment of dyeing wastewater, the schematic diagram of recycling treatment system; And
Fig. 8 shows the organic waste water minimizing of the present invention for treatment of dyeing wastewater, the detail drawing of recycling treatment system.
Embodiment
Further illustrate the present invention below by specific embodiment, but should be understood to, these embodiments are only used for the use specifically described more in detail, and should not be construed as limiting the present invention in any form.
General description is carried out to the material used in the present invention's test and test method in this part.Although for realizing many materials that the object of the invention uses and working method is well known in the art, the present invention still describes in detail as far as possible at this.It will be apparent to those skilled in the art that within a context, if not specified, material therefor of the present invention and working method are well known in the art.
embodiment 1
The present embodiment is for illustration of crushed coal pressure gasifying wastewater reduction of the present invention, recycling processing method and treatment system thereof.
Crushed coal pressure gasifying wastewater reduction as shown in Figure 1, recycling treatment system, described treatment system mainly comprises pretreatment unit, solid-liquid separation unit, nano-filtration unit, the first reverse osmosis units, the second reverse osmosis units, the evaporative crystallization unit that sequentially fluid is communicated with, and is connected to the dense unit for treating water of nanofiltration between the dense water water outlet of nano-filtration unit and solid-liquid separation unit water outlet.
The technical data of this treatment system is set as follows:
Pretreatment unit
The each subelement of pretreatment unit is followed successively by: pretreatment system and biochemical treatment system.
The each subsystem of pretreatment system is followed successively by: Tube separators, cavitation air flotation pond, and each subsystem of biochemical treatment unit is followed successively by: anaerobic pond, anoxic pond, Aerobic Pond.
Each significant parameter:
The hydraulic detention time of Tube separators: 1h
The hydraulic detention time of cavitation air flotation system: 30min
The hydraulic detention time of anaerobic pond reaction zone is 24h
The hydraulic detention time of anoxic pond reaction zone is 10h
The hydraulic detention time of Aerobic Pond reaction zone is 36h
(1) solid-liquid separation unit
The each subelement of solid-liquid separation unit is followed successively by: coagulating sedimentation, filtration, ultrafiltration, each significant parameter:
The hydraulic detention time 3h of coagulating sedimentation system
Filtering velocity 5 ~ the 10m/h of filtering system
Ultra-filtration membrane is PVDF external pressure hollow-fibre membrane
(2) nano-filtration unit
The each subsystem of nano-filtration unit is followed successively by: cartridge filter, nanofiltration, each significant parameter:
Cartridge filter filtering accuracy is 5 μm
Nanofiltration membrane type is polyamide composite film
(3) the dense unit for treating water of nanofiltration
The each subelement of the dense unit for treating water of nanofiltration is followed successively by: biochemical optimization system, melded system, MBR system, each significant parameter:
Biochemical optimization system is Fenton oxidation system, Fenton reaction times 3h
Melded system is " lime soften for sewage system+carbonate melded system "
MBR system is " anoxic+aerobic+built-in ultrafiltration membrane system ", sludge concentration 6000 ~ 12000mg/L
(4) first reverse osmosis units
The each subsystem of first reverse osmosis units is followed successively by: cartridge filter, the first reverse osmosis, each significant parameter:
Cartridge filter filtering accuracy is 5 μm
Reverse osmosis membrane type is polyamide composite film
Film original paper is pollution-resistant brackish water desalination reverse osmosis membrane original paper
(5) second reverse osmosis units
The each subsystem of second reverse osmosis units is followed successively by: cartridge filter, the second reverse osmosis, each significant parameter:
Cartridge filter filtering accuracy is 5 μm
Reverse osmosis membrane type is polyamide composite film
Film original paper is pollution-resistant seawater desalination reverse osmosis film original paper
(6) evaporative crystallization unit
The each subsystem of evaporative crystallization unit is followed successively by: vapo(u)rization system, crystal system, crystal salt separation system, each significant parameter:
Vapo(u)rization system is triple effect evaporation system
Crystal system is evaporation and crystallization system
Crystal salt separation system is centrifugal separation system
Crystal salt is mainly sodium-chlor
Evaporation condensate specific conductivity 50 μ s/cm
Crushed coal pressure gasifying waste water, its pH value is 8 ~ 9, COD is 4000mg/L, and the concentration of volatile phenol is 400mg/L, and the concentration of ammonia nitrogen is 250mg/L, and the concentration of petroleum substance is 70mg/L.
After premenstrual processing unit processes, water outlet COD≤200mg/L, the concentration≤1mg/L of volatile phenol, the concentration≤5mg/L of ammonia nitrogen, pH value 7 ~ 8, oil-contg≤5mg/L.
Waste water after pre-treatment, after solid-liquid separation unit process, produces water COD≤150mg/L, the concentration≤5mg/L of ammonia nitrogen, pH value 7 ~ 8, turbidity 0.05 ~ 1.0NTU, specific conductivity≤1500 μ s/cm, saltiness≤1000mg/L, total hardness≤300mg/L, the concentration≤120mg/L of sulfate radical.
Solid-liquid separation unit process gained waste water is after nano-filtration unit process, produce Water Sproading rate >=95%, produce water COD≤50mg/L, specific conductivity≤1000 μ s/cm, saltiness≤800mg/L, total hardness≤40mg/L, the concentration≤5mg/L of sulfate radical, dense water COD >=1000mg/L, specific conductivity >=8000 μ s/cm, saltiness >=5000mg/L, total hardness >=2200mg/L, the concentration >=1100mg/L of sulfate radical.
The dense water of nano-filtration unit process gained nanofiltration, after the dense unit for treating water process of nanofiltration, produces water COD≤100mg/L, specific conductivity≤4500 μ s/cm, saltiness≤3000mg/L, total hardness≤20mg/L.
The nanofiltration of nanofiltration dense unit for treating water process gained produces water after the first reverse osmosis units process, produce Water Sproading rate 75%, produce water TOC≤5mg/L, specific conductivity≤30 μ s/cm, saltiness≤25mg/L, dense water COD >=180mg/L, specific conductivity >=3900 μ s/cm, saltiness >=3100mg/L, total hardness >=160mg/L, the concentration >=20mg/L of sulfate radical.
First reverse osmosis concentrated water of the first reverse osmosis units process gained is after the second reverse osmosis units process, produce Water Sproading rate 70%, produce water TOC≤10mg/L, specific conductivity≤100 μ s/cm, saltiness≤70mg/L, dense water COD >=500mg/L, specific conductivity >=13000 μ s/cm, saltiness >=10000mg/L, total hardness >=530mg/L, the concentration >=60mg/L of sulfate radical.
Second reverse osmosis concentrated water of the second reverse osmosis units process gained is after evaporative crystallization cell processing, and the phlegma rate of recovery 90%, produce water TOC≤10mg/L, specific conductivity≤100 μ s/cm, saltiness≤70mg/L, crystal salt is sodium-chlor.
Nanofiltration is produced water and is met recirculating cooling water system moisturizing water quality requirement, and part is used as recirculated cooling water moisturizing.First reverse osmosis produced water, the second reverse osmosis produced water and evaporation condensate are used as power chemical water treatment system make-up water source.
embodiment 2
The present embodiment is for illustration of petroleum asphaltene minimizing of the present invention, recycling processing method and treatment system thereof.
Petroleum asphaltene minimizing as shown in Figure 2, recycling treatment system, described treatment system mainly comprises pretreatment unit, solid-liquid separation unit, nano-filtration unit, the first reverse osmosis units, the second reverse osmosis units, the evaporative crystallization unit that fluid is successively communicated with, and is connected to the dense unit for treating water of nanofiltration between the dense water water outlet of nano-filtration unit and solid-liquid separation unit water outlet.The technical data of the treatment system described in the present embodiment is set as follows:
(1) pretreatment unit
The each subelement of pretreatment unit is followed successively by: pretreatment system, biochemical treatment system and advanced treatment system.
The each subsystem of pretreatment system is followed successively by: Tube separators, cavitation air flotation pond, the each subsystem of biochemical treatment unit is followed successively by: anaerobism, anoxic, aerobic, settling tank, the each subsystem of advanced treatment system is followed successively by: coagulation and filtration system, ozone oxidation system, biological activated carbon system, each significant parameter:
The hydraulic detention time of oil trap: 1h
The hydraulic detention time of cavitation air flotation system: 30min
The hydraulic detention time of air-dissolving air-float system: 20min
The hydraulic detention time of anoxic pond reaction zone is 12h
The hydraulic detention time of Aerobic Pond reaction zone is 24h
The hydraulic detention time of settling tank is 4h
The filtering velocity of coagulation and filtration system is 5 ~ 10m/h, PAC dosage, 5 ~ 10mg/L
The ozone dosage of ozone oxidation system is 10 ~ 20mg/L
Biological activated carbon system hydraulic detention time is 1h
(2) solid-liquid separation unit
The each subelement of solid-liquid separation unit is followed successively by: cartridge filter, ultrafiltration, each significant parameter:
Cartridge filter filtering accuracy is 100 μm
Ultra-filtration membrane is PVDF external pressure hollow-fibre membrane
(3) nano-filtration unit
The each subsystem of nano-filtration unit is followed successively by: cartridge filter, nanofiltration, each significant parameter:
Cartridge filter filtering accuracy is 5 μm
Nanofiltration membrane type is polyamide composite film
(4) the dense unit for treating water of nanofiltration
The each subelement of the dense unit for treating water of nanofiltration is followed successively by: biochemical optimization system, melded system, MBR system, each significant parameter:
Biochemical optimization system is ozone oxidation system, oxidization time 2h
Melded system is " lime soften for sewage+carbonate softens "
The treatment process of MBR system is " anoxic+ultra-filtration membrane MBR membrane bioreactor system ", sludge concentration 6000 ~ 12000mg/L
(5) first reverse osmosis units
The each subsystem of first reverse osmosis units is followed successively by: cartridge filter, the first reverse osmosis, each significant parameter:
Cartridge filter filtering accuracy is 5 μm
Reverse osmosis membrane type is polyamide composite film
Film original paper is pollution-resistant brackish water desalination reverse osmosis membrane original paper
(6) second reverse osmosis units
The each subsystem of second reverse osmosis units is followed successively by: cartridge filter, the second reverse osmosis, each significant parameter:
Cartridge filter filtering accuracy is 5 μm
Reverse osmosis membrane type is polyamide composite film
Film original paper is pollution-resistant brackish water reverse osmosis membrane original paper
(7) evaporative crystallization unit
The each subsystem of evaporative crystallization unit is followed successively by: vapo(u)rization system, crystal system, crystal salt separation system, each significant parameter:
Vapo(u)rization system is four-effect evaporator system
Crystal system is evaporation and crystallization system
Crystal salt separation system is centrifugal separation system
Crystal salt is mainly sodium-chlor
Evaporation condensate specific conductivity 50 μ s/cm
Petroleum asphaltene, its pH value is 8 ~ 9, COD is 1000mg/L, the concentration of volatile phenol is 100mg/L, the concentration of ammonia nitrogen is 80mg/L, the concentration of petroleum substance is 300mg/L.
After premenstrual processing unit processes, the COD≤60mg/L of water outlet, the concentration≤1mg/L of volatile phenol, the concentration≤5mg/L of ammonia nitrogen, pH value 7 ~ 8, oil-contg≤5mg/L.
Waste water after pre-treatment, after solid-liquid separation unit process, produces the COD≤60mg/L of water, the concentration≤5mg/L of ammonia nitrogen, pH value 7 ~ 8, turbidity 0.05 ~ 1.0NTU, specific conductivity≤1200 μ s/cm, saltiness≤900mg/L, total hardness≤150mg/L, the concentration≤100mg/L of sulfate radical.
Solid-liquid separation unit process gained waste water is after nano-filtration unit process, produce Water Sproading rate >=95%, produce water COD≤20mg/L, specific conductivity≤900 μ s/cm, saltiness≤700mg/L, total hardness≤30mg/L, the concentration≤2mg/L of sulfate radical, dense water COD >=400mg/L, specific conductivity >=3900 μ s/cm, saltiness >=2700mg/L, total hardness >=1200mg/L, the concentration >=980mg/L of sulfate radical.
The dense water of nano-filtration unit process gained nanofiltration, after the dense unit for treating water process of nanofiltration, produces water COD≤60mg/L, specific conductivity≤3800 μ s/cm, saltiness≤2400mg/L, total hardness≤20mg/L.
The nanofiltration of nanofiltration dense unit for treating water gained produces water after the first reverse osmosis units process, produce Water Sproading rate 75%, produce water TOC≤5mg/L, specific conductivity≤30 μ s/cm, saltiness≤25mg/L, dense water COD >=60mg/L, specific conductivity >=3500 μ s/cm, saltiness >=2700mg/L, total hardness >=120mg/L.
First reverse osmosis concentrated water of the first reverse osmosis units process gained is after the second reverse osmosis units process, produce Water Sproading rate 75%, produce water TOC≤10mg/L, specific conductivity≤100 μ s/cm, saltiness≤70mg/L, dense water COD >=450mg/L, specific conductivity >=13700 μ s/cm, saltiness >=10600mg/L, total hardness >=480mg/L, the concentration >=50mg/L of sulfate radical.
Second reverse osmosis concentrated water of the second reverse osmosis units process gained is after evaporative crystallization cell processing, and the phlegma rate of recovery 95%, produce the TOC≤10mg/L of water, specific conductivity≤100 μ s/cm, saltiness≤70mg/L, crystal salt is sodium-chlor.
The leading indicator of solid-liquid separation product water reaches the requirement in " recirculated cooling water Standard of reclaimed water " (HGT3923-2007), and part nanofiltration is produced water and is used as clean recirculated cooling water moisturizing.First reverse osmosis produced water, the second reverse osmosis produced water and evaporation condensate are used as desalted water station make-up water source.
embodiment 3
The present embodiment is for illustration of dyeing waste water minimizing of the present invention, recycling processing method and treatment system thereof.
Dyeing waste water minimizing as shown in Figure 3, recycling treatment system, described treatment system comprises the pretreatment unit, solid-liquid separation unit, nano-filtration unit, the first reverse osmosis units, the second reverse osmosis units, the evaporative crystallization unit that sequentially connect, and is connected to the dense unit for treating water of nanofiltration between the dense water water outlet of nano-filtration unit and solid-liquid separation unit water outlet.The technical data of the treatment system of the present embodiment is set as follows:
(1) pretreatment unit
The each subsystem of pretreatment unit is followed successively by: hydrolysis acidification pool, Aerobic Pond, each significant parameter:
The hydraulic detention time of hydrolysis acidification pool is 24h
The hydraulic detention time of Aerobic Pond reaction zone is 20h
(2) solid-liquid separation unit
Solid-liquid separation unit is microfiltration membrane separation system, significant parameter:
Film original paper is PVDF hollow-fibre membrane
(3) nano-filtration unit
The each subsystem of nano-filtration unit is followed successively by: cartridge filter, nanofiltration, each significant parameter:
Cartridge filter filtering accuracy is 5 μm
Nanofiltration membrane type is polyamide composite film
(4) the dense unit for treating water of nanofiltration
The each subelement of the dense unit for treating water of nanofiltration is followed successively by: biochemical optimization system, melded system, MBR system, each significant parameter:
Biochemical optimization system is Fenton oxidation system, Fenton reaction times 3h
Melded system is " lime soften for sewage+carbonate softens "
MBR system treatment process is " anoxic+aerobic+built-in mocromembrane system ", sludge concentration 6000 ~ 12000mg/L
(5) first reverse osmosis units
The each subsystem of first reverse osmosis units is followed successively by: cartridge filter, the first reverse osmosis, each significant parameter:
Cartridge filter filtering accuracy is 5 μm
Reverse osmosis membrane type is polyamide composite film
Film original paper is pollution-resistant brackish water desalination reverse osmosis membrane original paper
(6) second reverse osmosis units
The each subsystem of second reverse osmosis units is followed successively by: cartridge filter, the second reverse osmosis, each significant parameter:
Cartridge filter filtering accuracy is 5 μm
Reverse osmosis membrane type is polyamide composite film
Film original paper is pollution-resistant seawater desalination reverse osmosis film original paper
(7) evaporative crystallization unit
The each subsystem of evaporative crystallization unit is followed successively by: vapo(u)rization system, crystal system, crystal salt separation system, each significant parameter:
Vapo(u)rization system is MVR vapo(u)rization system
Crystal system is evaporation and crystallization system
Crystal salt separation system is centrifugal separation system
Crystal salt is mainly sodium-chlor
Evaporation condensate specific conductivity 50 μ s/cm
Dyeing waste water, its pH value is 9 ~ 11, COD is 1200mg/L, BOD 5for 350mg/L, colourity 900 times.
After premenstrual processing unit processes, water outlet COD≤180mg/L, BOD 5≤ 30mg/L, the concentration≤5mg/L of ammonia nitrogen, pH value 6 ~ 9, colourity≤50 times.
Waste water after pre-treatment, after solid-liquid separation unit process, produces water COD≤150mg/L, the concentration≤5mg/L of ammonia nitrogen, pH value 6 ~ 9, colourity≤50 times, turbidity 0.05 ~ 1.0NTU, specific conductivity≤1600 μ s/cm, saltiness≤1100mg/L, total hardness≤200mg/L, sulfate radical≤300mg/L.
Solid-liquid separation unit process gained waste water is after nano-filtration unit process, produce Water Sproading rate >=95%, produce water COD≤10mg/L, specific conductivity≤950 μ s/cm, saltiness≤700mg/L, total hardness≤30mg/L, the concentration≤10mg/L of sulfate radical, dense water COD >=1400mg/L, specific conductivity >=7450 μ s/cm, saltiness >=4700mg/L, total hardness >=1700mg/L, the concentration >=2900mg/L of sulfate radical.
The dense water of nano-filtration unit process gained nanofiltration, after the dense unit for treating water process of nanofiltration, produces water COD≤100mg/L, specific conductivity≤5000 μ s/cm, saltiness≤3300mg/L, total hardness≤20mg/L.
The nanofiltration of nanofiltration dense unit for treating water process gained produces water after the first reverse osmosis units process, produce Water Sproading rate 75%, produce water TOC≤5mg/L, specific conductivity≤30 μ s/cm, saltiness≤25mg/L, dense water COD >=50mg/L, specific conductivity >=3700 μ s/cm, saltiness >=2700mg/L, total hardness >=120mg/L, the concentration >=40mg/L of sulfate radical.
First reverse osmosis concentrated water of the first reverse osmosis units process gained is after the second reverse osmosis units process, produce Water Sproading rate 75%, produce water TOC≤5mg/L, specific conductivity≤100 μ s/cm, saltiness≤70mg/L, dense water COD >=170mg/L, specific conductivity >=14500 μ s/cm, saltiness >=10700mg/L, total hardness >=480mg/L, the concentration >=160mg/L of sulfate radical.
Second reverse osmosis concentrated water of the second reverse osmosis units process gained is after evaporative crystallization cell processing, and the phlegma rate of recovery 95%, produce water TOC≤10mg/L, specific conductivity≤100 μ s/cm, saltiness≤70mg/L, crystal salt is sodium-chlor.
Nanofiltration is produced water and is met rinsing or dyeing water water quality requirement, and part can be used as rinsing or dyeing water, and the first reverse osmosis produced water, the second reverse osmosis produced water and evaporation condensate are used as boiler feed water make-up water source, also can be used for the operations such as dyeing.
Although to the description that present invention has been to a certain degree, significantly, under the condition not departing from the spirit and scope of the present invention, can carry out the suitable change of each condition.Be appreciated that and the invention is not restricted to described embodiment, and be attributed to the scope of claim, it comprises the equivalent replacement of described each factor.

Claims (10)

1. the minimizing of organic waste water, a recycling processing method, the treating method comprises following steps sequentially:
(1) pre-treatment is carried out to waste water, obtain the water outlet after pre-treatment; Wherein, described pre-treatment is selected from pre-treatment and/or biochemical treatment and/or advanced treatment; Described pre-treatment be selected from coagulation, oil removal, air supporting, precipitation, filtration, stripping one or more; Described advanced treatment be selected from coagulating sedimentation, absorption, advanced oxidation, biological filter process in one or more;
(2) solid-liquid separation process is carried out to the water outlet that step (1) obtains, obtain solid-liquid separation water outlet;
(3) nanofiltration process is carried out to the solid-liquid separation water outlet that step (2) obtains, obtain nanofiltration and produce water and the dense water of nanofiltration;
(4) carry out the dense water treatment of nanofiltration to the dense water of nanofiltration that step (3) obtains, obtain the dense water treatment water outlet of nanofiltration, the dense water treatment water outlet of described nanofiltration is back to step (3) and mixes with solid-liquid separation water outlet, carries out nanofiltration process; Wherein, the dense water treatment of described nanofiltration is selected from one or more in biochemical optimization process, sofening treatment, MBR process;
(5) nanofiltration obtained step (3) is produced water and is carried out the first reverse-osmosis treated, obtains the first reverse osmosis produced water and the first reverse osmosis concentrated water; Preferably, the part that water is produced in nanofiltration step (3) obtained is drawn, and to carry out reuse/discharge, or is used as the former water of advanced purification system;
(6) the second reverse-osmosis treated is carried out to the first reverse osmosis concentrated water that step (5) obtains, obtain the second reverse osmosis produced water and the second reverse osmosis concentrated water;
(7) evaporation process is carried out to the second reverse osmosis concentrated water that step (6) obtains, obtain evaporation concentration liquid and evaporation condensate; Preferably, crystallization treatment is carried out to evaporation concentration liquid, obtain crystal salt and crystallization concentrated solution.
2. treatment process according to claim 1, is characterized in that, in step (1), described biochemical treatment be selected from anaerobic treatment, acidication process, anaerobic treatment, aerobic treatment one or more; Wherein anaerobic treatment is selected from one or more in anaerobic filter process, upflow anaerobic sludge blanket process process, anaerobic fluidized bed process; Aerobic treatment is selected from contact-oxidation pool process, biological filter process, one or more in activated sludge tank process;
Preferably, described advanced oxidation is selected from one or more in ozone oxidation, Fenton oxidation, fenton-type reagent;
Preferably, the process of described biological filter is selected from one or more in ordinary biofilter process, BAF process, biological activated carbon filter process.
3. treatment process according to claim 1, is characterized in that, in step (2), described solid-liquid separation process be selected from precipitation, coagulating sedimentation, air supporting, filtration, membrane sepn one or more; Preferably, membrane sepn is that microfiltration membrane is separated and/or Ultra filtration membrane.
4. treatment process according to claim 1, is characterized in that, in step (3), nanofiltration process adopts nano filter membrance device to carry out; Preferably, cartridge filter is set before nanofiltration device;
Preferably, nanofiltration membrane is sulfonated polyether sulfone film and/or polyamide composite film.
5. treatment process according to claim 1, is characterized in that, in step (4), biochemical optimization method be selected from absorption, advanced oxidation, acidication one or more; Again preferably, advanced oxidation is selected from one or more in ozone oxidation, Fenton oxidation, fenton-type reagent;
Preferably, sofening treatment is selected from one or more in lime soften for sewage, carbonate deposition, ion-exchange; Again preferably, described lime soften for sewage is that white lime is softening and/or unslaked lime is softening; The carbonate used in described carbonate deposition is sodium carbonate and/or sodium bicarbonate; Described ion-exchange be selected from cation bed ion-exchange, anion bed ion-exchange, mixed bed ion exchange in one or more;
Preferably, MBR process adopts micro-filtration MBR membrane bioreactor and/or ultrafiltration MBR membrane bioreactor to carry out.
6. the treatment process according to any one of claim 1-5, is characterized in that, in step (5), the first reverse-osmosis treated adopts reverse osmosis membrane apparatus to carry out; Preferably, cartridge filter is set before reverse osmosis unit;
Preferably, the excessive filtering accuracy of described cartridge filter is 5 μm;
Preferably, the reverse osmosis membrane in the first reverse-osmosis treated is cellulose acetate membrane and/or polyamide composite film.
7. the treatment process according to any one of claim 1-5, is characterized in that, in step (6), the second reverse-osmosis treated adopts reverse osmosis membrane apparatus to carry out; Preferably, cartridge filter is set before reverse osmosis membrane apparatus;
Preferably, the excessive filtering accuracy of described cartridge filter is 5 μm;
Preferably, the reverse osmosis membrane in the second reverse-osmosis treated is pollution-resistant brackish water desalination film and/or pollution-resistant sea water desalination membrane.
8. the treatment process according to any one of claim 1-5, is characterized in that, in step (7), one or more in evaporative crystallization process employing vaporizer, crystallizer, crystal salt separator carry out; More preferably, vaporizer is MVR vaporizer or multiple-effect evaporator; Crystallizer is evaporative crystallizer or cooling crystallizer; Crystal salt separator is whizzer; Crystal salt is one or more in sodium-chlor, sodium sulfate, magnesium sulfate, SODIUMNITRATE.
9., for implementing the claims a system for treatment process according to any one of 1-8, this system comprises pretreatment unit that fluid is successively communicated with, solid-liquid separation unit, nano-filtration unit, is connected to the dense unit for treating water of nanofiltration, the first reverse osmosis units, the second reverse osmosis units and evaporative crystallization unit between the dense water water outlet of nano-filtration unit and solid-liquid separation unit water outlet;
Wherein, described pretreatment unit is pretreatment unit and/or biochemical treatment unit and/or advanced treatment unit, pretreatment unit be selected from coagulation basin, oil trap, air flotation pool, settling tank, filtering basin, stripping device one or more; Advanced treatment unit be selected from coagulating sedimentation unit, absorbing unit, advanced oxidation unit, biological filter one or more;
The dense unit for treating water of nanofiltration is selected from biochemical and optimizes unit and/or pliable cell and/or MBR unit;
Solid-liquid separation unit accepts the water outlet from pretreatment unit, and after carrying out solid-liquid separation process, nano-filtration unit is delivered in the solid-liquid separation water outlet obtained;
Nano-filtration unit accepts the solid-liquid separation water outlet from solid-liquid separation unit, after carrying out nanofiltration process, obtains nanofiltration and produces water and the dense water of nanofiltration, dense for nanofiltration water is delivered to the dense unit for treating water of nanofiltration;
The dense unit for treating water of nanofiltration accepts the dense water of nanofiltration from nano-filtration unit, after carrying out the dense water treatment of nanofiltration, obtains the dense water treatment water outlet of nanofiltration; After dense for nanofiltration water treatment water outlet being mixed with solid-liquid separation water outlet, send nano-filtration unit back to;
First reverse osmosis units accepts to produce water from the nanofiltration of nano-filtration unit, after carrying out the first reverse-osmosis treated, obtains the first reverse osmosis produced water and the first reverse osmosis concentrated water; First reverse osmosis concentrated water is delivered to the second reverse osmosis units;
Second reverse osmosis units accepts the first reverse osmosis concentrated water from the first reverse osmosis units, after carrying out the second reverse-osmosis treated, obtains the second reverse osmosis produced water and the second reverse osmosis concentrated water; Second reverse osmosis concentrated water is delivered to evaporative crystallization unit;
Evaporative crystallization unit accepts the second reverse osmosis concentrated water from the second reverse osmosis units, through evaporative crystallization, obtains crystal salt and evaporation condensate;
Preferably, the product water of solid-liquid separation unit, nano-filtration unit, the first reverse osmosis units, the second reverse osmosis units and evaporative crystallization unit delivers to reuse/blowdown system, or delivers to advanced purification system and be used as former water.
10. system according to claim 9, is characterized in that, biochemical treatment unit is anaerobic treatment unit and/or acidication and/or anaerobic treatment unit and/or aerobic treatment unit; More preferably, anaerobic treatment unit be selected from anaerobic filter, upflow anaerobic sludge blanket process, anaerobic fluidized bed in one or more; Aerobic treatment unit be selected from contact-oxidation pool, BAF, activated sludge tank one or more; More preferably, advanced oxidation unit is selected from one or more in ozone oxidation unit, Fenton oxidation unit, fenton-type reagent unit;
Preferably, solid-liquid separation unit is selected from one or more in precipitation unit, coagulating sedimentation unit, air flotation cell, filtering unit, film separation unit; More preferably, film separation unit is microfiltration membrane separating unit and/or Ultra filtration membrane unit;
Preferably, nano-filtration unit is nano filter membrance device; More preferably, nano-filtration unit also comprises the cartridge filter before being arranged on nano filter membrance device; Again preferably, nanofiltration membrane is sulfonated polyether sulfone film and/or polyamide composite film;
Preferably, described biochemical optimization unit is selected from one or more in absorbing unit, advanced oxidation unit, acidication unit; More preferably, advanced oxidation unit is selected from one or more in ozone oxidation unit, Fenton oxidation unit, fenton-type reagent unit; Preferably, pliable cell is one or more in lime soften for sewage unit, carbonate deposition unit, ion-exchange unit; More preferably, lime soften for sewage unit is white lime pliable cell and/or unslaked lime pliable cell; Carbonate deposition unit is sodium carbonate and/or sodium bicarbonate precipitation unit; Ion-exchange unit is one or more in cation bed ion-exchange unit, anion bed ion-exchange unit, mixed bed ion crosspoint; More preferably, MBR unit is micro-filtration MBR membrane biological reaction unit and/or ultrafiltration MBR membrane biological reaction unit;
Preferably, the first reverse osmosis units is reverse osmosis membrane apparatus; More preferably, described first reverse osmosis units also comprises the cartridge filter before being arranged on reverse osmosis membrane apparatus; Again preferably, the reverse osmosis membrane in the first reverse osmosis units is cellulose acetate membrane and/or polyamide composite film;
Preferably, the second reverse osmosis units is reverse osmosis membrane apparatus; More preferably, described second reverse osmosis units also comprises the cartridge filter before being arranged on reverse osmosis units; Again preferably, the reverse osmosis membrane in the second reverse osmosis units is pollution-resistant brackish water desalination film and/or pollution-resistant sea water desalination membrane;
Preferably, evaporative crystallization unit is selected from vaporizer, crystallizer, crystal salt separator; More preferably, vaporizer is MVR vaporizer or multiple-effect evaporator; Crystallizer is evaporative crystallizer or cooling crystallizer; Crystal salt separator is whizzer.
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