CN114716083A - Industrial strong brine zero-discharge treatment system and method - Google Patents
Industrial strong brine zero-discharge treatment system and method Download PDFInfo
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- 239000012267 brine Substances 0.000 title claims abstract description 79
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- 238000011282 treatment Methods 0.000 title claims abstract description 71
- 238000000034 method Methods 0.000 title claims abstract description 51
- 208000028659 discharge Diseases 0.000 title abstract description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 165
- 239000012528 membrane Substances 0.000 claims abstract description 116
- 238000000909 electrodialysis Methods 0.000 claims abstract description 89
- 238000001223 reverse osmosis Methods 0.000 claims abstract description 72
- 238000001728 nano-filtration Methods 0.000 claims abstract description 59
- 239000002253 acid Substances 0.000 claims abstract description 55
- 238000004519 manufacturing process Methods 0.000 claims abstract description 31
- 238000002425 crystallisation Methods 0.000 claims abstract description 30
- 230000008025 crystallization Effects 0.000 claims abstract description 30
- 239000000243 solution Substances 0.000 claims abstract description 21
- 150000003839 salts Chemical class 0.000 claims description 21
- 239000011575 calcium Substances 0.000 claims description 13
- 150000002500 ions Chemical class 0.000 claims description 13
- 238000010612 desalination reaction Methods 0.000 claims description 12
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 11
- 229910052791 calcium Inorganic materials 0.000 claims description 11
- 238000001704 evaporation Methods 0.000 claims description 8
- 230000008020 evaporation Effects 0.000 claims description 7
- 239000003014 ion exchange membrane Substances 0.000 claims description 5
- 238000004064 recycling Methods 0.000 abstract description 11
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- 238000012545 processing Methods 0.000 abstract description 3
- 230000008569 process Effects 0.000 description 21
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- 229920005989 resin Polymers 0.000 description 9
- 238000012360 testing method Methods 0.000 description 9
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 8
- 238000005352 clarification Methods 0.000 description 8
- 238000004062 sedimentation Methods 0.000 description 8
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 6
- 239000003513 alkali Substances 0.000 description 6
- 238000011033 desalting Methods 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- 239000002351 wastewater Substances 0.000 description 6
- 238000011084 recovery Methods 0.000 description 5
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- DWAQJAXMDSEUJJ-UHFFFAOYSA-M Sodium bisulfite Chemical compound [Na+].OS([O-])=O DWAQJAXMDSEUJJ-UHFFFAOYSA-M 0.000 description 4
- 229910000831 Steel Inorganic materials 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- 150000001450 anions Chemical class 0.000 description 4
- 230000000844 anti-bacterial effect Effects 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
- 239000003899 bactericide agent Substances 0.000 description 4
- 239000013043 chemical agent Substances 0.000 description 4
- 239000003638 chemical reducing agent Substances 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 238000011156 evaluation Methods 0.000 description 4
- MGIYRDNGCNKGJU-UHFFFAOYSA-N isothiazolinone Chemical compound O=C1C=CSN1 MGIYRDNGCNKGJU-UHFFFAOYSA-N 0.000 description 4
- 230000001590 oxidative effect Effects 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- 230000009467 reduction Effects 0.000 description 4
- 238000000926 separation method Methods 0.000 description 4
- 229910000029 sodium carbonate Inorganic materials 0.000 description 4
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 description 4
- 239000002910 solid waste Substances 0.000 description 4
- 239000010959 steel Substances 0.000 description 4
- 150000001768 cations Chemical class 0.000 description 3
- 239000000084 colloidal system Substances 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 239000005416 organic matter Substances 0.000 description 3
- 239000002244 precipitate Substances 0.000 description 3
- 230000008929 regeneration Effects 0.000 description 3
- 238000011069 regeneration method Methods 0.000 description 3
- WBHQBSYUUJJSRZ-UHFFFAOYSA-M sodium bisulfate Chemical compound [Na+].OS([O-])(=O)=O WBHQBSYUUJJSRZ-UHFFFAOYSA-M 0.000 description 3
- 229910000342 sodium bisulfate Inorganic materials 0.000 description 3
- 239000011780 sodium chloride Substances 0.000 description 3
- XZPVPNZTYPUODG-UHFFFAOYSA-M sodium;chloride;dihydrate Chemical compound O.O.[Na+].[Cl-] XZPVPNZTYPUODG-UHFFFAOYSA-M 0.000 description 3
- 238000000108 ultra-filtration Methods 0.000 description 3
- 239000002699 waste material Substances 0.000 description 3
- 235000008733 Citrus aurantifolia Nutrition 0.000 description 2
- 235000011941 Tilia x europaea Nutrition 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 2
- 239000000920 calcium hydroxide Substances 0.000 description 2
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000003912 environmental pollution Methods 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 239000004571 lime Substances 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 229920002401 polyacrylamide Polymers 0.000 description 2
- 239000002455 scale inhibitor Substances 0.000 description 2
- 239000013049 sediment Substances 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000002585 base Substances 0.000 description 1
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- 239000000835 fiber Substances 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 230000015784 hyperosmotic salinity response Effects 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000010842 industrial wastewater Substances 0.000 description 1
- 238000011221 initial treatment Methods 0.000 description 1
- 229910017053 inorganic salt Inorganic materials 0.000 description 1
- RUTXIHLAWFEWGM-UHFFFAOYSA-H iron(3+) sulfate Chemical compound [Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RUTXIHLAWFEWGM-UHFFFAOYSA-H 0.000 description 1
- 229910000360 iron(III) sulfate Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000011112 process operation Methods 0.000 description 1
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- 239000004576 sand Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000012498 ultrapure water Substances 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F9/00—Multistage treatment of water, waste water or sewage
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/02—Treatment of water, waste water, or sewage by heating
- C02F1/04—Treatment of water, waste water, or sewage by heating by distillation or evaporation
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/42—Treatment of water, waste water, or sewage by ion-exchange
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/44—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis
- C02F1/441—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis by reverse osmosis
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/44—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis
- C02F1/444—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis by ultrafiltration or microfiltration
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
- C02F1/469—Treatment of water, waste water, or sewage by electrochemical methods by electrochemical separation, e.g. by electro-osmosis, electrodialysis, electrophoresis
- C02F1/4693—Treatment of water, waste water, or sewage by electrochemical methods by electrochemical separation, e.g. by electro-osmosis, electrodialysis, electrophoresis electrodialysis
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A20/00—Water conservation; Efficient water supply; Efficient water use
- Y02A20/124—Water desalination
- Y02A20/131—Reverse-osmosis
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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)
- Water Treatment By Electricity Or Magnetism (AREA)
Abstract
The invention relates to an industrial strong brine zero-discharge treatment system which comprises an industrial strong brine tank, electrodialysis, a concentrated solution tank and an evaporative crystallization unit which are sequentially connected, wherein an electrodialysis water production outlet is connected with an electrodialysis water production tank, the electrodialysis water production tank is sequentially connected with a first pressure pump, an acid-resistant nanofiltration membrane, a second pressure pump and a reverse osmosis membrane, finally, a strong water outlet of the reverse osmosis membrane returns to the electrodialysis water production tank, and strong water of the acid-resistant nanofiltration membrane returns to the industrial strong brine tank. The invention also relates to a method for processing by using the processing system. The invention uses a simple and low-cost method to concentrate industrial strong brine, finally produces water for recycling, and evaporates and crystallizes the rest super strong brine, thereby achieving the aim of zero emission of the strong brine.
Description
Technical Field
The invention belongs to the field of industrial strong brine treatment, and particularly relates to an industrial strong brine zero-emission treatment system and method for concentrating industrial strong brine, recycling desalted water and evaporating and crystallizing the rest of super strong brine to achieve the aim of strong brine zero-emission.
Background
In industrial production, a plurality of enterprises can adopt a wastewater recovery technology, but the recovery and utilization of high-salinity and high-hardness wastewater is always a difficult problem, the hardness of the wastewater is reduced by adopting a double-alkali method in the traditional process, the hardness of the wastewater is reduced by using resin, and finally the wastewater is desalted by adopting a membrane method to reach the reuse water standard, and the acid-base regenerated solution and the reverse osmosis concentrated brine are evaporated and crystallized to achieve the purpose of zero discharge of the wastewater.
The traditional zero-emission process has long flow, a large amount of acid and alkali is added in the treatment process, the treatment capacity of the concentrated solution is large, the treatment cost is high, and the environmental pollution is large.
The traditional zero-emission process comprises the following steps:
as shown in figure 1, strong brine enters an industrial strong brine tank I, is conveyed into a high-density clarification tank II by a pump, and Na is added into the high-density clarification tank2CO3NaOH, etc., removing Ca from strong brine2+、Mg2+Ions are generated, the hardness is reduced, and the sediment enters a plate and frame filter press machine. The water produced by the high-density clarification tank enters a water producing tank III, in order to remove particles and colloid and meet the water inlet condition of SDI before entering the reverse osmosis membrane, the SDI sequentially passes through a multi-media filter IV, a resin softening tank IV and an ultrafiltration membrane IV and enters a middle water tank VII, then the SDI and the SDI sequentially enter a first-stage reverse osmosis ⑫ and a second-stage reverse osmosis ⑪ after being pumped, the first-stage reverse osmosis water and the second-stage reverse osmosis water produced enter a reuse water tank ⑬ for recycling, and the second-stage reverse osmosis concentrated water enters an ultra-concentrated water tank III 1 and finally enters an evaporative crystallization unit III 0. When the resin softening tank is out of work, hydrochloric acid or sodium chloride is used for regeneration, and the regenerated waste liquor is fed into the interior of the ultra-concentrated water tank and then evaporated and crystallized. The traditional process has the defect that a large amount of Na is added into a high-density clarification tank2CO3NaOH and the like, the precipitate needs to be dewatered and squeezed by a plate-and-frame filter press, when the resin softening tank fails, hydrochloric acid or sodium chloride needs to be used for regeneration, a large amount of acid or alkali or salt is added into the whole system to generate regenerated waste liquid, and the treatment capacity of an evaporation crystallization unit is increased; the traditional process has multi-mediumThe filter and the ultrafiltration have more treatment units and high operation cost, and the produced mud cakes can cause pollution to the environment.
Disclosure of Invention
The invention aims to provide a strong brine treatment system, which realizes zero discharge of industrial strong brine and can reduce the operation cost.
The invention adopts the following technical scheme:
the utility model provides an industry strong brine zero release processing system, is including the industry strong brine pond, electrodialysis, concentrate pond and the evaporation crystallization unit that connect gradually, electrodialysis water production outlet connects the electrodialysis and produces the pond, and the electrodialysis is produced the pond and is connected first force (forcing) pump, acid-resistant nanofiltration membrane, second force (forcing) pump and reverse osmosis membrane in proper order, and the dense water delivery port of reverse osmosis membrane gets back to in the electrodialysis water production pond again at last, the dense water of acid-resistant nanofiltration membrane gets back to in the industry strong brine pond again.
A treatment method utilizing an industrial strong brine zero-discharge treatment system is characterized in that industrial strong brine is stored in an industrial strong brine tank and is conveyed to electrodialysis for treatment through a water pump, the electrodialysis carries out desalination and concentration by taking direct current as driving force, organic matters and salt are separated through an ion exchange membrane, electrodialysis concentrated solution is stored in a concentrated solution tank and then enters an evaporator crystallization unit for crystallization treatment;
the electrodialysis water production enters an electrodialysis water production pool, and then enters an acid-resistant nanofiltration membrane through a first pressure pump;
returning the acid-resistant nanofiltration membrane concentrated water to an industrial concentrated salt water tank, and repeatedly removing ions and salt through electrodialysis;
and the produced water of the acid-resistant nanofiltration membrane is pressurized by a second pressure pump and then enters a reverse osmosis membrane, the strong brine of the reverse osmosis membrane returns to an electrodialysis water production tank, and is desalted again through the acid-resistant nanofiltration membrane, and the reverse osmosis produced water is recycled.
Preferably, the electrodialysis water production CODcr is, for example, more than 200mg/L, and the electrodialysis water production CODcr is biochemically treated to be less than 200mg/L and then enters the electrodialysis water production pool.
Preferably, the electrodialysis inflow water control conditions are as follows: TDS is less than or equal to 5 multiplied by 104mg/L, pH value less than or equal to 7.5, turbidity less than or equal to 0.1 NTU.
Preferably, the water inlet control condition of the acid-resistant nanofiltration membrane is that CODcr is less than or equal to 200mg/L, pH is less than or equal to 5, calcium hardness is less than 1200mg/L, and SDI is less than or equal to 5.
Preferably, the reverse osmosis membrane water inlet control condition CODcr is less than or equal to 60mg/L, the pH value is less than or equal to 6 and less than or equal to 9.5, and the SDI is less than or equal to 3.
Preferably, the reverse osmosis membrane is a secondary reverse osmosis membrane.
Preferably, the electrodialysis operation adopts the mode of controlling the highest water yield, and the concentration TDS reaches 2 x 105 mg/L.
The invention carries out electrodialysis desalination treatment on strong brine, concentrated solution generated by electrodialysis enters a crystallizer in an evaporation crystallization unit, water generated by electrodialysis enters an electrodialysis water generating pool and further passes through an acid-resistant nanofiltration membrane, and if COD (chemical oxygen demand) of inlet water of the acid-resistant nanofiltration membrane exceeds 200mg/L, biochemical and advanced oxidation treatment is carried out to ensure that the COD is less than 200 mg/L. The concentrated water of the acid-proof nanofiltration membrane returns to the industrial concentrated salt water tank, the produced water of the acid-proof nanofiltration membrane enters the reverse osmosis membrane, the concentrated water of the reverse osmosis membrane (primary or secondary) returns to the electrodialysis water tank, and the produced water of the reverse osmosis membrane is recycled as high-quality water.
The industrial strong brine is comprehensively treated by adopting electrodialysis, an acid-resistant nanofiltration membrane and a reverse osmosis membrane process, and replaces a double-alkali hardness reducing method, a resin hardness reducing method and a reverse osmosis membrane process which are adopted in the traditional process.
The electrodialysis operation of the invention adopts the highest water yield control mode, the TDS concentration can reach 2 multiplied by 105mg/L, the concentration of the concentrated solution is high, the total amount of the concentrated solution is reduced, and the treatment amount and the treatment cost of evaporative crystallization are greatly reduced.
According to the invention, water produced by electrodialysis enters an acid-resistant nanofiltration membrane, more than 80% of divalent ions are separated out, the acid-resistant nanofiltration membrane is operated under the condition that the pH is less than or equal to 5 by adjusting the pH, and scaling on the side surface of the nanofiltration membrane strong brine under high salinity and high hardness is avoided.
The concentrated water of the acid-resistant nanofiltration membrane returns to the industrial concentrated brine tank and enters the electrodialysis desalination again, so that the aim of electrodialysis repeated desalination is fulfilled.
The operation of the acid-resistant nanofiltration membrane adopts a highest water yield control mode, so that water is recovered to the maximum extent, and the yield of strong brine is reduced.
The acid-resistant nanofiltration produced water enters a reverse osmosis membrane, and the reverse osmosis membrane can remove more than 90% of ions and can obtain high-purity water for recycling. Most of divalent ions are removed by the acid-resistant nanofiltration membrane in the previous process, so that the scaling tendency of the reverse osmosis membrane is avoided, and a scale inhibitor is not required to be added before the reverse osmosis membrane.
The concentrated water of the reverse osmosis membrane returns to the electrodialysis water production pool and enters the acid-resistant nanofiltration membrane again, so that the aim of repeated desalination by the acid-resistant nanofiltration membrane is fulfilled.
The invention has the beneficial effects that:
the invention uses a simple and low-cost method to concentrate industrial strong brine, finally produces water for recycling, and evaporates and crystallizes the rest super strong brine, thereby achieving the purpose of zero emission of the strong brine. Compared with the traditional industrial strong brine zero-discharge process, the optimized zero-discharge industrial strong brine treatment method has the following advantages:
the process flow is short, the investment is low, the process operation is stable, and the treatment cost is low. Because the traditional industrial strong brine zero discharge process adopts a high-density sedimentation tank or a radial flow sedimentation tank and adds chemical hardness reduction methods such as lime, sodium carbonate and the like, the high-density sedimentation tank or the radial flow sedimentation tank can generate a large amount of precipitates (mainly salt scale such as calcium, magnesium, iron and the like), the precipitates need to enter a plate-and-frame filter press for further squeezing and dewatering, and simultaneously after the chemical hardness reduction of the lime, the sodium carbonate and the like, the water discharged from the high-density sedimentation tank or the radial flow sedimentation tank generates a large amount of particles and colloids, therefore, after the high-density sedimentation tank or the radial flow sedimentation tank, a conventional filtering unit (a multi-medium filter, a sand filter or a fiber bundle filter) and an ultrafiltration unit need to be added to meet the SDI water inlet condition before the reverse osmosis membrane.
And electrodialysis is adopted to carry out primary treatment on the strong brine, the electrodialysis has good characteristics of high salt tolerance and organic pollution resistance on inlet water, the treatment capacity of the concentrated solution is reduced by more than 10%, the process is stable, and the operation cost is low.
And thirdly, the electrodialysis is adopted to carry out primary desalination on the strong brine, the medicament addition is not needed, and compared with the traditional process that the dibasic hardness reduction and the resin hardness reduction consume a large amount of acid and alkali or sodium chloride, the addition of excessive acid, alkali and salt is avoided, so that when the strong brine is desalted through a reverse osmosis membrane, the energy consumption is low, the quality of produced water is good, the treatment cost is reduced, and the environmental pollution is reduced.
And fourthly, desalting the electrodialysis water by adopting the acid-resistant nanofiltration membrane, separating more than 80% of divalent ions, and avoiding the scaling tendency of strong brine on the surface of the acid-resistant nanofiltration membrane under high salinity because the acid-resistant nanofiltration membrane can operate under the condition that the pH is less than or equal to 5.
Fifthly, desalting the acid-resistant nanofiltration produced water by adopting a reverse osmosis membrane, wherein the desalting rate reaches more than 90 percent, so that high-quality produced water can be obtained to achieve the purpose of recycling, and secondary reverse osmosis can be adopted if necessary. Most of divalent ions are removed by the acid-resistant nanofiltration membrane in the previous process, so that the scaling tendency of strong brine on the reverse osmosis membrane can be avoided, and a scale inhibitor is not required to be added in front of the reverse osmosis membrane.
Sixthly, the water recovery rate of the whole system is more than 85 percent, the treatment capacity of the concentrated solution is less than 15 percent, the water consumption is greatly reduced, and the economic and social benefits are obvious.
Compared with the traditional method for pursuing the quality of the produced water by electrodialysis, the method for pursuing the high concentration of the concentrated water by partly sacrificing the quality of the produced water by utilizing the separating capacity of electrodialysis adopts a membrane treatment process to carry out secondary treatment on the poor electrodialysis produced water, thereby not only reducing the treatment cost of the evaporation crystallization process, but also solving the problem of water quality, and finally realizing the purpose of zero emission of industrial wastewater by using a method with low operation cost.
Drawings
FIG. 1 is a flow diagram of a conventional process;
FIG. 2 is a process flow diagram of the present invention.
Detailed Description
The industrial strong brine zero-discharge treatment process disclosed by the invention has 9 treatment units. The industrial strong brine is stored in an industrial strong brine tank, is conveyed to electrodialysis for concentration and separation through a water pump, and under the action of direct current, anions and cations enter an anion tank and an anode tank through an anion membrane and a cation membrane respectively. The anion membrane and the cation membrane are selective membranes, more than 80% of metal ions can be separated out by electrodialysis, the electrodialysis recovery rate can reach more than 85%, and the TDS of the concentrated solution can reach 2 x 105mg/L, which is convenient for further evaporation crystallization treatment. Electrodialysis desalination is carried out, and the TDS of the electrodialysis produced water is less than or equal to 1 multiplied by 104mg/L, inAnd (4) entering an electrodialysis water production pool, and if the electrodialysis water production CODcr is more than 200mg/L, carrying out biochemical treatment to ensure that the CODcr is less than or equal to 200 mg/L. The water produced by electrodialysis enters an acid-resistant nanofiltration membrane after being pressurized by a first pressure pump, and NaHSO is required to be added to prevent the acid-resistant nanofiltration membrane from being oxidized4And meanwhile, HCl is used for regulating the pH value, so that the pH value of inlet water is less than or equal to 5, and inorganic salt scaling is prevented. And returning the acid-resistant nanofiltration membrane concentrated brine to the industrial concentrated brine tank, and then entering the electrodialysis desalination again, wherein most of divalent ions and more than 80% of salt can be removed by the acid-resistant nanofiltration membrane. And the acid-resistant nanofiltration membrane produced water enters a reverse osmosis membrane after being pressurized by a second high-pressure pump, 95% of salt can be removed by the reverse osmosis membrane, the produced water reaches the recovery standard, and the reverse osmosis concentrated water enters an electrodialysis production water tank and enters the nanofiltration membrane again. In order to prevent the reverse osmosis membrane from being oxidized, NaHSO is added in front of the reverse osmosis membrane4And adding NaOH to adjust the pH value.
The electrodialysis operation adopts the highest water yield control mode, and the treatment capacity of the concentrated solution evaporation crystallization unit is reduced.
The operation of the acid-resistant nanofiltration membrane adopts a highest water yield control mode, so that water is recovered to the maximum extent, and the yield of strong brine is reduced.
Electrodialysis water inlet control conditions: TDS is less than or equal to 5 multiplied by 104mg/L, pH value less than or equal to 7.5 and turbidity less than or equal to 0.1 NTU.
The water inlet control condition of the acid-resistant nanofiltration membrane is as follows: CODcr is less than or equal to 200mg/L, pH is less than or equal to 5, calcium hardness is less than 1200mg/L, and SDI is less than or equal to 5.
Reverse osmosis membrane water inlet control conditions: CODcr is less than or equal to 60mg/L, pH is less than or equal to 9.5 and 6, and SDI is less than or equal to 3.
Example 1
In a water treatment station of a steel plant, the amount of industrial strong brine to be treated is 730m3The treatment method is the treatment method of the invention, and the specific treatment steps are as follows:
(1) the industrial strong brine is stored in an industrial strong brine tank and is conveyed to electrodialysis through a water pump for treatment, the electrodialysis uses direct current as driving force for desalination and L concentration, organic matter and salt separation is carried out through an ion exchange membrane, and electrodialysis concentrated solution is stored in a concentrated solution tank and then enters an evaporator crystallization unit for thorough treatment. And the electrodialysis water enters an electrodialysis water production pool and then enters an acid-resistant nanofiltration membrane through a pressure pump. And returning the concentrated water of the acid-resistant nanofiltration membrane to an industrial concentrated salt water tank, repeatedly removing ions and salt through electrodialysis, operating the acid-resistant nanofiltration membrane under the condition that the pH value is less than or equal to 5, pressurizing the produced water of the nanofiltration membrane by a pressurizing pump, then entering a reverse osmosis membrane, returning the strong brine of the reverse osmosis membrane to the electrodialysis water tank, desalting again through the nanofiltration membrane, and recycling the reverse osmosis produced water.
(2) Industrial strong brine water quality: CODcr: 60mg/L, pH: 6.7, turbidity: 0.1NTU, TDS: 6000 mg/L.
(3) Chemical Oxygen Demand (COD) of the influent water quality test result of the acid-resistant nanofiltration membranecr: 180mg/L, pH: 3.5, calcium hard: 700mg/L, SDI: 4.
(4) and (3) testing the water quality of inlet water of the reverse osmosis membrane: CODcr：40mg/L，pH：7.5， SDI：1。
(5) Chemical agents: non-oxidizing type bactericide: isothiazolinone; reducing agent: sodium bisulfite. Hydrochloric acid; sodium bisulfate; sodium hydroxide.
(6) Water inlet amount of the evaporative crystallization unit: 109m3H, operating cost of the evaporative crystallization unit: 80 yuan/ton, solid waste generation amount of evaporative crystallization: 529 tons/day.
Evaluation of the effects: the investment of fixed assets is 2200 ten thousand yuan, and the treatment cost of industrial strong brine is 8 yuan/ton. And (3) reverse osmosis water production quality: TDS of 20mg/L, calcium hardness: 0mg/L, pH: 7.5.
comparative example 1
Example 1 in a Water treatment plant of an iron and Steel works, the amount of industrial strong brine to be treated was 560m3The treatment method is a traditional concentrated brine treatment scheme and comprises the following specific treatment steps:
(1) pumping industrial concentrated brine into a high-density clarification tank, adding sodium carbonate, calcium hydroxide, hydrochloric acid, sulfuric acid, polyferric sulfate and polyacrylamide into the high-density clarification tank, and removing Ca in the concentrated brine2+、Mg2+The hardness of the ions is reduced, and the sediment enters a plate-and-frame filter press to be pressed into mud cakes to be transported outside. The high-density clarification tank produces water and gets into and produces the pond, in order to get rid of granule and colloid to satisfy the preceding SDI water inlet condition of reverse osmosis membrane, in proper order through many medium filter, resin softening tank, milipore filter get into middle pond, thenPumping the water into a first-stage reverse osmosis unit and a second-stage reverse osmosis unit in sequence, recycling the first-stage reverse osmosis produced water and the second-stage reverse osmosis produced water in a recycling pool, feeding the second-stage reverse osmosis concentrated water into a super-concentrated pool, and finally feeding the second-stage reverse osmosis concentrated water into an evaporative crystallization unit. When the resin softening tank fails, hydrochloric acid is used for regeneration, and the regenerated waste liquid enters an ultra-concentrated water tank to be evaporated and crystallized.
(2) Industrial strong brine water quality: CODcr:50mg/L, pH: 6.8, turbidity: 0.1NTU, TDS: 4500 mg/L.
(3) And (3) testing results of the effluent of the high-density clarification tank: CODcr: 40mg/L, pH: 8.5, turbidity: 1 NTU.
(4) The test result of the water quality of the inlet water of the first-stage reverse osmosis membrane is as follows: CODcr：25mg/L，PH：8， SDI：0.8。
(5) And (3) testing the water quality of the concentrated water of the second-stage reverse osmosis membrane: pH: 7.6, TDS: 500 mg/L, turbidity: 0.1 NTU.
(6) Chemical agents: non-oxidizing type bactericide: isothiazolinone; reducing agent: sodium bisulfite. Hydrochloric acid; sodium hydroxide; sodium carbonate; calcium hydroxide; sulfuric acid; polymeric ferric sulfate; polyacrylamide.
(7) Mud cake yield: 35 tons/day.
(8) The use amount of HCl for regenerating the resin softening tank is as follows: 10 tons/day.
(9) Water inlet amount of the evaporative crystallization unit: 145m3H, operating cost of the evaporative crystallization unit: 85 yuan/ton, solid waste generation amount of evaporative crystallization: 345 tons/day.
Evaluation of the effects: the investment of fixed assets is 4600 ten thousand yuan, and the treatment cost of industrial strong brine is 15 yuan/ton. The quality of the second-stage reverse osmosis produced water is as follows: TDS: 15mg/L, calcium hard: 0mg/L, pH: 7.5.
example 2
The water quantity of industrial strong brine to be treated in the water treatment station of the steel plant is 60m3The treatment method is the treatment method of the invention, and the specific treatment steps are as follows:
(1) the industrial strong brine is stored in an industrial strong brine tank and is conveyed to electrodialysis through a water pump for treatment, the electrodialysis uses direct current as driving force for desalination and L concentration, organic matter and salt separation is carried out through an ion exchange membrane, and electrodialysis concentrated solution is stored in a concentrated solution tank and then enters an evaporator crystallization unit for thorough treatment. And the electrodialysis water enters an electrodialysis water production pool and then enters an acid-resistant nanofiltration membrane through a pressure pump. And returning the concentrated water of the acid-resistant nanofiltration membrane to an industrial concentrated salt water tank, repeatedly removing ions and salt through electrodialysis, operating the acid-resistant nanofiltration membrane under the condition that the pH value is less than or equal to 5, pressurizing the produced water of the nanofiltration membrane by a pressurizing pump, then entering a reverse osmosis membrane, returning the strong brine of the reverse osmosis membrane to the electrodialysis water tank, desalting again through the nanofiltration membrane, and recycling the reverse osmosis produced water.
(2) Industrial strong brine water quality: CODcr: 60mg/L, pH: 7.5, turbidity: 0.1NTU, TDS: 50000 mg/L.
(3) Chemical Oxygen Demand (COD) as result of acid-resistant nano-filtering membrane water quality testcr: 200mg/L, pH: 5, calcium hardness: 1200mg/L, SDI: 5.
(4) the reverse osmosis membrane influent water quality test result: CODcr：60mg/L，pH：9.5， SDI：3。
(5) Chemical agents: non-oxidizing type bactericide: isothiazolinone; reducing agent: sodium bisulfite. Hydrochloric acid; sodium bisulfate; sodium hydroxide.
(6) Water inlet amount of the evaporative crystallization unit: 12m3H, operating cost of the evaporative crystallization unit: 80 yuan/ton, solid waste generation amount of evaporative crystallization: 54 tons/day.
Evaluation of the effects: the investment of fixed assets is 350 ten thousand yuan, and the treatment cost of industrial strong brine is 10 yuan/ton. And (3) reverse osmosis water production quality: TDS of 70mg/L, calcium hardness: 0mg/L, pH: 8.5.
example 3
The water quantity of industrial strong brine to be treated in the water treatment station of the steel plant is 20m3The treatment method is the treatment method of the invention, and the specific treatment steps are as follows:
(1) the industrial strong brine is stored in an industrial strong brine tank and is conveyed to electrodialysis through a water pump for treatment, the electrodialysis uses direct current as driving force for desalination and L concentration, organic matter and salt separation is carried out through an ion exchange membrane, and electrodialysis concentrated solution is stored in a concentrated solution tank and then enters an evaporator crystallization unit for thorough treatment. And the electrodialysis water enters an electrodialysis water production pool and then enters an acid-resistant nanofiltration membrane through a pressure pump. And returning the concentrated water of the acid-resistant nanofiltration membrane to an industrial concentrated salt water tank, repeatedly removing ions and salt through electrodialysis, operating the acid-resistant nanofiltration membrane under the condition that the pH value is less than or equal to 5, pressurizing the produced water of the nanofiltration membrane by a pressurizing pump, then entering a reverse osmosis membrane, returning the strong brine of the reverse osmosis membrane to the electrodialysis water tank, desalting again through the nanofiltration membrane, and recycling the reverse osmosis produced water.
(2) Industrial strong brine quality: CODcr: 60mg/L, pH: 6.5, turbidity: 0.1NTU, TDS: 20000 mg/L.
(3) Chemical Oxygen Demand (COD) as result of acid-resistant nano-filtering membrane water quality testcr: 160mg/L, pH: 3, calcium hardness: 870mg/L, SDI: 4.
(4) and (3) testing the water quality of inlet water of the reverse osmosis membrane: CODcr：40mg/L，pH：7.5， SDI：1。
(5) Chemical agents: non-oxidizing type bactericide: isothiazolinone; reducing agent: sodium bisulfite. Hydrochloric acid; sodium bisulfate; sodium hydroxide.
(6) Water inlet amount of the evaporative crystallization unit: 5.5m3H, operating cost of the evaporative crystallization unit: 120 yuan/ton, solid waste generation amount of evaporative crystallization: 15 tons/day.
Evaluation of the effects: the investment of fixed assets is 350 ten thousand yuan, and the treatment cost of industrial strong brine is 15 yuan/ton. And (3) reverse osmosis water production quality: TDS of 50mg/L, calcium hardness: 0mg/L, pH: 7.1.
the above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents thereof, and all such modifications are intended to be included in the scope of the present invention.
Claims (8)
1. The zero-emission treatment system for the industrial concentrated brine is characterized by comprising an industrial concentrated brine tank, electrodialysis, a concentrated solution tank and an evaporation crystallization unit which are sequentially connected, wherein an electrodialysis water production outlet is connected with an electrodialysis water production tank, the electrodialysis water production tank is sequentially connected with a first pressure pump, an acid-resistant nanofiltration membrane, a second pressure pump and a reverse osmosis membrane, a concentrated water outlet of the reverse osmosis membrane returns to the electrodialysis water production tank, and concentrated water of the acid-resistant nanofiltration membrane returns to the industrial concentrated brine tank.
2. The treatment method utilizing the industrial concentrated brine zero-emission treatment system as claimed in claim 1, wherein the industrial concentrated brine is stored in an industrial concentrated brine tank and is conveyed to electrodialysis for treatment through a water pump, the electrodialysis is used for desalination and concentration by taking direct current as a driving force and is used for separating organic matters and salts through an ion exchange membrane, and the electrodialysis concentrated solution is stored in a concentrated solution tank and then enters an evaporator crystallization unit for crystallization treatment;
the electrodialysis water enters an electrodialysis water production pool and then enters an acid-resistant nanofiltration membrane through a first pressure pump;
returning the acid-resistant nanofiltration membrane concentrated water to an industrial concentrated salt water tank, and repeatedly removing ions and salt through electrodialysis;
and the produced water of the acid-resistant nanofiltration membrane is pressurized by a second pressurizing pump and then enters a reverse osmosis membrane, the strong brine of the reverse osmosis membrane returns to the electrodialytic water production tank, and is desalted again through the acid-resistant nanofiltration membrane, and the produced water of the reverse osmosis is recycled.
3. The treatment method of claim 2, wherein the electrodialysis water production CODcr is greater than 200mg/L, and the electrodialysis water production is carried out until the CODcr is less than 200mg/L, and then the treated water is introduced into the electrodialysis water production tank.
4. The treatment method utilizing the industrial concentrated brine zero emission treatment system according to claim 2, wherein the electrodialysis inflow control conditions are as follows: TDS is less than or equal to 5 multiplied by 104mg/L, pH value less than or equal to 7.5 and turbidity less than or equal to 0.1 NTU.
5. The treatment method utilizing the industrial concentrated brine zero-emission treatment system according to claim 2, wherein the acid-resistant nanofiltration membrane water inlet control condition CODcr is less than or equal to 200mg/L, the pH is less than or equal to 5, the calcium hardness is less than 1200mg/L, and the SDI is less than or equal to 5.
6. The treatment method of claim 2, wherein the reverse osmosis membrane influent control conditions CODcr is less than or equal to 60mg/L, pH is less than or equal to 6 and less than or equal to 9.5, and SDI is less than or equal to 3.
7. The treatment method for zero discharge of industrial concentrated brine according to claim 2, wherein the reverse osmosis membrane is a secondary reverse osmosis membrane.
8. The treatment method of claim 2, wherein the electrodialysis operation adopts the highest water yield control mode, and the concentration TDS reaches 2 x 105mg/L。
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