CN108623104A - A kind of high-salinity wastewater zero-emission processing method and processing device based on NF membrane allotment - Google Patents
A kind of high-salinity wastewater zero-emission processing method and processing device based on NF membrane allotment Download PDFInfo
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- CN108623104A CN108623104A CN201810778712.4A CN201810778712A CN108623104A CN 108623104 A CN108623104 A CN 108623104A CN 201810778712 A CN201810778712 A CN 201810778712A CN 108623104 A CN108623104 A CN 108623104A
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- sodium chloride
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- 239000002351 wastewater Substances 0.000 title claims abstract description 86
- 239000012528 membrane Substances 0.000 title claims abstract description 78
- 238000003672 processing method Methods 0.000 title abstract description 4
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims abstract description 135
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 124
- 238000000034 method Methods 0.000 claims abstract description 111
- 239000013078 crystal Substances 0.000 claims abstract description 77
- 239000011780 sodium chloride Substances 0.000 claims abstract description 64
- 150000003839 salts Chemical class 0.000 claims abstract description 52
- 238000001728 nano-filtration Methods 0.000 claims abstract description 46
- 239000012452 mother liquor Substances 0.000 claims abstract description 33
- 239000011734 sodium Substances 0.000 claims abstract description 27
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims abstract description 22
- 239000007788 liquid Substances 0.000 claims abstract description 19
- 239000012535 impurity Substances 0.000 claims abstract description 14
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims abstract description 8
- 229910052708 sodium Inorganic materials 0.000 claims abstract description 7
- 229910052938 sodium sulfate Inorganic materials 0.000 claims description 82
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 67
- 238000002425 crystallisation Methods 0.000 claims description 57
- 238000001223 reverse osmosis Methods 0.000 claims description 53
- 230000008025 crystallization Effects 0.000 claims description 52
- 230000008569 process Effects 0.000 claims description 50
- 239000007832 Na2SO4 Substances 0.000 claims description 46
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 40
- 235000011152 sodium sulphate Nutrition 0.000 claims description 36
- 238000007254 oxidation reaction Methods 0.000 claims description 35
- 230000003647 oxidation Effects 0.000 claims description 34
- 238000000108 ultra-filtration Methods 0.000 claims description 34
- 239000013505 freshwater Substances 0.000 claims description 28
- 238000004519 manufacturing process Methods 0.000 claims description 23
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 claims description 20
- 239000012267 brine Substances 0.000 claims description 19
- 239000002699 waste material Substances 0.000 claims description 18
- 238000001704 evaporation Methods 0.000 claims description 16
- 238000001914 filtration Methods 0.000 claims description 16
- 238000000926 separation method Methods 0.000 claims description 15
- 238000000909 electrodialysis Methods 0.000 claims description 14
- 238000005516 engineering process Methods 0.000 claims description 13
- 230000008020 evaporation Effects 0.000 claims description 13
- 238000005660 chlorination reaction Methods 0.000 claims description 7
- 238000009287 sand filtration Methods 0.000 claims description 7
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 claims description 6
- 238000009298 carbon filtering Methods 0.000 claims description 6
- 239000003456 ion exchange resin Substances 0.000 claims description 6
- 229920003303 ion-exchange polymer Polymers 0.000 claims description 6
- 230000008859 change Effects 0.000 claims description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 4
- 239000003814 drug Substances 0.000 claims description 4
- 229910052760 oxygen Inorganic materials 0.000 claims description 4
- 239000001301 oxygen Substances 0.000 claims description 4
- 238000001556 precipitation Methods 0.000 claims description 4
- 230000006835 compression Effects 0.000 claims description 3
- 238000007906 compression Methods 0.000 claims description 3
- 238000006385 ozonation reaction Methods 0.000 claims description 3
- 239000004576 sand Substances 0.000 claims description 3
- 239000012141 concentrate Substances 0.000 abstract description 13
- 239000002253 acid Substances 0.000 abstract description 9
- 238000002156 mixing Methods 0.000 abstract description 7
- 239000010413 mother solution Substances 0.000 abstract description 7
- 239000012530 fluid Substances 0.000 abstract description 2
- 230000000149 penetrating effect Effects 0.000 abstract description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 abstract 1
- 239000011593 sulfur Substances 0.000 abstract 1
- 229910052717 sulfur Inorganic materials 0.000 abstract 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 13
- 238000011084 recovery Methods 0.000 description 13
- 230000000694 effects Effects 0.000 description 6
- 230000004907 flux Effects 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- 150000001768 cations Chemical class 0.000 description 5
- 238000004064 recycling Methods 0.000 description 5
- 238000004062 sedimentation Methods 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- 241000196324 Embryophyta Species 0.000 description 4
- 241001529739 Prunella <angiosperm> Species 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 4
- 239000003245 coal Substances 0.000 description 4
- 239000010842 industrial wastewater Substances 0.000 description 4
- 238000001764 infiltration Methods 0.000 description 4
- 230000001590 oxidative effect Effects 0.000 description 4
- 239000004952 Polyamide Substances 0.000 description 3
- 239000004642 Polyimide Substances 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 229920002301 cellulose acetate Polymers 0.000 description 3
- 238000004140 cleaning Methods 0.000 description 3
- 238000007667 floating Methods 0.000 description 3
- 229920002647 polyamide Polymers 0.000 description 3
- 229920001721 polyimide Polymers 0.000 description 3
- 238000010992 reflux Methods 0.000 description 3
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- 238000011001 backwashing Methods 0.000 description 2
- 238000005119 centrifugation Methods 0.000 description 2
- 239000003610 charcoal Substances 0.000 description 2
- JEGUKCSWCFPDGT-UHFFFAOYSA-N h2o hydrate Chemical compound O.O JEGUKCSWCFPDGT-UHFFFAOYSA-N 0.000 description 2
- 229920002492 poly(sulfone) Polymers 0.000 description 2
- 229920002239 polyacrylonitrile Polymers 0.000 description 2
- 229920000728 polyester Polymers 0.000 description 2
- -1 polyethylene Polymers 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 230000000087 stabilizing effect Effects 0.000 description 2
- 229920002554 vinyl polymer Polymers 0.000 description 2
- 238000009279 wet oxidation reaction Methods 0.000 description 2
- WFLOTYSKFUPZQB-UHFFFAOYSA-N 1,2-difluoroethene Chemical group FC=CF WFLOTYSKFUPZQB-UHFFFAOYSA-N 0.000 description 1
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- 241000894006 Bacteria Species 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 241000233855 Orchidaceae Species 0.000 description 1
- 239000004695 Polyether sulfone Substances 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 206010044565 Tremor Diseases 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- 230000002745 absorbent Effects 0.000 description 1
- 239000002250 absorbent Substances 0.000 description 1
- 230000000274 adsorptive effect Effects 0.000 description 1
- 230000004520 agglutination Effects 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 238000006065 biodegradation reaction Methods 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 238000003889 chemical engineering Methods 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 235000012489 doughnuts Nutrition 0.000 description 1
- 238000004043 dyeing Methods 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 239000008235 industrial water Substances 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 229910017053 inorganic salt Inorganic materials 0.000 description 1
- 238000009434 installation Methods 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- PALNZFJYSCMLBK-UHFFFAOYSA-K magnesium;potassium;trichloride;hexahydrate Chemical compound O.O.O.O.O.O.[Mg+2].[Cl-].[Cl-].[Cl-].[K+] PALNZFJYSCMLBK-UHFFFAOYSA-K 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 230000001699 photocatalysis Effects 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 229920006393 polyether sulfone Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- 238000004080 punching Methods 0.000 description 1
- 239000008213 purified water Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000001172 regenerating effect Effects 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- PANBYUAFMMOFOV-UHFFFAOYSA-N sodium;sulfuric acid Chemical compound [Na].OS(O)(=O)=O PANBYUAFMMOFOV-UHFFFAOYSA-N 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000009284 supercritical water oxidation Methods 0.000 description 1
- 239000003643 water by type Substances 0.000 description 1
- 230000010148 water-pollination Effects 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
Classifications
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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
- C01—INORGANIC CHEMISTRY
- C01D—COMPOUNDS OF ALKALI METALS, i.e. LITHIUM, SODIUM, POTASSIUM, RUBIDIUM, CAESIUM, OR FRANCIUM
- C01D3/00—Halides of sodium, potassium or alkali metals in general
- C01D3/04—Chlorides
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01D—COMPOUNDS OF ALKALI METALS, i.e. LITHIUM, SODIUM, POTASSIUM, RUBIDIUM, CAESIUM, OR FRANCIUM
- C01D3/00—Halides of sodium, potassium or alkali metals in general
- C01D3/14—Purification
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01D—COMPOUNDS OF ALKALI METALS, i.e. LITHIUM, SODIUM, POTASSIUM, RUBIDIUM, CAESIUM, OR FRANCIUM
- C01D5/00—Sulfates or sulfites of sodium, potassium or alkali metals in general
- C01D5/16—Purification
-
- 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
- C02F1/001—Processes for the treatment of water whereby the filtration technique is of importance
-
- 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
- C02F1/048—Purification of waste water by 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
- C02F1/30—Treatment of water, waste water, or sewage by irradiation
- C02F1/302—Treatment of water, waste water, or sewage by irradiation with microwaves
-
- 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
-
- 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
- C02F1/442—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis by nanofiltration
-
- 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
-
- 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
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/722—Oxidation by peroxides
-
- 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
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/725—Treatment of water, waste water, or sewage by oxidation by catalytic oxidation
-
- 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
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/78—Treatment of water, waste water, or sewage by oxidation with ozone
-
- 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
- C02F2001/007—Processes including a sedimentation step
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
- C02F2103/26—Nature of the water, waste water, sewage or sludge to be treated from the processing of plants or parts thereof
- C02F2103/28—Nature of the water, waste water, sewage or sludge to be treated from the processing of plants or parts thereof from the paper or cellulose industry
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2301/00—General aspects of water treatment
- C02F2301/08—Multistage treatments, e.g. repetition of the same process step under different conditions
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2305/00—Use of specific compounds during water treatment
- C02F2305/02—Specific form of oxidant
- C02F2305/026—Fenton's reagent
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F3/00—Biological 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
- C02F5/00—Softening water; Preventing scale; Adding scale preventatives or scale removers to water, e.g. adding sequestering agents
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- 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
Abstract
The present invention relates to a kind of high-salinity wastewater zero-emission processing method and processing devices based on NF membrane mixing system.The technique key step is as follows：By the preprocessed system removal of impurities of high-salt wastewater, salt concentrate, after softening, concentrated water after softening enters nanofiltration mixing system, allocate the concentration of a divalent salts, make the concentration ratio of a divalent salts of nanofiltration concentrated water between 0.01~0.1, nanofiltration mixing system concentrated water enters the acquisition of sulfate crystal system and meets Nacl requirement divalent product salt and sodium chloride-containing mother liquor, nanofiltration mixing system penetrating fluid enters sodium chloride crystal system after upgrading system again and obtains sodium chloride salt product and sulfur acid mother liquid of sodium, sodium chloride crystalline mother solution enters after removal of impurities in sulfate crystal system, sulfate crystal mother liquor enters sodium chloride crystal system after removal of impurities, it realizes wastewater zero discharge and stabilizes the fluctuation of salinity in crystal system.
Description
Technical field
The present invention relates to a kind of high-salinity wastewater zero-emission processing method and processing devices based on NF membrane allotment, belong to water process
Technical field.
Background technology
The waste water of the discharges such as paper industry, printing and dyeing industry, chemical engineering industry, pharmaceuticals industry contains certain density inorganic
Salt, all referred in wastewater zero discharge processing procedure how the technique for detaching inorganic salts from waste water.For brine waste zero
Discharge reduces COD and SS using advanced oxidation pretreatment, is concentrated on this basis using reverse osmosis membrane, with cycles of concentration
Rising, the hardness in waste water also gradually rises." two alkaline process " or " resin tenderizer " removing can be used in waste water after concentrated
Hardness in waste water.Waste water through removing hardness is tied after the techniques such as reverse osmosis or electrodialysis further concentration using evaporation
Brilliant technique obtains Nacl.The clear water that film concentration process generates is used for each production workshop section according to water quality difference.Such brine waste
Technique of zero discharge Chinese invention patent（CN103508602A, CN104071808A）It has been reported that but not related in these patents
And how to realize the separation problem of a divalent salts, obtained carnallite is difficult to recycling.
Brine waste zero emission technique is divided into cycle pretreatment, cycle minimizing and zero by Chinese patent CN105540972A
Three parts of exhaust unit.The separation of sal prunella is realized during evaporative crystallization technique.The technique is mainly in brine waste
Monovalent salt and the larger system of divalent salts concentration difference, can be obtained by controlling the operating condition of crystallization processes technical grade monovalent salt and
Divalent salts, due to industrial wastewater complicated component and monovalent salt is difficult to meet the separation of sal prunella with divalent salts concentration difference, this is specially
The restricted application of profit.
Chinese patent CN104370405A carries out a point salt treatment using nanofiltration to high concentration brine, by nanofiltration fresh water into
It is used for regenerating softener after row concentration.Nanofiltration concentrated water obtains solid content for evaporative crystallization, can get the divalent salts production of high-purity
Object, but the fresh water of nanofiltration does not do concentrate and obtains monovalence product salt, the outer row for causing this part brine waste or the interior enrichment of system, it should
Patent addresses only the problem of part salt utilizes.
Invention content
The technical problem to be solved by the present invention is to：For the concentration ratio of sodium chloride in brine waste and sodium sulphate discomfort
Close using method for crystallising separation the problem of, using nanofiltration technique in brine waste monovalent salt and divalent salinity adjust
Section so that waste water of the NF membrane after proportion adjustment can further be concentrated using reverse osmosis or electrodialysis process, concentration
Brine waste can obtain sodium chloride and sodium sulphate Nacl by corresponding crystallization processes respectively.
The first aspect of the invention：
A kind of high-salinity wastewater zero-emission method, includes the following steps：
1st step cleans the preprocessed system of brine waste；
2nd step carries out concentration to the waste water that the 1st step obtains；
3rd step carries out sofening treatment to the waste water that the 2nd step obtains；
4th step is handled the waste water that the 3rd step obtains using nanofiltration membrane, adjusts the NaCl and Na in waste water2SO4Concentration ratio
Example；
The concentrated water of 5th step, NF membrane is sent into Na2SO4Crystal system obtains Na by Crystallization Separation2SO4Nacl and first
Mother liquor；The fresh water of NF membrane is concentrated and then is sent into NaCl crystal system, and NaCl Nacls are obtained by Crystallization Separation
And second mother liquor；
6th step, the first mother liquor, which is sent into NaCl crystal systems, carries out crystallization treatment, and the second mother liquor is sent into Na2SO4Crystal system into
Row crystallization treatment.
In one embodiment, pretreatment system is discharged COD between 10~200mg/L in the 1st step, SS 3~
50mg/L。
In one embodiment, the pretreatment in the 1st step refers to pre-filtering, biofilter, precipitation, oxidation or ultrafiltration
In one or more combinations.
In one embodiment, pre-filtering is one or more in sand filtration, multi-medium filtering or activated carbon filtering
Combination.
In one embodiment, oxidation is using one in ozonation technology, Fenton oxidation technology or microwave oxidation
Kind or a variety of combinations；Biofilter refers to activated carbon bio-filter.
In one embodiment, concentration makes in waste water TDS in 20~60g/L；Concentration process is dense using NF membrane
One or more process combinations in contracting, reverse osmosis concentration or electrodialysis concentration.
In one embodiment, melded system goes out the water hardness between 20~200mg/L in the 3rd step；Softening process can
Using one or more process combinations in film softening, medicament softening or ion exchange resin softening.
In one embodiment, in the 4th step, the NaCl in NF membrane concentrated water and Na2SO4The concentration mass ratio of concentration
0.01~0.07：1；Na in the concentrated water of NF membrane2SO4Mass concentration 8~15%.
In one embodiment, in the 5th step, the fresh water of NF membrane carry out concentration be using high pressure reverse osmosis membrane technique,
The combination of one or more of DTRO techniques, electrodialysis process, MVR evaporation technologies or multiple-effect evaporation technique；NF membrane fresh water
NaCl mass concentrations are between 10~20% after concentration.
In one embodiment, the first mother liquor is re-fed into NaCl crystal systems after concentration and carries out at crystallization
Reason, the second mother liquor are re-fed into Na after crossing concentration2SO4Crystal system carries out crystallization treatment.
The second aspect of the invention：
A kind of high-salinity wastewater zero-emission processing unit, including：
Pretreatment system, for carrying out pretreatment removal of impurities to high-salt wastewater；
Concentration systems are connected to pretreatment system, and the waste water for being obtained to pretreatment system carries out concentration；
Melded system is connected to concentration systems, for carrying out sofening treatment to the waste water after concentration；
NF membrane is connected to melded system, the separation for carrying out a divalent salts to the production water after sofening treatment；
Sulfate crystal system is connected to the dope side of NF membrane, for nanofiltration dope crystallization treatment, obtaining Na2SO4；
Sodium chloride crystal system is connected to the light liquid side of NF membrane, for the light liquid crystallization treatment of nanofiltration, obtaining NaCl.
In one embodiment, the mother liquor outlet of sulfate crystal system is connected to sodium chloride crystal system, sodium chloride
The mother liquor outlet of crystal system is connected to sulfate crystal system.
In one embodiment, the pretreatment system includes pre-filtrating equipment, biofilter, settler, oxygen
Makeup set or ultrafiltration apparatus in one or more combinations.
In one embodiment, pre-filtrating equipment is sand filtering device, multi-medium filtering device or activated carbon filtering dress
One or more combinations in setting.
In one embodiment, bacteria filter device is activated carbon bio-filter device.
In one embodiment, oxidation unit is ozone-oxidizing device, Fenton oxidation device or microwave oxidation unit
In one or more combinations.
In one embodiment, the concentration systems include nanofiltration film condensing device, reverse osmosis concentrated compression apparatus or
One or more combinations in electrodialysis enrichment facility.
In one embodiment, the light liquid side of NF membrane is connect by enrichment facility with sodium chloride crystal system.
In one embodiment, enrichment facility is selected from high pressure reverse osmosis membrane apparatus, DTRO devices, electrodialysis plant, MVR
The combination of one or more of vaporising device or multi-effect evaporating device.
Advantageous effect
The targeted brine waste wide adaptability of the present invention adjusts monovalent salt by controlling nanofiltration cycles of concentration and rejection
With the ratio of divalent salts, meet follow-up NaCl and Na2SO4The requirement for crystallizing reuse technology respectively, realizes wastewater zero discharge, and obtain
The monovalent salt and divalent product salt for obtaining the high technical grade of purity, have the advantages that energy-efficient emission reduction.
The present invention main innovation point be by NF membrane be used for in high-salt wastewater monovalent salt and divalent salts ratio into
Row is adjusted, and meets NaCl and Na2SO4The requirement crystallized respectively recycles the mother liquor of crystallization process, reduces mother liquor amount,
Improve the efficiency that sal prunella joint process salt utilizes.The monovalent salt of high-purity is finally obtained while realizing brine waste zero emission
With divalent salts, the recycling of water and inorganic salts is realized.
In addition, due in NaCl and Na2SO4During crystallizing respectively, the NaCl and Na in feed liquid are crystallized2SO4Concentration
It is bigger than differing, more it is conducive to the crystal salt that crystallization process forms high-purity.And since the salinity in high-salt wastewater can be sent out
Raw periodically fluctuation, is easy to cause the fluctuation for obtaining the generating period of the concentration in light liquid and dope in nanofiltration process, influences
To crystallization process.Therefore, by being returned again to later to upper level using the further concentrate of reverse osmosis membrane to the mother liquor after crystallization
Crystal system can effectively make NaCl and Na2SO4Concentration ratio fluctuation numerical value reduce, it is suppressed that the shakiness in crystallization process
Qualitatively occur.
Description of the drawings
Fig. 1 is method overall flow figure provided by the invention.
Fig. 2 is installation drawing provided by the invention.
Wherein, 1, pretreatment system；2, concentration systems；3, melded system；4, NF membrane；5, sulfate crystal system；6、
Sodium chloride crystal system.
Specific implementation mode
Below by specific implementation mode, invention is further described in detail.But those skilled in the art will manage
Solution, the following example is merely to illustrate the present invention, and should not be taken as limiting the scope of the invention.Specific skill is not specified in embodiment
Art or condition person carry out according to technology or condition described in document in the art or according to product description.Examination used
Production firm person is not specified in agent or instrument, and being can be with conventional products that are commercially available.
The value expressed using range format should be interpreted as not only in a flexible way including clearly enumerating as range
The numerical value of limit value, but also include all single numbers or the subinterval covered in the range, like each numerical value and sub-district
Between be expressly recited out.For example, the concentration range of " about 0.1% to about 5% " should be understood as including not only clearly enumerating
The concentration of about 0.1% to about 5% further includes the single concentration in how（Such as, 1%, 2%, 3% and 4%）The subinterval and（Example
Such as, 0.1% to 0.5%, 1% to 2.2%, 3.3% to 4.4%）.
" one embodiment " for addressing in the present specification, " another embodiment ", " embodiment " etc., refer to
In conjunction with the specific features of embodiment description, structure or it is included at least one embodiment generally described herein.
It is not centainly to refer to the same embodiment that statement of the same race, which occur, in multiple places in the description.Furthermore, it is understood that in conjunction with any
When embodiment describes a specific features, structure or feature, what is advocated is that this spy is realized in conjunction with other embodiment
Sign, structure or feature are also fallen in the application scope of the claimed.
It should be understood that when an element is mentioned with another element " connection ", it can be direct with other elements
It is connected or is indirectly connected with other elements, and inserted with element between them.Unless there are clearly opposite explanation, otherwise term
It includes listed element that " comprising " and " having ", which is interpreted as statement, and non-excluded arbitrary other elements.
Word "include", "comprise" used herein, " having " or its any other variant are intended to cover non-exclusionism
Including.E.g., including technique, method, article or the equipment for listing element are not necessarily limited by those elements, but may include
Other are not explicitly listed or belong to this technique, method, article or the intrinsic element of equipment.
The present invention relates to a kind of technique of high-salinity wastewater zero-emission, required high-salt wastewater to be processed be primarily referred to as containing
NaCl、Na2SO4, the substances such as COD waste water, wherein also containing some Ca2+、Mg2+Hardness etc..High-salt wastewater mainly can be with
Middle water that middle water and tail water in paper-making process after treatment, which can also be coal chemical industrial waste water, to be obtained by processing and
Tail water etc..Some typical water quality situations are：COD is in COD in 10~200mg/L, 50~1000 mg/L of total hardness（With CaCO3
Meter）, TDS is in 1000~20000 mg/L, and total suspended matter SS is in 3~50mg/L, and NaCl concentration is in 200~5000mg/L, Na2SO4
200~5000mg/L of concentration range.Method of the invention is particularly suitable for NaCl and Na2SO4Concentration proportion can not be direct
The case where the two is detached by way of evaporative crystallization；Such as NaCl and Na2SO4Mass concentration ratio 10：1~1：10 this
A range can also be 5：1~1：5, can also be 2：1~1：2.
Main technological process is as follows：
Step 1：By the preprocessed system removal of impurities of high-salt wastewater, pretreatment system water outlet；
Step 2：Enter salt upgrading system after removal of impurities, makes in waste water that for TDS in 20~60g/L, reverse osmosis freshwater enters reuse water system
System；
Step 3, salt upgrading system concentrated water enter melded system, and melded system goes out the water hardness between 50~200mg/L；
Concentrated water after step 4, softening enters nanofiltration mixing system, allocates the concentration of a divalent salts, makes a divalent of nanofiltration concentrated water
The concentration ratio of salt is between 0.01~0.1；
Step 5, nanofiltration mixing system concentrated water enter Na2SO4Crystal system acquisition meets Nacl requirement Na2SO4Nacl and mother
Liquid；
Step 6, nanofiltration mixing system penetrating fluid after upgrading system again enter NaCl crystal systems obtain NaCl Nacls and
Mother liquor；
Step 7, Na2SO4The condensed water of crystal system and NaCl crystal systems enters reuse water system Na2SO4Crystal system discharges
Mother liquor enters after removal of impurities in NaCl crystal systems, and NaCl crystal systems discharge mother liquor and enter Na after removal of impurities2SO4Crystal system
In, realize wastewater zero discharge；
Step 8, each system purified water meet different reuse requirements after the allotment of reuse water system, realize quality classification water supply.
Further, pretreatment unit described in step 1 is mainly to carry out pre- removal of impurities processing to water quality using some conventional
Process, main purpose is to get rid of the impurity that removal is easier in waste water, and mitigate subsequent membrane process, evaporation process etc.
Load, and water quality can be improved, pretreatment here can be carried out according to conventional processing step, may include pre-filtering,
It is one or more in precipitation, oxidation technology.Wherein pre-filtering is usually that can enumerate centrifugation mode, expression separation side
Formula, filter type, floating separate mode, sedimentation separation mode.As the mode of centrifugation, horizontal continuous centrifugal point may be exemplified
It disembarks (processing of spiral decanter), detach board-like centrifugal separator, filter centrifugal, tall building Pu Lesi type UCF ultracentrifuges, make
For filter type, band filter, belt press, flypress, precoat filter, filter press are may be exemplified, is detached as floating
Mode may be exemplified continuous floating separator, as sedimentation separation mode, may be exemplified agglutination sedimentation separation machine, sinks rapidly
Seperator etc. is dropped, but is not particularly limited in above-mentioned any one.However it can be reduced by above-mentioned any one or combinations thereof
To the load of film when secondary filter film and/or ultrafiltration membrane treatment.It is particularly preferred that sand filtration, more Jie may be used in pretreating process
One or more combinations in matter filtering, activated carbon filtering.Here biofilter process refers to using with high-specific surface area
Sorbing material as carrier in water macromolecular or other impurity be removed, carrier used herein above may be used often
The organic or inorganic adsorbing material of rule, such as：The sorbing materials such as macroporous absorbent resin, zeolite, activated carbon；Bioactivity carbon filtration
Using lower to flow pattern formula, water inlet dissolved oxygen content generally in 5~10mg/L or so, can fully ensure that biodegradation to dissolved oxygen in pond
Demand；Two-part air-water backwashing may be used in filter tank, i.e., is discharged first with air bump rinse operation, again with the sand filtration of non-chlorination anti-
Punching, backwashing period are 1~10 day；In biofilter if when being loaded using activated carbon as carrier, generally use iodine number and Asia
First orchid adsorptive value carries out the standard of evaluation activated carbon, can be respectively 300~2000 mg/g and 50~500mg/g with adsorbance, living
Property carbon build-up density can be 50~600g/L.Precipitation described here refers to by gravitational settling or in other outer force effects
Under sedimentation using the method that detaches granule foreign with waste water, the method that may be used is sedimentation basin etc.；Oxidation is profit
With pollutant in oxidizing Decomposition Wastewater, the method to purify waste water, when being handled using advanced oxidation, mainly Fenton
Oxidizing process, ozone co-oxidation method, wet oxidation process, supercritical water oxidation method, photocatalytic oxidation and ultrasonic oxidation method etc. are several
Class particularly preferably uses in ozonation technology, Fenton technology, microwave oxidation and one or more is combined processing.Using
When ozone oxidation, ozone concentration can be 10~500ppm, and oxidizing temperature can be 10~50 DEG C；When using Fenton oxidation, Fe2+
And H2O2Concentration can be respectively 10~50mg/L and 20~900mg/L, and system pH is 3~6, and reaction temperature is 10~60 DEG C,
Reaction time is 10~240min；When being aoxidized using microwave, 400~3000MHz of frequency, 10~60 DEG C of oxidizing temperature, processing
20~200min of time.The ultrafiltration used in pretreatment refers to being carried out to the colloid in water, big molecular impurity by ultrafiltration membrane
The process of filter, " ultrafiltration membrane " in this specification refer to the filter membrane and/or molecular cut off that aperture is 0.001~0.01 μm
For 1000~300000 or so filter membrane, inoranic membrane and organic film may be used in the material of ultrafiltration membrane, is further divided into thin
Aqueous and hydrophily.As hydrophobic organic film, it is not limited to this, polysulfones can be enumerated, polyether sulfone, polyethers, gathered partially
Difluoroethylene, polyethylene, polypropylene etc..As hydrophilic organic film, be not limited to this, can enumerate polyacrylonitrile,
Polyamide, polyimides, cellulose acetate etc..Its filter core shape includes that flat membrane, tubular film, spiral membrane, doughnut are (hollow
Silk) film etc..
Further, the salt concentration systems described in step 2, cycles of concentration is between 2~20 times, according to water inlet salinity
Suitable cycles of concentration is selected, 10~40g/L of its salinity is for preferred salinity but according to salt component in water after concentration
Difference and water inlet salinity variation can suitably adjust, which is not the decision condition of process implementing.The salt concentrate of step 2
System is using one or more process combinations in NF membrane concentration, reverse osmosis concentration, electrodialysis concentration.
NF membrane involved in institute of the invention is defined as " preventing the drive of the pressure of the particle less than 2nm and the macromolecular of dissolving
The film of dynamic film ", can use cellulose acetate based polymer, polyamide, sulfonated polysulfone, polyacrylonitrile, polyester, polyimides and
The high molecular materials such as polyvinyl.Reverse osmosis membrane in the present invention can use cellulose acetate Type of Collective object, polyamides
The high molecular materials such as amine, polyester, polyimides, polyvinyl.The operating pressure of NF membrane can control 0.5~
4.0MPa, the operating pressure of reverse osmosis membrane can control the range in 1.0MPa~10MPa.
Further, the purpose of the softening process of the 3rd step gets rid of the Ca in waste water2+、Mg2+It is soft that film can be used in ion
Change, medicament softening（Such as NaOH and Na is added2CO3）, ion exchange resin softening.
Further, the NaCl and Na in common middle water2SO4Concentration proportion cannot meet respectively crystallization obtain NaCl
And Na2SO4Requirement when, NF membrane is used to that monovalent salt and the divalent salts ratio in high-salt wastewater to be adjusted by the present invention, is expired
Sufficient NaCl and Na2SO4The requirement crystallized respectively recycles the mother liquor of crystallization process, reduces mother liquor amount, improves sal prunella
The efficiency that joint process salt utilizes.The monovalent salt and divalent of high-purity are finally obtained while realizing brine waste zero emission
Salt realizes the recycling of water and inorganic salts.NaCl and Na in the nanofiltration concentrated water of 4th step2SO4Mass concentration ratio 0.01
~0.07 is selection process.
Further, the upgrading system again of the 6th step uses high pressure reverse osmosis membrane technique, DTRO techniques, electrodialysis process,
MVR evaporation technologies or multiple-effect evaporation technique may be used.
Further, NaCl mass concentrations are between 10~20% after the nanofiltration fresh water of the 4th step concentrates.
Further, Na after the nanofiltration concentrated water concentration of the 4th step2SO4Mass concentration is between 8~15%.
Further, the 5th NaCl crystal systems, the Na described in step 6 step2SO4The evaporative crystallization that crystal system uses
Technique is one kind in multiple-effect evaporation or MVR evaporations.
Further, the dedoping step described in step 7 step is using one in ozone oxidation, wet oxidation or light electrolysis oxidation
Kind or multiple combinations technique.
Further, the reuse water system described in the 8th step can realize quality classification water supply according to each system producing water water quality, be used for
It is one or more in boiler feedwater front end, industrial water, plant area's reclaimed water, recirculated water, landscape water.
Further, Na2SO4Crystal system mother liquor is re-fed into NaCl crystal systems after concentration and carries out at crystallization
Reason, NaCl crystal system mother liquors are re-fed into Na after crossing concentration2SO4Crystal system carries out crystallization treatment.Due to the monovalence in waste water
It can occur constantly to fluctuate with the concentration of divalent salts, and then influence whether the process of subsequent nanofiltration, crystallization so that technological parameter
The variation for carrying out constantly being adapted to salinity in water is needed, therefore operating process can be caused unstable, crystal salt pure
Degree cannot reach requirement.Meanwhile in NaCl and Na2SO4During crystallizing respectively, the NaCl and Na in feed liquid are crystallized2SO4's
Concentration ratio difference is bigger, is more conducive to the crystal salt that crystallization process forms high-purity.Such as：In the process crystallized to NaCl
In, the NaCl in crystal solution and Na2SO4Concentration proportion be C1(NaCl)/C1(Na2SO4), when by Na2SO4It is obtained after crystallization
Mainly contain the mother liquor of NaCl（Concentration is calculated as C2And C (NaCl),2(NaCl)> C1(NaCl)）Further added after concentration
During being crystallized to NaCl, you can so that the concentration on the molecule of ratio increases, improve concentration proportion；According to numerical value
Calculating could be aware that, as 10 ＜ C1(NaCl)/C1(Na2SO4) ＜ 100 when fluctuation, makes molecular concentration increase that can make in ranges
The fluctuating range of whole ratio is obviously reduced, and plays the effect for stabilizing fluctuation.Similarly Na2SO4Crystallization process in, a divalent
The concentration proportion of salt is C1(Na2SO4)/C1(NaCl), what is obtained after crystallizing NaCl mainly contains Na2SO4Mother liquor concentrations
Afterwards, the C that will be obtained2(Na2SO4) concentrate is back to Na2SO4Crystallization process in after, due to C2(Na2SO4)> C1(Na2SO4),
Similarly play the role of stabilizing crystallization process fluctuation of concentration.Therefore, by using reverse osmosis membrane to the mother liquor after crystallization
It is returned again to the crystal system of upper level after further concentrate, can effectively make NaCl and Na2SO4Concentration ratio fluctuation
Numerical value reduces, it is suppressed that the instable generation in crystallization process.
Based on above method, processing unit provided by the invention is as shown in Fig. 2, include：
Pretreatment system 1, for carrying out pretreatment removal of impurities to high-salt wastewater；
Concentration systems 2 are connected to pretreatment system 1, and the waste water for being obtained to pretreatment system 1 carries out concentration；
Melded system 3 is connected to concentration systems 2, for carrying out sofening treatment to the waste water after concentration；
NF membrane 4 is connected to melded system 3, the separation for carrying out a divalent salts to the production water after sofening treatment；
Sulfate crystal system 5 is connected to the dope side of NF membrane 4, for nanofiltration dope crystallization treatment, obtaining Na2SO4；
Sodium chloride crystal system 6 is connected to the light liquid side of NF membrane 4, for the light liquid crystallization treatment of nanofiltration, obtaining NaCl.
In one embodiment, sulfate crystal system 5, mother liquor outlet be connected to sodium chloride crystal system 6, chlorination
The mother liquor outlet of sodium crystal system 6 is connected to sulfate crystal system 5.
In one embodiment, the pretreatment system 1 includes pre-filtrating equipment, biofilter, oxidation unit, sinks
One or more combinations in shallow lake device, oxidation unit or ultrafiltration apparatus.
In one embodiment, pre-filtrating equipment is sand filtering device, multi-medium filtering device or activated carbon filtering dress
One or more combinations in setting.
In one embodiment, oxidation unit is ozone-oxidizing device, Fenton oxidation device or microwave oxidation unit
In one or more combination biofilters refer to activated carbon bio-filter device.
In one embodiment, the concentration systems 2 include nanofiltration film condensing device, reverse osmosis concentrated compression apparatus or
One or more combinations in electrodialysis enrichment facility.
In one embodiment, the light liquid side of NF membrane 4 is connect by enrichment facility with sodium chloride crystal system.
In one embodiment, enrichment facility is selected from high pressure reverse osmosis membrane apparatus, DTRO devices, electrodialysis plant, MVR
The combination of one or more of vaporising device or multi-effect evaporating device.
Embodiment 1
Wastewater zero discharge and Nacl recycling are realized using nanofiltration and crystallization joint production process for certain pulp-making waste-water.Slurrying
Waste water raw water day output is 40000 tons.Main water quality parameter see the table below：
Pulp-making waste-water raw water carries out in advance water using sand filtration and ozone, activated carbon bio-filter technique after the homogeneous of homogeneous pond
Processing, ozone concentration 150ppm, ozone oxidation time 40min；Hydraulic detention time 15min；The activated carbon bio-filter charcoal height of bed
Spend 2.0m, 25~30 DEG C for the treatment of temperature, air-land combat 20min；Waste water SS is down to 12~18mg/L after pretreatment,
COD concentration is down to 45~53mg/L, and the pretreated water rate of recovery is more than 97%.
Enter ultrafiltration system, the molecular cut off 100kDa of ultrafiltration membrane, ultrafiltration work pressure by pretreated brine waste
Power 0.3MPa, ultrafiltration operating flux 50L/（m2·h）, the ultrafiltration membrane cleaning frequency is more than 90 days, and ultrafiltration production water SDI is turbid less than 2.5
Degree is less than 0.2NTU, and the ultrafiltration system rate of recovery is more than 93%.
Ultrafiltration production water enters first-stage reverse osmosis system, reverse osmosis operating pressure 1.5MPa, 30 DEG C of temperature, the reverse osmosis rate of recovery
65%, 15 L/ of average flux（m2·h）, production water TDS is less than 105mg/L.Water yield per day is 24500m3.First-stage reverse osmosis concentrated water into
Enter weak-acid ion exchange resin bed melded system, waste water hardness is down to 170 in 1200~1430mg/L after melded system
~187mg/L is down to 26mg/L by weak acid cation bed hardness, meets the reverse osmosis requirement of back segment.
Reverse osmosis concentrated water after softened enters two sections of counter-infiltration systems, reverse osmosis operating pressure 2.0MPa, 30 DEG C of temperature,
Water inlet TDS is 10250~10560mg/L, and COD is 187~202mg/L, 3520~3640mg/L of sodium chloride concentration, and sodium sulphate is dense
Spend 6300~6550mg/L, day output 13500m3.The water rate of recovery is 75%, fresh water yield 10120m3/ d, concentrated water amount
3380m3/d.It producing water TDS and is less than 210mg/L, concentrated water TDS is 40750~41300mg/L, sodium chloride concentration 13450 in concentrated water~
13920mg/L, 24700~25530mg/L of sodium sulfate concentration, 392~434mg/L of hardness.Concentrated water is soft again by weak acid cation bed
Hardness is reduced to 4~6mg/L after change.
Two-pass reverse osmosis concentrated water carries out inorganic salts ratio allotment by NF membrane, and operating pressure 54bar is handled through nanofiltration
Afterwards, fresh water amount is 2910m3/ d, 14700~15340mg/L of sodium chloride concentration, 260~285mg/L of fresh water sodium sulfate concentration.It receives
After filter fresh water uses high pressure is reverse osmosis and homogeneous membrane electrodialytic technique is further to concentrate, concentration liquid measure is 245m3/ d, sodium chloride are dense
Spend 191100~203700mg/L, 5380~5500mg/L of sodium sulfate concentration.Nanofiltration concentrated water amount is 480m3/ d, sodium chloride concentration
11320~11890mg/L, 174200~17950mg/L of sodium sulfate concentration.
Nanofiltration fresh water is after reverse osmosis membrane concentrates, NaCl concentration 31100~31880mg/L, NaCl and Na2SO4Quality it is dense
Degree is than about 53:1, meet the production requirement into NaCl crystallization processes sections.Sodium chloride crystal system uses triple effect evaporation, uses
Advection feed-often imitates out the mode of operation of salt-mother liquor reflux, and control crystallization temperature is between 40~50 DEG C, in crystalline mother solution
Na2SO4Mass concentration 5380mg/L, send to sulfate crystal system reuse, day obtains 45.7 tons of sodium chloride.Nanofiltration concentrated water into
Enter sulfate crystal system, sulfate crystal system carries out Na using MVR techniques2SO4Crystallization, control crystallization temperature is 90~105
Between DEG C, Na2SO4Mass concentration ratio with NaCl is about 13:1, meet and enters Na2SO4The technological requirement of crystallization, crystalline mother solution
The mass concentration 58400mg/L of middle NaCl is sent to sodium chloride crystal system reuse, which produces 82.5 tons of anhydrous sodium sulfate daily.
The sodium chloride purity of two kinds of techniques reaches 98.3%, and sodium sulphate purity reaches 99.0%.
Using Nanofiltration-membrane technique in brine waste sodium chloride and sodium sulfate concentration be adjusted, fresh water and concentrated water chlorination
Sodium and sodium sulphate ratio meet the requirement for carrying out sodium sulphate or sodium chloride joint production process, finally the zero-emission of realization waste water, and from
The sodium chloride and sodium sulfate salt that can be recycled are obtained in waste water.
Embodiment 2
The existing Sewage Disposal of certain coal chemical industry enterprises one, wastewater discharge 2750m3/ h, waste water energy, which meets qualified discharge, to be wanted
It asks.It is as follows to discharge water water quality index：
Inorganic salts ingredients are mainly sodium chloride and sodium sulphate in waste water.Zero-emission is carried out to waste water with crystallization joint production process using nanofiltration
Put processing.
Coal chemical industrial waste water is delivered to zero-emission raw water after the homogeneous of homogeneous pond using sand filtration and ozone, activated carbon from plant area
Absorbing process pre-processes water, ozone concentration 200ppm, ozone oxidation time 50min；20 DEG C of activated carbon adsorption temperature,
Hydraulic detention time 12min；Waste water SS is down to 5~9mg/L after pretreatment, and COD concentration is down to 20~31mg/L, pretreatment
The water rate of recovery is more than 98%.
Enter ultrafiltration system, the molecular cut off 50kDa of ultrafiltration membrane, ultrafiltration operating pressure by pretreated brine waste
0.4MPa, ultrafiltration operating flux 45L/（m2·h）, the ultrafiltration membrane cleaning frequency is more than 60 days, and ultrafiltration produces water SDI and is less than 2, and turbidity is low
In 0.3NTU, the ultrafiltration system rate of recovery is more than 92%.
Ultrafiltration production water enters first-stage reverse osmosis system, reverse osmosis operating pressure 2.0MPa, and the reverse osmosis rate of recovery 60% is averaged
15 L/ of flux（m2·h）, production water TDS is less than 50 mg/L, water yield 1625m3/h.First-stage reverse osmosis concentrated water enters faintly acid
Ion exchange resin bed melded system, waste water hardness drops 30~42mg/L, warp in 1050~1250mg/L after melded system
It crosses weak acid cation bed hardness and is down to 4mg/L hereinafter, meeting the reverse osmosis requirement of back segment.
Reverse osmosis concentrated water after softened enters two sections of counter-infiltration systems, reverse osmosis operating pressure 1.5MPa, and water inlet TDS is
4700~5230mg/L, COD are 38~47mg/L, 735~920mg/L of sodium chloride concentration, 3860~4340mg/ of sodium sulfate concentration
L, treating capacity 1150m3/h.The water rate of recovery is 75%, fresh water yield 860m3/ h, concentrated water amount 290m3/h.Production water TDS is less than
100mg/L, concentrated water TDS are 18500~20560mg/L, 2900~3130mg/L of sodium chloride concentration in concentrated water, sodium sulfate concentration
15460~17240mg/L, 76~85mg/L of hardness.
Two sections of reverse osmosis concentrated waters enter three sections of counter-infiltration systems, and water inlet TDS is 18500~19840mg/L, COD for 150~
167mg/L, 2900~3170mg/L of sodium chloride concentration, 15460~16710mg/L of sodium sulfate concentration, treating capacity 290m3/h。
The water rate of recovery is 60%, fresh water yield 175m3/ h, concentrated water amount 115m3/h.It produces water TDS and is less than 400mg/L, concentrated water TDS is
46250~48220mg/L, 7050~7280mg/L of sodium chloride concentration, 38600~40530mg/L of sodium sulfate concentration in concentrated water, firmly
Spend 76~87mg/L.
Three-level reverse osmosis concentrated water carries out inorganic salts ratio allotment by NF membrane, and operating pressure 48bar is handled through nanofiltration
Afterwards, fresh water amount is 77m3/ h, 7120~7330mg/L of sodium chloride concentration, 390~419mg/L of fresh water sodium sulfate concentration.Nanofiltration is light
After water uses high pressure is reverse osmosis and homogeneous membrane electrodialytic technique is further to concentrate, concentration liquid measure is 5.1m3/ h, sodium chloride concentration
106080~113500mg/L, 5840~6010mg/L of sodium sulfate concentration.Nanofiltration concentrated water amount is 38m3/ h, sodium chloride concentration 7035
~7230mg/L, 115800~123400mg/L of sodium sulfate concentration.
Nanofiltration fresh water is after reverse osmosis membrane concentrates, NaCl and Na2SO4Mass concentration ratio be about 18:1, meet and enters chlorination
The production requirement of sodium crystal system.Sodium chloride crystal system uses triple effect evaporation, and salt-mother liquor is often imitated out using advection charging-
The mode of operation of reflux, control crystallization temperature is between 40~50 DEG C, Na in crystalline mother solution2SO4Mass concentration 3070mg/L,
It send to sulfate crystal system reuse, day obtains 12.7 tons of sodium chloride.Nanofiltration concentrated water enters sulfate crystal system, sodium sulphate knot
Crystallographic system system uses MVR techniques, and control crystallization temperature is between 90~105 DEG C, Na2SO4Mass concentration ratio with NaCl is about 16:
1, meet the technological requirement into sodium chloride and sodium sulphate, the mass concentration 33120mg/L of NaCl, send to chlorination in crystalline mother solution
Sodium crystal system reuse, the technique produce 102.6 tons of anhydrous sodium sulfate daily.The sodium chloride purity of two kinds of techniques reaches 98.4%, sulfuric acid
Sodium purity reaches 99.3%.
Using Nanofiltration-membrane technique in coal chemical industrial waste water sodium chloride and sodium sulfate concentration be adjusted, fresh water and concentrated water chlorine
Change sodium and sodium sulphate ratio meets the requirement for carrying out sodium chloride and sulfate crystal technique, finally realizes the zero-emission of waste water, and
The sodium chloride and sodium sulfate salt of technical grade are obtained from waste water.
Embodiment 3
Wastewater zero discharge and Nacl recycling are realized using nanofiltration and crystallization joint production process for certain pulp-making waste-water.Slurrying
Waste water raw water day output is 40000 tons.Main water quality parameter see the table below：
Pulp-making waste-water raw water carries out in advance water using sand filtration and ozone, activated carbon bio-filter technique after the homogeneous of homogeneous pond
Processing, ozone concentration 150ppm, ozone oxidation time 40min；Hydraulic detention time 15min；The activated carbon bio-filter charcoal height of bed
Spend 2.0m, 25~30 DEG C for the treatment of temperature, air-land combat 20min；Waste water SS is down to 12~18mg/L after pretreatment,
COD concentration is down to 45~53mg/L, and the pretreated water rate of recovery is more than 97%.
Enter ultrafiltration system, the molecular cut off 100kDa of ultrafiltration membrane, ultrafiltration work pressure by pretreated brine waste
Power 0.3MPa, ultrafiltration operating flux 50L/（m2·h）, the ultrafiltration membrane cleaning frequency is more than 90 days, and ultrafiltration production water SDI is turbid less than 2.5
Degree is less than 0.2NTU, and the ultrafiltration system rate of recovery is more than 93%.
Ultrafiltration production water enters first-stage reverse osmosis system, reverse osmosis operating pressure 1.5MPa, 30 DEG C of temperature, the reverse osmosis rate of recovery
65%, 15 L/ of average flux（m2·h）, production water TDS is less than 105mg/L.Water yield per day is 24500m3.First-stage reverse osmosis concentrated water into
Enter weak-acid ion exchange resin bed melded system, waste water hardness is down to 170 in 1200~1430mg/L after melded system
~187mg/L is down to 26mg/L by weak acid cation bed hardness, meets the reverse osmosis requirement of back segment.
Reverse osmosis concentrated water after softened enters two sections of counter-infiltration systems, reverse osmosis operating pressure 2.0MPa, 30 DEG C of temperature,
Water inlet TDS is 10250~10560mg/L, and COD is 187~202mg/L, 3520~3640mg/L of sodium chloride concentration, and sodium sulphate is dense
Spend 6300~6550mg/L, day output 13500m3.The water rate of recovery is 75%, fresh water yield 10120m3/ d, concentrated water amount
3380m3/d.It producing water TDS and is less than 210mg/L, concentrated water TDS is 40750~41300mg/L, sodium chloride concentration 13450 in concentrated water~
13920mg/L, 24700~25530mg/L of sodium sulfate concentration, 392~434mg/L of hardness.Concentrated water is soft again by weak acid cation bed
Hardness is reduced to 4~6mg/L after change.
Two-pass reverse osmosis concentrated water carries out inorganic salts ratio allotment by NF membrane, and operating pressure 54bar is handled through nanofiltration
Afterwards, fresh water amount is 2910m3/ d, 14700~15340mg/L of sodium chloride concentration, 260~285mg/L of fresh water sodium sulfate concentration.It receives
After filter fresh water uses high pressure is reverse osmosis and homogeneous membrane electrodialytic technique is further to concentrate, concentration liquid measure is 245m3/ d, sodium chloride are dense
Spend 191100~203700mg/L, 5380~5500mg/L of sodium sulfate concentration.Nanofiltration concentrated water amount is 480m3/ d, sodium chloride concentration
11320~11890mg/L, 174200~17950mg/L of sodium sulfate concentration.
Nanofiltration fresh water is after reverse osmosis membrane concentrates, NaCl concentration 31100~31880mg/L, NaCl and Na2SO4Quality it is dense
Degree is than about 53:1, meet the production requirement into NaCl crystallization processes sections.Sodium chloride crystal system uses triple effect evaporation, uses
Advection feed-often imitates out the mode of operation of salt-mother liquor reflux, and control crystallization temperature is between 40~50 DEG C, crystalline mother solution warp
Na after high pressure reverse osmosis concentration2SO4Mass concentration 217710mg/L, send to sulfate crystal system reuse, day obtains sodium chloride
48.6 tons.Nanofiltration concentrated water enters sulfate crystal system, and sulfate crystal system carries out Na using MVR techniques2SO4Crystallization, control
Crystallization temperature is between 90~105 DEG C, Na2SO4Mass concentration ratio with NaCl is about 13:1, meet and enters Na2SO4Crystallization
Technological requirement, the mass concentration 63320mg/L of crystalline mother solution middle NaCl after high pressure reverse osmosis concentration, send to sodium chloride system of crystallization
System reuse, the technique produce 84.7 tons of anhydrous sodium sulfate daily.The sodium chloride purity of two kinds of techniques reaches 99.0%, and sodium sulphate purity reaches
To 99.4%.
Using Nanofiltration-membrane technique in brine waste sodium chloride and sodium sulfate concentration be adjusted, fresh water and concentrated water chlorination
Sodium and sodium sulphate ratio meet the requirement for carrying out sodium sulphate or sodium chloride joint production process, finally the zero-emission of realization waste water, and from
The sodium chloride and sodium sulfate salt that can be recycled are obtained in waste water.
Claims (10)
1. a kind of high-salinity wastewater zero-emission method, which is characterized in that include the following steps：
1st step cleans the preprocessed system of brine waste；
2nd step carries out concentration to the waste water that the 1st step obtains；
3rd step carries out sofening treatment to the waste water that the 2nd step obtains；
4th step is handled the waste water that the 3rd step obtains using nanofiltration membrane, adjusts the NaCl and Na in waste water2SO4Concentration ratio
Example；
The concentrated water of 5th step, NF membrane is sent into Na2SO4Crystal system obtains Na by Crystallization Separation2SO4Nacl and the first mother
Liquid；The fresh water of NF membrane is concentrated and then is sent into NaCl crystal system, by Crystallization Separation obtain NaCl Nacls with
And second mother liquor；
6th step, the first mother liquor, which is sent into NaCl crystal systems, carries out crystallization treatment, and the second mother liquor is sent into Na2SO4Crystal system into
Row crystallization treatment.
2. high-salinity wastewater zero-emission method according to claim 1, which is characterized in that pretreatment system is discharged in the 1st step
COD is between 10~200mg/L, and SS is in 3~50mg/L；Pretreatment in 1st step refers to pre-filtering, biofilter, precipitation, oxygen
One or more combinations in change or ultrafiltration；Pre-filtering is one kind in sand filtration, multi-medium filtering or activated carbon filtering
Or a variety of combination；Biofilter refers to activated carbon bio-filter；Oxidation using ozonation technology, Fenton oxidation technology or
One or more combinations in microwave oxidation.
3. high-salinity wastewater zero-emission method according to claim 1, which is characterized in that concentration makes TDS in waste water exist
20~60g/L；Concentration process is using one or more technique groups in NF membrane concentration, reverse osmosis concentration or electrodialysis concentration
It closes.
4. high-salinity wastewater zero-emission method according to claim 1, which is characterized in that melded system goes out hydraulic in the 3rd step
Degree is between 20~200mg/L；One kind in film softening, medicament softening or ion exchange resin softening can be used in softening process
Or kinds of processes combination.
5. high-salinity wastewater zero-emission method according to claim 1, which is characterized in that in the 4th step, in NF membrane concentrated water
NaCl and Na2SO4The concentration mass ratio of concentration（0.01~0.07）：1；Na in the concentrated water of NF membrane2SO4Mass concentration 8~
15%；In 5th step, the fresh water of NF membrane carry out concentration be using high pressure reverse osmosis membrane technique, DTRO techniques, electrodialysis process,
The combination of one or more of MVR evaporation technologies or multiple-effect evaporation technique；NaCl mass concentrations exist after the concentration of NF membrane fresh water
Between 10~20%.
6. high-salinity wastewater zero-emission method according to claim 1, which is characterized in that sulfate crystal mother liquor is by concentration
It is re-fed into later in NaCl crystal systems and carries out crystallization treatment, Na is re-fed into after the contracting of chlorination mother liquid of sodium overrich2SO4Crystal system
Carry out crystallization treatment.
7. a kind of high-salinity wastewater zero-emission processing unit, which is characterized in that including：
Pretreatment system（1）, for carrying out pretreatment removal of impurities to high-salt wastewater；
Concentration systems（2）, it is connected to pretreatment system（1）, for pretreatment system（1）Obtained waste water carries out at concentration
Reason；
Melded system（3）, it is connected to concentration systems（2）, for carrying out sofening treatment to the waste water after concentration；
NF membrane（4）, it is connected to melded system（3）, the separation for carrying out a divalent salts to the production water after sofening treatment；
Sulfate crystal system（5）, it is connected to NF membrane（4）Dope side obtain for nanofiltration dope crystallization treatment
Na2SO4；
Sodium chloride crystal system（6）, it is connected to NF membrane（4）Light liquid side obtain for the light liquid crystallization treatment of nanofiltration
NaCl。
8. high-salinity wastewater zero-emission processing unit according to claim 11, which is characterized in that sulfate crystal system
（5）, mother liquor outlet be connected to sodium chloride crystal system（6）, sodium chloride crystal system（6）Mother liquor outlet be connected to sodium sulphate
Crystal system（5）；The pretreatment system（1）Including pre-filtrating equipment, biofilter, oxidation unit, settler, oxidation
One or more combinations in device or ultrafiltration apparatus；Pre-filtrating equipment be sand filtering device, multi-medium filtering device or
One or more combinations in active carbon filtering device；Oxidation unit is ozone-oxidizing device, Fenton oxidation device or micro-
One or more combination biofilters in wave oxidation unit refer to activated carbon bio-filter device；The concentration systems
（2）Including one or more combinations in nanofiltration film condensing device, reverse osmosis concentrated compression apparatus or electrodialysis enrichment facility.
9. high-salinity wastewater zero-emission processing unit according to claim 7, which is characterized in that NF membrane（4）Light liquid side
It is connect with sodium chloride crystal system by enrichment facility.
10. high-salinity wastewater zero-emission processing unit according to claim 9, which is characterized in that enrichment facility is selected from high pressure
The group of one or more of reverse osmosis membrane apparatus, DTRO devices, electrodialysis plant, MVR vaporising devices or multi-effect evaporating device
It closes.
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