CN108117222A - A kind of coal chemical industry brine waste zero emission processing method - Google Patents
A kind of coal chemical industry brine waste zero emission processing method Download PDFInfo
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- CN108117222A CN108117222A CN201611072961.9A CN201611072961A CN108117222A CN 108117222 A CN108117222 A CN 108117222A CN 201611072961 A CN201611072961 A CN 201611072961A CN 108117222 A CN108117222 A CN 108117222A
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- Prior art keywords
- water
- reverse osmosis
- salt
- electrodialysis
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- 239000012267 brine Substances 0.000 title claims abstract description 30
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 title claims abstract description 30
- 239000002699 waste material Substances 0.000 title claims abstract description 30
- 239000003245 coal Substances 0.000 title claims abstract description 27
- 239000000126 substance Substances 0.000 title claims abstract description 25
- 238000003672 processing method Methods 0.000 title claims abstract description 7
- 238000001223 reverse osmosis Methods 0.000 claims abstract description 76
- 238000000034 method Methods 0.000 claims abstract description 64
- 150000003839 salts Chemical class 0.000 claims abstract description 60
- 239000002351 wastewater Substances 0.000 claims abstract description 44
- 238000002425 crystallisation Methods 0.000 claims abstract description 36
- 230000008025 crystallization Effects 0.000 claims abstract description 36
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims abstract description 35
- 238000000909 electrodialysis Methods 0.000 claims abstract description 35
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims abstract description 34
- 239000011780 sodium chloride Substances 0.000 claims abstract description 18
- 230000003647 oxidation Effects 0.000 claims abstract description 17
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 17
- 239000013078 crystal Substances 0.000 claims abstract description 14
- 229910052938 sodium sulfate Inorganic materials 0.000 claims abstract description 11
- 235000011152 sodium sulphate Nutrition 0.000 claims abstract description 11
- 239000012141 concentrate Substances 0.000 claims abstract description 9
- 238000004064 recycling Methods 0.000 claims abstract description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 94
- 239000012528 membrane Substances 0.000 claims description 50
- 238000000108 ultra-filtration Methods 0.000 claims description 24
- 238000005516 engineering process Methods 0.000 claims description 19
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 18
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 18
- 239000013505 freshwater Substances 0.000 claims description 17
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 15
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 14
- 239000002068 microbial inoculum Substances 0.000 claims description 14
- 239000003795 chemical substances by application Substances 0.000 claims description 13
- 239000012452 mother liquor Substances 0.000 claims description 13
- 239000010865 sewage Substances 0.000 claims description 12
- 238000001914 filtration Methods 0.000 claims description 11
- 238000001816 cooling Methods 0.000 claims description 10
- 238000004821 distillation Methods 0.000 claims description 10
- 239000007952 growth promoter Substances 0.000 claims description 10
- 238000004519 manufacturing process Methods 0.000 claims description 10
- 229920002401 polyacrylamide Polymers 0.000 claims description 10
- 238000001704 evaporation Methods 0.000 claims description 9
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 claims description 9
- 230000000844 anti-bacterial effect Effects 0.000 claims description 7
- 239000003899 bactericide agent Substances 0.000 claims description 7
- 159000000007 calcium salts Chemical class 0.000 claims description 7
- 238000007710 freezing Methods 0.000 claims description 7
- 239000007788 liquid Substances 0.000 claims description 7
- 230000000813 microbial effect Effects 0.000 claims description 7
- 230000001590 oxidative effect Effects 0.000 claims description 7
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 7
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 6
- 239000000701 coagulant Substances 0.000 claims description 6
- 238000005189 flocculation Methods 0.000 claims description 6
- 230000016615 flocculation Effects 0.000 claims description 6
- 230000008014 freezing Effects 0.000 claims description 6
- 159000000003 magnesium salts Chemical class 0.000 claims description 6
- 229910052751 metal Inorganic materials 0.000 claims description 6
- 239000002184 metal Substances 0.000 claims description 6
- 238000001556 precipitation Methods 0.000 claims description 6
- 239000004902 Softening Agent Substances 0.000 claims description 5
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical group [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 claims description 5
- 239000003814 drug Substances 0.000 claims description 5
- 230000008020 evaporation Effects 0.000 claims description 5
- 238000004062 sedimentation Methods 0.000 claims description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 4
- AVXURJPOCDRRFD-UHFFFAOYSA-N Hydroxylamine Chemical compound ON AVXURJPOCDRRFD-UHFFFAOYSA-N 0.000 claims description 4
- 230000001112 coagulating effect Effects 0.000 claims description 4
- -1 mantoquita Chemical class 0.000 claims description 4
- 244000005700 microbiome Species 0.000 claims description 4
- 239000010413 mother solution Substances 0.000 claims description 4
- 150000007524 organic acids Chemical class 0.000 claims description 4
- 229920000768 polyamine Polymers 0.000 claims description 4
- 239000011148 porous material Substances 0.000 claims description 4
- 239000000920 calcium hydroxide Substances 0.000 claims description 3
- 229910001861 calcium hydroxide Inorganic materials 0.000 claims description 3
- 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 claims description 3
- 229910000360 iron(III) sulfate Inorganic materials 0.000 claims description 3
- 239000013049 sediment Substances 0.000 claims description 3
- 150000001875 compounds Chemical class 0.000 claims description 2
- 229910052757 nitrogen Inorganic materials 0.000 claims description 2
- 230000001351 cycling effect Effects 0.000 claims 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims 1
- 239000010931 gold Substances 0.000 claims 1
- 229910052737 gold Inorganic materials 0.000 claims 1
- 238000011084 recovery Methods 0.000 abstract description 9
- 238000004148 unit process Methods 0.000 abstract description 2
- 238000006243 chemical reaction Methods 0.000 description 20
- 239000010408 film Substances 0.000 description 19
- 239000000047 product Substances 0.000 description 15
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 12
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 11
- 238000005345 coagulation Methods 0.000 description 9
- 230000015271 coagulation Effects 0.000 description 9
- 230000000694 effects Effects 0.000 description 7
- 239000010842 industrial wastewater Substances 0.000 description 7
- 239000007787 solid Substances 0.000 description 6
- 208000028659 discharge Diseases 0.000 description 5
- 239000003344 environmental pollutant Substances 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 231100000719 pollutant Toxicity 0.000 description 5
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 4
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
- 235000011116 calcium hydroxide Nutrition 0.000 description 4
- 238000005370 electroosmosis Methods 0.000 description 4
- JEGUKCSWCFPDGT-UHFFFAOYSA-N h2o hydrate Chemical compound O.O JEGUKCSWCFPDGT-UHFFFAOYSA-N 0.000 description 4
- 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 4
- 238000001728 nano-filtration Methods 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- 238000000926 separation method Methods 0.000 description 4
- 239000010802 sludge Substances 0.000 description 4
- 238000003889 chemical engineering Methods 0.000 description 3
- 230000035484 reaction time Effects 0.000 description 3
- 238000007670 refining Methods 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 238000005273 aeration Methods 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 229910052925 anhydrite Inorganic materials 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L calcium carbonate Substances [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- 229910000019 calcium carbonate Inorganic materials 0.000 description 2
- 230000001276 controlling effect Effects 0.000 description 2
- 229910000366 copper(II) sulfate Inorganic materials 0.000 description 2
- 230000001186 cumulative effect Effects 0.000 description 2
- 230000007812 deficiency Effects 0.000 description 2
- 238000011033 desalting Methods 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 238000011081 inoculation Methods 0.000 description 2
- 229910000359 iron(II) sulfate Inorganic materials 0.000 description 2
- 239000011777 magnesium Substances 0.000 description 2
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 2
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 2
- 238000009738 saturating Methods 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 description 2
- ATHGHQPFGPMSJY-UHFFFAOYSA-N spermidine Chemical compound NCCCCNCCCN ATHGHQPFGPMSJY-UHFFFAOYSA-N 0.000 description 2
- PFNFFQXMRSDOHW-UHFFFAOYSA-N spermine Chemical compound NCCCNCCCCNCCCN PFNFFQXMRSDOHW-UHFFFAOYSA-N 0.000 description 2
- 238000002207 thermal evaporation Methods 0.000 description 2
- FRXSZNDVFUDTIR-UHFFFAOYSA-N 6-methoxy-1,2,3,4-tetrahydroquinoline Chemical group N1CCCC2=CC(OC)=CC=C21 FRXSZNDVFUDTIR-UHFFFAOYSA-N 0.000 description 1
- 241000894006 Bacteria Species 0.000 description 1
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 229910021592 Copper(II) chloride Inorganic materials 0.000 description 1
- 229910021577 Iron(II) chloride Inorganic materials 0.000 description 1
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- HMNQNULAYXDEEQ-UHFFFAOYSA-N acetic acid;hydroxylamine Chemical compound ON.CC(O)=O HMNQNULAYXDEEQ-UHFFFAOYSA-N 0.000 description 1
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 1
- 239000001110 calcium chloride Substances 0.000 description 1
- 229910001628 calcium chloride Inorganic materials 0.000 description 1
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 description 1
- 238000001311 chemical methods and process Methods 0.000 description 1
- 230000009194 climbing Effects 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 150000001879 copper Chemical class 0.000 description 1
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 1
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 1
- 238000009295 crossflow filtration Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000000502 dialysis Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 230000009977 dual effect Effects 0.000 description 1
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 description 1
- 230000003631 expected effect Effects 0.000 description 1
- 239000011552 falling film Substances 0.000 description 1
- QJMMOFKVXUHETR-UHFFFAOYSA-N formic acid;hydroxylamine Chemical compound ON.OC=O QJMMOFKVXUHETR-UHFFFAOYSA-N 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000002309 gasification Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 230000008595 infiltration Effects 0.000 description 1
- 238000001764 infiltration Methods 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 239000003456 ion exchange resin Substances 0.000 description 1
- 229920003303 ion-exchange polymer Polymers 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- NMCUIPGRVMDVDB-UHFFFAOYSA-L iron dichloride Chemical compound Cl[Fe]Cl NMCUIPGRVMDVDB-UHFFFAOYSA-L 0.000 description 1
- 239000010808 liquid waste Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- AHEWZZJEDQVLOP-UHFFFAOYSA-N monobromobimane Chemical compound BrCC1=C(C)C(=O)N2N1C(C)=C(C)C2=O AHEWZZJEDQVLOP-UHFFFAOYSA-N 0.000 description 1
- 230000035772 mutation Effects 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 239000003002 pH adjusting agent Substances 0.000 description 1
- 239000012466 permeate Substances 0.000 description 1
- 239000002957 persistent organic pollutant Substances 0.000 description 1
- 238000000247 postprecipitation Methods 0.000 description 1
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 1
- 238000002203 pretreatment Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 230000003014 reinforcing effect Effects 0.000 description 1
- 239000011833 salt mixture Substances 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 238000004088 simulation Methods 0.000 description 1
- 235000010344 sodium nitrate Nutrition 0.000 description 1
- 239000004317 sodium nitrate Substances 0.000 description 1
- 239000004449 solid propellant Substances 0.000 description 1
- 239000002910 solid waste Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 229940063673 spermidine Drugs 0.000 description 1
- 229940063675 spermine Drugs 0.000 description 1
- 238000010977 unit operation Methods 0.000 description 1
Classifications
-
- 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
- C02F1/001—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
-
- 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
-
- 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
- C02F1/52—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
- C02F1/5236—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using inorganic agents
-
- 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
- C02F1/52—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
- C02F1/54—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using organic material
- C02F1/56—Macromolecular compounds
-
- 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
- C02F1/66—Treatment of water, waste water, or sewage by neutralisation; pH adjustment
-
- 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
- C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
- C02F2103/34—Nature of the water, waste water, sewage or sludge to be treated from industrial activities not provided for in groups C02F2103/12 - C02F2103/32
- C02F2103/36—Nature of the water, waste water, sewage or sludge to be treated from industrial activities not provided for in groups C02F2103/12 - C02F2103/32 from the manufacture of organic compounds
-
- 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
- C02F3/02—Aerobic processes
- C02F3/12—Activated sludge processes
Landscapes
- 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 present invention relates to a kind of coal chemical industry brine waste zero emission processing methods, include the following steps：(1) pre-process；(2) reverse-osmosis treated；（3）Advanced oxidation processing；（4）Biochemical treatment；(5) electrodialysis concentrates；(6) circulation crystallization.Compared with prior art, the brine waste zero emission that the method for the present invention provides divides salt treatment process method, while coal chemical industry wastewater zero emission or near-zero release is realized, the rate of recovery of salt is improved, and the sodium sulphate, saltcake and sodium chloride of high-quality can be recycled, realizes the recycling of crystal salt, film process unit process is stablized, service cycle is long, at low cost, the good economy performance of entire technique.
Description
Technical field
The invention belongs to environmental technology fields, and in particular to brine waste zero emission processing method, particularly coal chemical industry work
The Zero discharge treatment method of industry high slat-containing wastewater.
Background technology
Coal chemical industry is using coal as raw material, through chemical process it is made to be converted into the mistake of gas, liquid, solid fuel and chemicals
Journey.Coal chemical industry mainly includes coal gasification, liquefaction, destructive distillation and tar production and carbide acetylene chemical industry etc..Coal Chemical Engineering Project consumes
Water is huge, and the waste water water of generation is also high.And the most Coal Chemical Engineering Project in China is all distributed in water resource and lacks and lack
Receive the Northwest of sewage body.With the continuous adjustment of national environmental protection policy, the waste water of coal chemical industry enterprises needs to carry out maximum limit
Reuse is spent, reaches zero-emission.
Coal chemical industrial waste water is commonly divided into organic wastewater and brine waste.Brine waste mainly includes circulating sewage and change
Water station draining etc. is learned, for waste water recycling to greatest extent, it is generally the case that organic wastewater is through coagulation, two stage treatment and depth
After degree processing, brine waste processing system is also entered, carries out further reaching circulating water system water quality except salt treatment
Requirement.
Brine waste Treatment for Reuse mainly includes two class technologies, and one kind is membrane separation technique, and another kind of is thermal evaporation techniques.
Energy consumption is huge directly in a manner that thermal evaporation techniques obtain recycle-water for brine waste, therefore membrane separation technique is the master of this field
Flow Technique.Mainly there is film separation unit technology to include reverse osmosis, positive infiltration, Bipolar Membrane, dialysis, electrodialysis, microwave film, ultrafiltration
Film, NF membrane, biomembrane etc. for the waste water of separate sources, generally may be employed one of which membrane technology and handled,
Processing can be combined.Key technology difficulty of the membrane technology in application is membrane pollution problem, due to the complicated components of waste water,
There is tremendous influence to the service efficiency and service life of film.Currently used method is to carry out the pre- of depth to processing waste water
Processing and different type membrane technology are applied in combination, but the cost of depth pretreatment can greatly increase, existing combination skill
Art does not obtain expected effect, especially in the saliferous wastewater processing technology of coal chemical technology, some existing groups
Although conjunction technology can obtain higher recycle-water yield, without solving the problems, such as fouling membrane and membrane lifetime.
The target of saliferous wastewater processing technology is wastewater zero discharge, this just needs in solid form to return the salt in waste water
It receives, due to salt complicated components in waste water, it is more difficult to obtain meeting the salt for selling quality standard.The more acquisition salt-mixture of existing method,
It is difficult to sell and use, form reluctant solid waste.It, will be useless although theoretically can be by various process for separation and purification
Salt in water obtains the higher mono-salt of purity respectively, but since component is more, causes complex process, and cost increases, economically
It is difficult to bear.The particularly presence of Organic Pollutants in Wastewater and nitrogen-containing pollutant not only brings fouling membrane, while to carnallite
Integrated treatment and recycling bring difficulty, can not realize real near-zero release.Therefore how suitable technology is used
Organic pollution and nitrogen-containing pollutant in efficient process saline sewage are to ensure that subsequent film minimizing unit being capable of stable operation
Premise, only as far as possible reduce concentrate in pollutant concentration, can just make the carnallite finally generated realize comprehensive utilization into
For possibility.
CN104016529A discloses a kind of coal chemical industry brine waste processing side based on multi-stage countercurrent pole-reversing electroosmosis device
Method can improve 10 times or more of concentrated water concentration, fresh water yield to more than 85%.The technology passes through ozone oxidation, Multistage Membranes mistake
Filter and multi-stage countercurrent pole-reversing electroosmosis technology, improve fresh-water recovery rate, and alleviate electric dialyzator film to a certain extent
The problem of pollution, but pretreatment is of high cost, pre-processes the stability of film unit without good solution, electric dialyzator obtains
Recycle-water is still containing a small amount of salt, and general effect is general, and strong brine is not further processed scheme, fails to realize zero-emission
It puts.
CN104230124A disclose a kind of coal chemical industrial waste water carry out categorised collection, dual treatment technique and special set
It is standby, while the rate of recovery of water is improved, and obtain industrial salt.But the reverse osmosis in this process, independently used using three
Saturating unit using ion exchange even depth pretreatment mode, it is necessary to be pre-processed；Isolate and purify the film point of water and organic dope
More difficult acquisition ideal effect for current from unit；The Nacl of generation is mixed salt, it is difficult to sell or use.
CN103508602A discloses a kind of technique for the high salinity zero discharge of industrial waste water that film is integrated with evaporative crystallization, will
Industrial wastewater is delivered to reverse osmosis units, per-meate side effluent reuse, after filtering repeatedly after ultrafiltration pretreatment by high-pressure pump
Concentrate carry out electrodialysis process, the material after electrodialysis concentrates is evaporated and crystallizes, and obtains salt slurry and condensed water, right
Salt slurry is post-processed, recycling condensing water, electrodialysis fresh water reuse.This method is used reverse osmosis with electrodialysis simple combination,
Effect alone is each played, electrodialysis fresh water needs to reach reuse requirement, and intractability is high, and energy consumption is big, and fouling membrane is serious, whole
The stability deficiency of covering device, the solid salt in addition obtained is still mixed salt.
CN105565569A discloses a kind of the reinforcing depth concentration systems and its technique of high saliferous industrial wastewater, high saliferous
The adjusted pond of industrial wastewater adjusts-softens sedimentation basin precipitation-V-type filter-reverse osmosis dress of-one section of ultrafiltration apparatus intensive filtration
Putting concentration-ion exchange resin device goes hardness-nanofiltration device to divide salt；Wherein：Nanofiltration device concentrated water-frequently pole-reversing electroosmosis dress
Put concentration, production water-advanced oxidation device oxidation-total water producing tank, concentrated water-freezing and crystallizing system crystallization-sulfate crystal；It receives
Filter device production-two sections of reverse osmosis unit concentration-frequently pole-reversing electroosmosis devices of water concentrate again, produce water-advanced oxidation device oxygen
Change-total water producing tank, concentrated water-MVR evaporated crystallization devices crystallization-sodium chloride crystallization.This method is by nanofiltration, frequently pole-reversing electric osmose
The membrane technologies such as analysis, reverse osmosis are combined, but the effect between different membrane technologies does not effectively integrate, and pretreatment needs ion to hand over
Even depth processing is changed, cost is higher；Although having respectively obtained sodium chloride crystallization and sulfate crystal, by analysis and test,
Which obtains the purity of crystal salt if necessary to ensure, then needs a certain amount of high-concentration salt-containing wastewater of outer row, it is impossible to realize
Zero-emission, the salt rate of recovery also need to further improve.
To sum up, the treatment process of brine waste particularly Coal Chemical Engineering Industry brine waste is provided in Sewage treatment rate, Nacl
Source, the salt rate of recovery, film unit steady running, reduce production cost, realize the complex arts effect such as zero-emission in terms of, it is necessary into
The optimization of one step.
The content of the invention
For deficiency existing for current brine waste treatment process, the present invention provides a kind of processing of brine waste zero emission
Method, particularly coal chemical industry brine waste zero emission processing method are realizing the same of coal chemical industry wastewater zero emission or near-zero release
When, the rate of recovery of salt is improved, and the sodium sulphate, saltcake and sodium chloride of high-quality can be recycled, the recycling of crystal salt is realized,
Multistage Membranes processing unit process is stablized, and service cycle is long, at low cost, the good economy performance of entire technique.
Coal chemical industry brine waste zero emission processing method of the present invention, including step：
（1）Pretreatment.Pretreatment includes softening, coagulating sedimentation, coarse filtration and ultra-filtration process, and pretreatment water outlet carries out reverse osmosis place
Reason.According to water water quality, pretreatment can also include the processes such as oil removing, biochemical treatment, the even amount processing of homogeneous.
（2）Reverse-osmosis treated.Reverse osmosis and the reverse osmosis combination of high pressure preventing membrane pollution combination membrane process is pressed in, it is pre- to locate
Reverse osmosis, the reverse osmosis production water reuse of middle pressure is pressed in reason water outlet in carrying out first, the reverse osmosis concentrated water of middle pressure and electrodialysis cell
Fresh water is jointly reverse osmosis into horizontal high voltage, the reverse osmosis production water reuse of high pressure, and the reverse osmosis concentrated water of high pressure carries out electrodialysis concentration.It returns
Needed for finger is reused for commercial plant or other purposes.
（3）Advanced oxidation processing：High pressure reverse osmosis concentrated water carries out advanced oxidation processing first, mainly using Fenton oxidation
Mode, improve brine waste in organic pollution biodegradability.
（4）Biochemical treatment.Advanced oxidation unit water outlet enters biochemical unit, is added using in existing membrane bioreactor
The mode of salt tolerant microbial inoculum and microbial growth promoters realizes the removal of COD and total nitrogen.The microbial inoculum is salt tolerant microbial inoculum.It is described
Microbial growth promoters include metal salt, polyamines and organic acid azanol, and the metal salt is by calcium salt, mantoquita, magnesium salts
And/or ferrous salt composition.
（5）Electrodialysis concentrates.Biochemical unit water outlet is softened, after the pretreatment of coagulating sedimentation, coarse filtration and ultrafiltration, then
It carries out electrodialysis further to be concentrated, electrodialysis fresh water Xun Huan is as high pressure feed water by reverse osmosis, and the concentrated water generated is followed
Ring crystallizes.
（6）Circulation crystallization.Electrodialysis concentrated water carries out flush distillation crystallization first, obtains sulfate crystal and a mother liquor,
One time mother liquor carries out freezing and crystallizing, obtains saltcake and secondary mother liquid, and secondary mother liquid carries out double evaporation-cooling crystallization, obtains sodium chloride knot
Brilliant and mother liquor three times, three times Recycling Mother Solution to flush distillation crystallize, realize sewage zero-discharge.
Further, in the step (1), softening, flocculation and precipitation process carry out in highly dense clarifying basin, coarse filtration mistake
Journey carries out in V-type filter tank, and the average pore size of ultrafiltration membrane is 1-100 nm.The even amount process of homogeneous carries out in regulating reservoir.
Further, in the step (1), highly dense clarifying basin front end is equipped with medicine machine, adds softening agent and flocculation
Agent, highly dense clarifying basin exit also are provided with medicine machine, any one for adding hydrochloric acid or sulfuric acid respectively adjusts pH to 6.5-
7.5 and non oxidizing bactericide.
Further, in the step (1), softening agent is the different addition differences of water quality according to coal chemical industry brine waste
The one or more of the calcium hydroxide of concentration, sodium hydroxide and sodium carbonate；Coagulant is the water quality according to coal chemical industry brine waste
Difference adds in the compound coagulant of suitable coagulant, coagulant preferred polymeric ferric sulfate (PFS) and polyacrylamide (PAM),
The concentration of PFS is that the concentration of 5-200 mg/L, PAM are 0.5-12 mg/L.
Further, in the step (1), after preprocessed technique, waste water index, which will be controlled to hardness, is less than 200
Mg/L, COD are less than 70 mg/L, and turbidity is less than 3 NTU.
Further, in the step (2), the operating pressure of middle pressure reverse osmosis membrane is 1-3 MPa, high pressure reverse osmosis membrane
Operating pressure be 3-6 MPa, middle press mold and high-pressure membrane use cross-flow filtration.Middle press mold and high-pressure membrane can select this field
It is common reverse osmosis to use film.
Further, in the step (2), after two steps ro separating technology, the reverse osmosis generation of high pressure is dense
The TDS of water is up to 50000 more than mg/L.
Further, in the step (3), advanced oxidation is using Fenton oxidation, in Fenton reaction tanks
It carries out, chemicals dosing plant is equipped in Fonten reaction tanks inlet, hydrochloric acid and sulfuric acid any one is added, by high-pressure membrane concentrated water
PH is adjusted to 2-4, and the concentration difference of the COD in water adds the ferrous salt and hydrogen peroxide of various concentration, can successively or together
When ferrous salt and hydrogen peroxide are added in into the waste water, still, the two must be added in waste water independently of one another, it is impossible to be used
First the two is mixed and adds this mode in waste water.When the entire reaction time is 1-4 small.
Further, in the step (4), mainly using membrane bioreactor and specific salt tolerant microbial inoculum and micro- is added
Biological growth accelerating agent come realize in high saline sewage organic pollution depth remove.Existing membrane bioreactor, such as
It can be biological aerated filter（BAF）, membrane bioreactor（MBR）, moving bed membrane bioreactor（MBBR）Deng, it is preferred to use
BAF.The operating condition of membrane bioreactor is：Temperature is 20-40 DEG C, pH 7-9, dissolved oxygen concentration 0.5-1.5mg/L.
Step of the present invention（4）Microbial inoculum using the Facultative Halophiles described in CN201210130645.8 or CN201210130644.3
Agent, dosage are the 0.01%-0.1% of handled wastewater volume per hour.Microbial growth promoters can be according to
It is prepared by CN201410585430.4, CN201410585449.9 and CN201410585485.5 the method.
Step of the present invention（4）The proportioning of active principle is as follows in the microbial growth promoters：Metal salt is 40-100
Parts by weight are preferably 50-80 parts by weight, and polyamines are 5-30 parts by weight, preferably 10-20 parts by weight, organic acid azanol
It is preferably 2-10 parts by weight for 0.5-15 parts by weight.The metal salt is made of calcium salt, mantoquita, magnesium salts and/or ferrous salt,
Middle metal salt can be calcium salt, magnesium salts and mantoquita, wherein Ca2+、Mg2+And Cu2+Molar ratio be（5-15）:（5-25）:（0.5-
5）, it is preferably（8-12）:（10-20）:（1-4）；Either calcium salt, ferrous salt and mantoquita, wherein Ca2+、Fe2+And Cu2+Mole
Than for（5-15）:（1-8）:（0.5-5）, it is preferably（8-12）:（2-6）:（1-4）；Either calcium salt, magnesium salts, ferrous salt and copper
Salt, wherein Ca2+、Mg2+、Fe2+And Cu2+Molar ratio be（5-15）:（5-25）:（1-8）:（0.5-5）, it is preferably（8-12）:
（10-20）:（2-6）:（1-4）.
In the present invention, the calcium salt in the growth promoter is CaSO4Or CaCl2, preferably CaSO4；Magnesium salts is MgSO4
Or Mg Cl2, preferably MgSO4；Ferrous salt is FeSO4Or FeCl2, preferably FeSO4；Mantoquita is CuSO4Or CuCl2, preferably
CuSO4。
In the present invention, the polyamines in the growth promoter are the mixture of spermine, spermidine or both.Institute
The organic acid azanol stated is the mixture of formic acid azanol, hydroxylamine acetate or both.
In the present invention, the dosage of the growth promoter is according to accelerating agent active principle total concentration in sewage disposal system
1-20mg/L is added, and preferably 5-15mg/L is added.
Further, in the step (5), softening, flocculation sediment process carry out in highly dense clarifying basin, coarse filtration process
It is carried out in V-type filter tank, the average pore size of ultrafiltration membrane is 1-100 nm.Highly dense clarifying basin front end is equipped with medicine machine, adds soft
Agent and flocculant, highly dense clarifying basin exit also are provided with medicine machine, add pH adjusting agent and adjust pH to 6.5-7.5, press
It needs to add non oxidizing bactericide simultaneously.
Further, in the step (5), softening agent be according to the water quality of biochemical treatment water outlet it is different add in it is different dense
The one or more of the calcium hydroxide of degree, sodium hydroxide and sodium carbonate；For flocculant using PAM, concentration is 2-16 mg/L.
Electrodialysis water inlet index, which will be controlled to hardness, after above-mentioned pretreatment is less than 50 mg/L, COD less than 70 mg/L, and turbidity is less than
3 NTU。
Further, in the step (5), after being concentrated by electrodialysis, the TDS in concentrated water is up to 200000
More than mg/L.Electrodialysis fresh water TDS is 25000 below mg/L, generally in 10000 more than mg/L, preferably in 15000 mg/L
More than.
Further, in the step (6）In, when flush distillation crystallizes, the temperature of evaporation and concentration is 50~150 DEG C, knot
Brilliant temperature is 50~100 DEG C；When double evaporation-cooling crystallizes, the temperature of evaporation and concentration is 50~150 DEG C, and crystallization temperature is 30~50
℃；The temperature of freezing and crystallizing is 0~-8 DEG C.
Further, in the step (6), the device that when evaporative crystallization uses includes evaporator and crystallizer.Evaporation
Device is respectively any one of natural-circulation evaporator, forced-circulation evaporator, climbing film evaporator or falling film evaporator；Crystallizer
Any one respectively in Oslo crystallizers, DP crystallizers or more mutation of pattern.Evaporator and crystallizer can be these
The existing equipment in field is designed by the prior art.
Further, in the step (6), sodium sulphate, saltcake and the sodium chloride of generation are collected by centrifugal dehydrator.
The purity of generation sodium sulphate can reach more than 95%, and product quality reaches III class certified products quality mark of national standard industrial anhydrous sodium sulfate
It is accurate.The purity of the sodium chloride of generation can reach more than 98%, and product quality reaches national standard refining industrial salt two level quality standard.Awns
Nitre product quality more than 90%.Product purity is calculated in mass percent.
The method of the present invention obtains following complex art effect：
1. aggregate measures ensure that film unit（Reverse osmosis and electrodialysis）Stable operation.Using the reverse osmosis of two-stage different pressures
Unit, while by the electrodialysis cell of particular manner of operation（Still there is relatively high salt content in fresh water）Organic combination is to reverse osmosis
In saturating flow, three's flow and condition coordinated while ensureing cycles of concentration, going out water speed, realize film unit
The problem of long period stable operation, membrane lifetime caused by effectively controlling membrane pollution problem and film frequent regeneration is reduced.Using
During the present invention program, film unit can be shown with steady running 3 years or more, experiment and simulation if the coordinated groups is not used to collaborate
The cooperation of journey and condition, under identical pretreatment condition, film unit can only generally be run 1~1.5 year.
2. pre-treatment unit operations are at low cost.By the flow of film unit and condition coordinated, reduce film unit into
The severity requirement of water index, water inlet pretreatment operation can substantially reduce operating cost.For example, the present invention can be with use cost
The modes such as relatively low softening, flocculation sediment, coarse filtration, ultrafiltration, these methods are at low cost, operating stablize, be not required in the prior art from
The pretreatment units of high cost such as sub- exchange, nanofiltration.
3. biochemical unit is used cooperatively by salt tolerant microbial inoculum and accelerating agent, the nitrate anion in sewage can be removed, is removed
Sodium nitrate ingredient in follow-up carnallite reduces the intractability of carnallite.It is organic can also to remove part for biochemical unit simultaneously
Pollutant reduces the processing cost of the operations such as front end Fenton oxidation unit and post precipitation.
4. point salt scheme is on the basis of ensureing to crystallize purity salt, discharging any waste liquor, does not realize zero-emission really.To sodium sulphate
It is crystallized using two kinds of crystallization modes, respectively with the two kinds of product crystallizations of sulfate crystal and sodium chloride crystal, by its in waste water
Its impurity is reasonably allocated in different crystallized products, and the unqualified problem of purity salt is crystallized caused by avoiding mother liquor complete alternation,
Ensure to realize wastewater zero discharge on the premise of crystal salt is up-to-standard.If sodium sulphate is separated using a kind of crystalline salt form, warp
Experiments have shown that obtain two kinds of crystal salts（Sodium sulphate and sodium chloride）Purity is unqualified；If it is intended to ensure that two kinds of crystallization purity salts close
Lattice then need outer row's salt bearing liquid wastes.Therefore, the present invention program is realizing coal chemical industry wastewater zero emission or while near-zero release,
The rate of recovery of salt is improved, and the sodium sulphate, saltcake and sodium chloride of high-quality can be recycled, realizes the recycling of crystal salt.Together
When, since the technique of sub-prime salt is in end, technique is also simplified, reduces construction cost.
Description of the drawings
Fig. 1 is the cell arrangement composition and connection relationship diagram for realizing the method for the present invention.
Specific embodiment
Below in conjunction with Fig. 1, a kind of coal chemical industry brine waste zero emission whole process treatment process is described in further detail, it is of the invention
Protection domain is not limited to embodiment disclosed below.Wherein each unit is using this field conventional equipment or equipment, with reference to this hair
Bright following specific embodiments, those skilled in the art can carry out conventional adjustment according to waste water quality, obtain different quality
Processing control condition is optimized, each unit is made to reach controlled effluent quality requirement, realizes final technological effect.
Microbial growth promoters involved in the present invention are prepared according to 1 ratio of table and formula, and the promoter concentration is
0.5g/L。
The formula and ratio of 1 microbial growth promoters of table
Salt tolerant microbial inoculum involved in the present invention is prepared according to the proportioning shown in table 2, and the bacterium being related to exists
It is fully disclosed in CN201210130645.8 and CN201210130644.3.
The composition and ratio of the different microbial inoculums of table 2
| Microbial inoculum | Thalline forms | Proportioning |
| Ⅱ-A | FSDN-A:SDN-3:DN-3: FDN-1:FDN-2 | 1:0.5:0.5:0.5:0.5 |
| Ⅱ-B | FSDN-C:SDN-3:DN-3: FDN-1:FDN-2 | 1:0.5:0.5:0.5:0.5 |
Embodiment 1
The mean concentration of high each pollutant of saliferous industrial wastewater is：COD is 80 mg/L, total hardness is (with CaCO3Meter) it is 1500
Mg/L, total alkalinity are (with CaCO3Meter) for 800 mg/L, silica it is that 30 mg/L, TDS are 5000 mg/L, wherein, nitrate anion
Ion concentration is 40mg/L, and chlorine ion concentration is 700 mg/L, sulfate ion concentration is 1000 mg/L, pH value 8.Such as Fig. 1
It is shown, using the coal chemical industry brine waste zero emission treatment process, include the following steps：
（1）Brine waste enters highly dense clarifying basin, and according to the water quality of brine waste, 1.8 are added in the reaction zone of highly dense clarifying basin
G/L calcium hydroxides so that after pH value maintains 10.5-11.0, add 2.0 g/L sodium carbonate, then add the PFS of 10 mg/L
Coagulation, the PAM of 1mg/L help solidifying, after the abundant coagulation of reaction zone, the settling section precipitation in highly dense pond are entered, finally highly dense
The exit of clarifying basin adds hydrochloric acid or sulfuric acid adjusts pH to 7 or so, and adds non oxidizing bactericide and prevent fouling membrane.Through
After processing, highly dense clarifying basin goes out the water hardness less than 200 mg/L.
（2）Suspended matter, colloidal solid in water removal etc. is removed in highly dense clarifying basin water outlet through V-type filter tank, most at last in waste water
Turbidity control is controlled in 50 mg/L or so, entered in ultrafiltration apparatus in 3 NTU or so, COD.The operating pressure of ultrafiltration apparatus
For 0.05 MPa, after being further processed through ultrafiltration, finally so that waste water index to reach hardness small less than 200 mg/L, COD
In 50 mg/L, nitrate ion concentration 40mg/L, turbidity is less than 1 NTU.
（3）Waste water after preprocessed enters reverse osmosis unit and is concentrated, and it is reverse osmosis that reverse osmosis unit includes middle pressure
It is reverse osmosis with high pressure, and the safeguard equipped with 25 μm of millipore filter as water inlet.It is anti-that middle pressure reverse osmosis unit, which uses,
The middle pressure reverse osmosis membrane of pollution, operating pressure are 2 MPa or so；The fresh water of the reverse osmosis concentrated water of middle pressure and electrodialysis cell enters
In high pressure reverse osmosis unit, high pressure reverse osmosis unit operating pressure is in 3.5 MPa or so, and middle pressure is reverse osmosis and high pressure is reverse osmosis
Fresh water COD is less than 30 mg/L, and TDS is less than 300 mg/L, and hardness is less than 10 mg/L, and reaching circulating cooling make-up water water quality index will
It asks.The service life of reverse osmosis membrane assembly can reach 3 years or more.Reverse osmosis concentrated water TDS reaches 50000 mg/L, wherein containing
COD concentration average out to 530 mg/L, nitrate ion concentration average out to 380mg/L.
（4）The reverse osmosis concentrated water of high pressure enters Fenton reaction tanks, the inlet of Fenton reaction tanks add hydrochloric acid or
Sulfuric acid adjusts pH value to 3 or so, adds mass ratio successively in Fenton reaction tanks as 20:1 hydrogen peroxide and it is ferrous from
Son, and the mass ratio of hydrogen peroxide and COD is made to reach 2:1,2 h of reaction time.After Fenton oxidation, the COD in water is dense
It spends for 500 mg/L, nitrate ion concentration average out to 380mg/L.
（5）The water outlet of Fenton reaction tanks enters in biological aerated filter the removal for carrying out COD and nitrate anion.Aeration and biological
Started in advance according to sludge concentration 4000mg/L inoculation of activated-sludge in filter tank.Operating condition is：Temperature is 27 DEG C, and pH is
7.5, dissolved oxygen concentration 1.0mg/L.0.1% according to handled wastewater volume per hour in biological aerated filter add it is resistance to
II-A of salt microbial inoculum, while add microorganism growth according to accelerating agent active principle total concentration 15mg/L in sewage disposal system and promote
I-A of agent.It is less than 200 mg/L by biological aerated filter treated effluent COD concentration, nitrate ion concentration is less than
100mg/L。
（6）The water outlet of biochemical unit enters highly dense clarifying basin, according to its water quality, is added in the reaction zone of highly dense clarifying basin
Sodium hydroxide so that after pH value maintains 11.5 or so, 2.2 g/L sodium carbonate are added, then add the PFS coagulations of 50 mg/L,
The PAM of 5mg/L help it is solidifying, after the abundant coagulation of reaction zone, enter highly dense pond settling section precipitation, finally in highly dense clarifying basin
Exit add hydrochloric acid or sulfuric acid adjusts pH to 7 or so, and add non oxidizing bactericide and prevent fouling membrane.Through processing
Afterwards, highly dense clarifying basin goes out the water hardness less than 50 mg/L.
（7）Suspended matter, colloidal solid in water removal etc. is removed in highly dense clarifying basin water outlet through V-type filter tank, most at last in waste water
Turbidity is controlled in 3 NTU or so, is entered in ultrafiltration apparatus.The operating pressure of ultrafiltration apparatus be 0.05 MPa, through ultrafiltration into
After the processing of one step, finally so that waste water index hardness is less than 50 mg/L, COD and is less than 70 mg/L, turbidity is less than 1 NTU.
（8）Waste water enters electrodialysis plant and further concentrates, and working voltage is 40 V, in order to ensure electrodialytic long week
Phase stable operation will produce water（Fresh water）TDS be set to 15000 mg/L or so, enter in high pressure reverse osmosis membrane and further carry out
Desalting processing；TDS in its concentrated water then reaches 200000 more than mg/L, into evaporative crystallization unit.By the way that electrodialysis is controlled to fill
Put production water still have higher salt content, and with reverse osmosis units organic assembling, realize reverse osmosis units long period stablize fortune
While turning, the long period steady running of electrodialysis cell is also ensured.
（9）In flush distillation crystallization apparatus, under the evaporating temperature, 50-80 DEG C of crystallization temperature at 100 DEG C, obtain
Product quality reaches the sodium sulphate of III class certified products quality standard of national standard industrial anhydrous sodium sulfate；Remaining mother liquor is crystallized to enter
It is further obtained under -5 DEG C or so of crystallization temperature in freezing and crystallizing device, purity is more than 90% saltcake；Remaining liquid
Body is entered back into double evaporation-cooling crystallization apparatus, and product matter is obtained under the evaporating temperature, 30-50 DEG C of crystallization temperature at 100 DEG C
Amount reaches the sodium chloride of national standard refining industrial salt two level quality standard, and double evaporation-cooling is controlled to crystallize remaining crystalline mother solution TDS and is
400000 more than mg/L, then remaining salt in evaporative crystallization mother liquor again is recycled in flush distillation crystallization, by following
Ring process and condition control, realize that three kinds of crystallized product purity are qualified, and improve the rate of recovery of water and salt.For circulating mother liquor
COD is cumulative too high（Such as reach 10000 mg/L or so）When, it can be by being recycled to Fenton reaction tanks or other means progress
Processing.
Embodiment 2
As shown in Figure 1, the waste water identical with embodiment 1 is handled using the coal chemical industry brine waste zero emission treatment process,
Include the following steps：
（1）Brine waste enters highly dense clarifying basin, and according to the water quality of brine waste, 1.8 are added in the reaction zone of highly dense clarifying basin
G/L calcium hydroxides so that after pH value maintains 11.0-11.5, add 2.5 g/L sodium carbonate, then add the PFS of 50 mg/L
Coagulation, the PAM of 5mg/L help solidifying, after the abundant coagulation of reaction zone, the settling section precipitation in highly dense pond are entered, finally highly dense
The exit of clarifying basin adds hydrochloric acid or sulfuric acid adjusts pH to 7 or so, and adds non oxidizing bactericide and prevent fouling membrane.Through
After processing, highly dense clarifying basin goes out the water hardness less than 200 mg/L.
（2）Suspended matter, colloidal solid in water removal etc. is removed in highly dense clarifying basin water outlet through V-type filter tank, most at last in waste water
Turbidity control is controlled in 50 mg/L or so, entered in ultrafiltration apparatus in 3 NTU or so, COD.The operating pressure of ultrafiltration apparatus
For 0.05 MPa, after being further processed through ultrafiltration, finally so that waste water index to reach hardness small less than 200 mg/L, COD
In 50 mg/L, nitrate ion concentration 40mg/L, turbidity is less than 1 NTU.
（3）Waste water after preprocessed enters reverse osmosis unit and is concentrated, and it is reverse osmosis that reverse osmosis unit includes middle pressure
It is reverse osmosis with high pressure, and the safeguard equipped with 25 μm of millipore filter as water inlet.It is anti-that middle pressure reverse osmosis unit, which uses,
The middle pressure reverse osmosis membrane of pollution, operating pressure are 1.5 MPa or so；The fresh water of the reverse osmosis concentrated water of middle pressure and electrodialysis cell into
Enter in high pressure reverse osmosis unit, high pressure reverse osmosis unit operating pressure is in 4.0 MPa or so, and middle pressure is reverse osmosis and high pressure is reverse osmosis
Fresh water COD be less than 30 mg/L, TDS be less than 300 mg/L, hardness be less than 10 mg/L, reach circulating cooling make-up water water quality index will
It asks.The service life of reverse osmosis membrane assembly can reach 3 years or more.Reverse osmosis concentrated water TDS reaches 50000 mg/L, wherein containing
COD concentration average out to 530 mg/L, nitrate ion concentration average out to 380mg/L.
（4）The reverse osmosis concentrated water of high pressure enters Fenton reaction tanks, the inlet of Fenton reaction tanks add hydrochloric acid or
Sulfuric acid adjusts pH value to 3 or so, adds mass ratio successively in Fenton reaction tanks as 10:1 hydrogen peroxide and it is ferrous from
Son, and the mass ratio of hydrogen peroxide and COD is made to reach 2:1,1.5 h of reaction time.After Fenton oxidation, the COD in water
Concentration is 500 mg/L, nitrate ion concentration average out to 380mg/L.
（5）The water outlet of Fenton reaction tanks enters in biological aerated filter the removal for carrying out COD and nitrate anion.Aeration and biological
Started in advance according to sludge concentration 4000mg/L inoculation of activated-sludge in filter tank.Operating condition is：Temperature is 27 DEG C, and pH is
7.5, dissolved oxygen concentration 1.0mg/L.0.1% according to handled wastewater volume per hour in biological aerated filter add it is resistance to
II-B of salt microbial inoculum, while add microorganism growth according to accelerating agent active principle total concentration 15mg/L in sewage disposal system and promote
I-B of agent.It is less than 200 mg/L by biological aerated filter treated effluent COD concentration, nitrate ion concentration is less than
100mg/L。
（6）The water outlet of biochemical unit enters highly dense clarifying basin, according to its water quality, is added in the reaction zone of highly dense clarifying basin
Sodium hydroxide so that after pH value maintains 11.5 or so, 2.5 g/L sodium carbonate are added, then add the PFS coagulations of 50 mg/L,
The PAM of 5mg/L help it is solidifying, after the abundant coagulation of reaction zone, enter highly dense pond settling section precipitation, finally in highly dense clarifying basin
Exit add hydrochloric acid or sulfuric acid adjusts pH to 7 or so, and add non oxidizing bactericide and prevent fouling membrane.Through processing
Afterwards, highly dense clarifying basin goes out the water hardness less than 50 mg/L.
（7）Suspended matter, colloidal solid in water removal etc. is removed in highly dense clarifying basin water outlet through V-type filter tank, most at last in waste water
Turbidity is controlled in 3 NTU or so, is entered in ultrafiltration apparatus.The operating pressure of ultrafiltration apparatus be 0.05 MPa, through ultrafiltration into
After the processing of one step, finally so that waste water index hardness is less than 50 mg/L, COD and is less than 70 mg/L, turbidity is less than 1 NTU.
（8）Waste water enters electrodialysis plant and further concentrates, and working voltage is 40 V, in order to ensure electrodialytic length
Cycle stability is run, and will produce water（Fresh water）TDS be set to 20000 mg/L or so, enter in high pressure reverse osmosis membrane further into
Row desalting processing；TDS in its concentrated water then reaches 200000 more than mg/L, into evaporative crystallization unit.By controlling electrodialysis
Device production water still have higher salt content, and with reverse osmosis units organic assembling, realize reverse osmosis units long period stablize
While operating, the long period steady running of electrodialysis cell is also ensured.
（9）In flush distillation crystallization apparatus, under the evaporating temperature, 80-100 DEG C of crystallization temperature at 110 DEG C, obtain
Product quality reaches the sodium sulphate of III class certified products quality standard of national standard industrial anhydrous sodium sulfate；Remaining mother liquor is crystallized to enter
It is further obtained under -5 DEG C or so of crystallization temperature in freezing and crystallizing device, purity is more than 92% saltcake；Remaining liquid
Body is entered back into double evaporation-cooling crystallization apparatus, and product matter is obtained under the evaporating temperature, 30-50 DEG C of crystallization temperature at 100 DEG C
Amount reaches the sodium chloride of national standard refining industrial salt two level quality standard, and double evaporation-cooling is controlled to crystallize remaining crystalline mother solution TDS and is
400000 more than mg/L, then remaining salt in evaporative crystallization mother liquor again is recycled in flush distillation crystallization, by following
Ring process and condition control, realize that three kinds of crystallized product purity are qualified, and improve the rate of recovery of water and salt.For circulating mother liquor
COD is cumulative too high（Such as reach 10000 mg/L or so）When, it can be by being recycled to Fenton reaction tanks or other means progress
Processing.
Claims (15)
1. a kind of coal chemical industry brine waste zero emission processing method, including step：
（1）Pretreatment；Pretreatment includes softening, coagulating sedimentation, coarse filtration and ultra-filtration process, and pretreatment water outlet carries out reverse osmosis place
Reason；
（2）Reverse-osmosis treated；Reverse osmosis and the reverse osmosis combination of high pressure preventing membrane pollution combination membrane process is pressed in, is pre-processed out
Water presses the fresh water of reverse osmosis, the reverse osmosis production water reuse of middle pressure, the reverse osmosis concentrated water of middle pressure and electrodialysis cell in carrying out first
Jointly reverse osmosis into horizontal high voltage, the reverse osmosis production water reuse of high pressure, the reverse osmosis concentrated water of high pressure carries out electrodialysis concentration；
（3）Advanced oxidation processing：High pressure reverse osmosis concentrated water carries out advanced oxidation processing first, the main side for using Fenton oxidation
Formula improves the biodegradability of organic pollution in brine waste；
（4）Biochemical treatment；Advanced oxidation unit water outlet enters biochemical unit, using adding salt tolerant microbial inoculum in membrane bioreactor
With the mode of microbial growth promoters, the removal of COD and total nitrogen is realized；
（5）Electrodialysis concentrates；Biochemical treatment water outlet is softened, after the pretreatment of coagulating sedimentation, coarse filtration and ultrafiltration, then carries out
Electrodialysis is further concentrated, and electrodialysis fresh water Xun Huan is as high pressure feed water by reverse osmosis, and the concentrated water generated carries out cycling knot
It is brilliant；
（6）Circulation crystallization；Electrodialysis concentrated water carries out flush distillation crystallization first, obtains sulfate crystal and a mother liquor, once
Mother liquor carries out freezing and crystallizing, obtains saltcake and secondary mother liquid, and secondary mother liquid carries out double evaporation-cooling crystallization, obtain sodium chloride crystallization and
Mother liquor three times, three times Recycling Mother Solution to flush distillation crystallize, realize sewage zero-discharge.
2. according to the method for claim 1, it is characterised in that：In step (1), softening, flocculation and precipitation process are highly dense
It is carried out in clarifying basin, coarse filtration process carries out in V-type filter tank, and the average pore size of ultrafiltration membrane is 1-100 nm.
3. according to the method for claim 2, it is characterised in that：In step (1), highly dense clarifying basin front end is set equipped with dosing
It is standby, add softening agent and flocculant, highly dense clarifying basin exit is equipped with medicine machine, adds any one of hydrochloric acid or sulfuric acid respectively
Kind adjusts pH to 6.5-7.5 and non oxidizing bactericide.
4. according to the method for claim 1, it is characterised in that：In step (1), softening agent is calcium hydroxide, sodium hydroxide
With the one or more of sodium carbonate；Coagulant is the compound coagulant of bodied ferric sulfate and polyacrylamide, bodied ferric sulfate
Concentration is 5-200 mg/L, and the concentration of polyacrylamide is 0.5-12 mg/L.
5. according to the method for claim 1, it is characterised in that：In step (1), after preprocessed technique, waste water index
Control to hardness is less than 200 mg/L, COD and is less than 70 mg/L, turbidity is less than 3 NTU.
6. according to the method for claim 1, it is characterised in that：In step (2), the operating pressure of middle pressure reverse osmosis membrane is 1-
3 MPa, the operating pressure of high pressure reverse osmosis membrane is 3-6 MPa.
7. according to the method described in claim 1 or 6, it is characterised in that：In step (2), by two steps ro separating technology
Afterwards, the reverse osmosis TDS for generating concentrated water of high pressure reaches 50000 more than mg/L.
8. according to the method for claim 1, it is characterised in that：In step (4), the salt tolerant microbial inoculum that biochemical treatment adds uses
Salt tolerant microbial inoculum described in CN201210130645.8 or CN201210130644.3, dosage are handled wastewater volume per hour
0.01%-0.1%.
9. according to the method for claim 1, it is characterised in that：In step (4), the microorganism growth that biochemical treatment adds promotees
The proportioning of active principle is as follows into agent：Metal salt is 40-100 parts by weight, is preferably 50-80 parts by weight, and polyamines are
5-30 parts by weight are preferably 10-20 parts by weight, and organic acid azanol is 0.5-15 parts by weight, is preferably 2-10 parts by weight；The gold
Belong to salt to be made of calcium salt, mantoquita, magnesium salts and/or ferrous salt.
10. according to the method for claim 1, it is characterised in that：In step (4), the microorganism that biochemical treatment adds grows
The dosage of accelerating agent is added according to accelerating agent active principle total concentration 1-20mg/L in sewage disposal system, preferably 5-
15mg/L is added.
11. according to the method for claim 1, it is characterised in that：In step (5), softening, flocculation sediment process are highly dense clear
It is carried out in clear pond, coarse filtration process carries out in V-type filter tank, and the average pore size of ultrafiltration membrane is 1-100 nm.
12. according to the method for claim 11, it is characterised in that：In step (5), electrodialysis water inlet index will be controlled to hard
Degree is less than 50 mg/L, COD and is less than 70 mg/L, and turbidity is less than 3 NTU.
13. according to the method for claim 1, it is characterised in that：In step (5), after being concentrated by electrodialysis, in concentrated water
TDS be up to 200000 more than mg/L；Electrodialysis fresh water TDS is 25000 below mg/L.
14. according to the method for claim 1, it is characterised in that：In step (6), when flush distillation crystallizes, evaporation and concentration
Temperature is 50~150 DEG C, and crystallization temperature is 50~100 DEG C, obtains sulfate crystal；When double evaporation-cooling crystallizes, it is concentrated by evaporation
Temperature for 50~150 DEG C, crystallization temperature is 30~50 DEG C, obtains sodium chloride crystallization；The temperature of freezing and crystallizing is 0~-8
DEG C, obtain sodium chloride crystal.
15. according to the method for claim 1, it is characterised in that：In step (6), the purity of sodium sulphate is generated in mass
For more than 95%, the sodium chloride purity of generation is in mass more than 98%, the saltcake production purity of generation in mass for 90% with
On.
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