CN105800885A - Resource recycling and treatment system of high-concentration degradation-resistant salt-containing organic waste water - Google Patents
Resource recycling and treatment system of high-concentration degradation-resistant salt-containing organic waste water Download PDFInfo
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- CN105800885A CN105800885A CN201610342912.6A CN201610342912A CN105800885A CN 105800885 A CN105800885 A CN 105800885A CN 201610342912 A CN201610342912 A CN 201610342912A CN 105800885 A CN105800885 A CN 105800885A
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- Prior art keywords
- water
- water outlet
- containing organic
- filter
- reverse osmosis
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 228
- 150000003839 salts Chemical class 0.000 title claims abstract description 50
- 238000004064 recycling Methods 0.000 title claims abstract description 31
- 230000015556 catabolic process Effects 0.000 title claims abstract description 16
- 238000006731 degradation reaction Methods 0.000 title claims abstract description 16
- 239000010815 organic waste Substances 0.000 title abstract 4
- 239000002351 wastewater Substances 0.000 claims abstract description 105
- 238000000034 method Methods 0.000 claims abstract description 103
- 238000000909 electrodialysis Methods 0.000 claims abstract description 85
- 230000008569 process Effects 0.000 claims abstract description 80
- 238000001223 reverse osmosis Methods 0.000 claims abstract description 64
- 239000012528 membrane Substances 0.000 claims abstract description 58
- 239000011347 resin Substances 0.000 claims abstract description 56
- 229920005989 resin Polymers 0.000 claims abstract description 56
- 238000000108 ultra-filtration Methods 0.000 claims abstract description 52
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 50
- 230000003647 oxidation Effects 0.000 claims abstract description 46
- 238000001728 nano-filtration Methods 0.000 claims abstract description 33
- 238000001914 filtration Methods 0.000 claims abstract description 17
- 238000010612 desalination reaction Methods 0.000 claims abstract description 11
- 238000011109 contamination Methods 0.000 claims abstract description 8
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 96
- 239000000126 substance Substances 0.000 claims description 52
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 51
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 46
- 229910052748 manganese Inorganic materials 0.000 claims description 37
- 239000011572 manganese Substances 0.000 claims description 37
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 36
- 239000004576 sand Substances 0.000 claims description 36
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 33
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims description 31
- 238000002425 crystallisation Methods 0.000 claims description 31
- 230000008025 crystallization Effects 0.000 claims description 31
- 239000011737 fluorine Substances 0.000 claims description 31
- 229910052731 fluorine Inorganic materials 0.000 claims description 31
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 30
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 27
- 238000004140 cleaning Methods 0.000 claims description 25
- 230000008929 regeneration Effects 0.000 claims description 24
- 238000011069 regeneration method Methods 0.000 claims description 24
- 230000008685 targeting Effects 0.000 claims description 22
- 239000000047 product Substances 0.000 claims description 21
- 239000003054 catalyst Substances 0.000 claims description 20
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 19
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 claims description 16
- 239000003795 chemical substances by application Substances 0.000 claims description 16
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 14
- 239000002253 acid Substances 0.000 claims description 14
- 238000005188 flotation Methods 0.000 claims description 13
- 230000004044 response Effects 0.000 claims description 13
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 12
- 230000003197 catalytic effect Effects 0.000 claims description 12
- 230000001105 regulatory effect Effects 0.000 claims description 12
- 239000000835 fiber Substances 0.000 claims description 11
- 230000006872 improvement Effects 0.000 claims description 11
- 229910017053 inorganic salt Inorganic materials 0.000 claims description 11
- 239000007787 solid Substances 0.000 claims description 11
- 239000002699 waste material Substances 0.000 claims description 11
- 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 10
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 claims description 10
- 239000003729 cation exchange resin Substances 0.000 claims description 10
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 claims description 9
- JLVVSXFLKOJNIY-UHFFFAOYSA-N Magnesium ion Chemical compound [Mg+2] JLVVSXFLKOJNIY-UHFFFAOYSA-N 0.000 claims description 9
- 239000001110 calcium chloride Substances 0.000 claims description 9
- 229910001628 calcium chloride Inorganic materials 0.000 claims description 9
- 229910001629 magnesium chloride Inorganic materials 0.000 claims description 9
- 229910001425 magnesium ion Inorganic materials 0.000 claims description 9
- 239000007832 Na2SO4 Substances 0.000 claims description 8
- -1 iron ion Chemical class 0.000 claims description 8
- 239000000463 material Substances 0.000 claims description 8
- 244000005700 microbiome Species 0.000 claims description 8
- 239000002245 particle Substances 0.000 claims description 8
- 239000011780 sodium chloride Substances 0.000 claims description 8
- 229910052938 sodium sulfate Inorganic materials 0.000 claims description 8
- 239000000725 suspension Substances 0.000 claims description 8
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 7
- 239000006004 Quartz sand Substances 0.000 claims description 7
- RHZUVFJBSILHOK-UHFFFAOYSA-N anthracen-1-ylmethanolate Chemical compound C1=CC=C2C=C3C(C[O-])=CC=CC3=CC2=C1 RHZUVFJBSILHOK-UHFFFAOYSA-N 0.000 claims description 7
- 239000003830 anthracite Substances 0.000 claims description 7
- 230000018044 dehydration Effects 0.000 claims description 7
- 238000006297 dehydration reaction Methods 0.000 claims description 7
- 230000000694 effects Effects 0.000 claims description 7
- 150000002500 ions Chemical class 0.000 claims description 7
- 229910052757 nitrogen Inorganic materials 0.000 claims description 7
- 229910052698 phosphorus Inorganic materials 0.000 claims description 7
- 239000011574 phosphorus Substances 0.000 claims description 7
- 239000000084 colloidal system Substances 0.000 claims description 6
- 239000011790 ferrous sulphate Substances 0.000 claims description 6
- 235000003891 ferrous sulphate Nutrition 0.000 claims description 6
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 6
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 claims description 6
- 229910000359 iron(II) sulfate Inorganic materials 0.000 claims description 6
- 239000007788 liquid Substances 0.000 claims description 6
- 239000010802 sludge Substances 0.000 claims description 6
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 5
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical group 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 description 5
- 229920001429 chelating resin Polymers 0.000 claims description 5
- 238000000354 decomposition reaction Methods 0.000 claims description 5
- 238000011049 filling Methods 0.000 claims description 5
- 239000001257 hydrogen Substances 0.000 claims description 5
- 229910052739 hydrogen Inorganic materials 0.000 claims description 5
- 230000001939 inductive effect Effects 0.000 claims description 5
- 230000001590 oxidative effect Effects 0.000 claims description 5
- 238000005273 aeration Methods 0.000 claims description 4
- WUKWITHWXAAZEY-UHFFFAOYSA-L calcium difluoride Chemical compound [F-].[F-].[Ca+2] WUKWITHWXAAZEY-UHFFFAOYSA-L 0.000 claims description 4
- 229910001634 calcium fluoride Inorganic materials 0.000 claims description 4
- 238000005119 centrifugation Methods 0.000 claims description 4
- 239000003153 chemical reaction reagent Substances 0.000 claims description 4
- 239000012141 concentrate Substances 0.000 claims description 4
- 239000000356 contaminant Substances 0.000 claims description 4
- 239000013078 crystal Substances 0.000 claims description 4
- 229910052742 iron Inorganic materials 0.000 claims description 4
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 claims description 3
- WAEMQWOKJMHJLA-UHFFFAOYSA-N Manganese(2+) Chemical compound [Mn+2] WAEMQWOKJMHJLA-UHFFFAOYSA-N 0.000 claims description 3
- 230000015572 biosynthetic process Effects 0.000 claims description 3
- 229910001424 calcium ion Inorganic materials 0.000 claims description 3
- 229910001437 manganese ion Inorganic materials 0.000 claims description 3
- 239000002244 precipitate Substances 0.000 claims description 3
- 230000000717 retained effect Effects 0.000 claims description 3
- 238000003756 stirring Methods 0.000 claims description 3
- 239000000498 cooling water Substances 0.000 abstract description 12
- 238000005516 engineering process Methods 0.000 abstract description 12
- 238000004519 manufacturing process Methods 0.000 abstract description 4
- 238000005842 biochemical reaction Methods 0.000 abstract description 2
- 239000005416 organic matter Substances 0.000 abstract 2
- 238000006115 defluorination reaction Methods 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 45
- 239000003921 oil Substances 0.000 description 11
- 230000003134 recirculating effect Effects 0.000 description 9
- 239000001117 sulphuric acid Substances 0.000 description 9
- 235000011149 sulphuric acid Nutrition 0.000 description 9
- 238000006243 chemical reaction Methods 0.000 description 7
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 6
- XKMRRTOUMJRJIA-UHFFFAOYSA-N ammonia nh3 Chemical compound N.N XKMRRTOUMJRJIA-UHFFFAOYSA-N 0.000 description 6
- 239000011575 calcium Substances 0.000 description 6
- 229910052791 calcium Inorganic materials 0.000 description 6
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 4
- 239000011449 brick Substances 0.000 description 4
- 239000004566 building material Substances 0.000 description 4
- VTYYLEPIZMXCLO-UHFFFAOYSA-L calcium carbonate Substances [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 4
- 229910000019 calcium carbonate Inorganic materials 0.000 description 4
- 239000004568 cement Substances 0.000 description 4
- 239000000919 ceramic Substances 0.000 description 4
- 239000004567 concrete Substances 0.000 description 4
- 239000003344 environmental pollutant Substances 0.000 description 4
- 231100000719 pollutant Toxicity 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 239000000377 silicon dioxide Substances 0.000 description 4
- 239000006227 byproduct Substances 0.000 description 3
- JEGUKCSWCFPDGT-UHFFFAOYSA-N h2o hydrate Chemical compound O.O JEGUKCSWCFPDGT-UHFFFAOYSA-N 0.000 description 3
- 239000010842 industrial wastewater Substances 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 238000003825 pressing Methods 0.000 description 3
- 239000010865 sewage Substances 0.000 description 3
- XFXPMWWXUTWYJX-UHFFFAOYSA-N Cyanide Chemical compound N#[C-] XFXPMWWXUTWYJX-UHFFFAOYSA-N 0.000 description 2
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 2
- 230000002159 abnormal effect Effects 0.000 description 2
- 150000001491 aromatic compounds Chemical class 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 239000003245 coal Substances 0.000 description 2
- 239000003034 coal gas Substances 0.000 description 2
- 238000004043 dyeing Methods 0.000 description 2
- 239000000796 flavoring agent Substances 0.000 description 2
- 235000019634 flavors Nutrition 0.000 description 2
- 229910001385 heavy metal Inorganic materials 0.000 description 2
- 150000002391 heterocyclic compounds Chemical class 0.000 description 2
- 239000010808 liquid waste Substances 0.000 description 2
- 230000007774 longterm Effects 0.000 description 2
- 238000005272 metallurgy Methods 0.000 description 2
- 230000003020 moisturizing effect Effects 0.000 description 2
- 230000001473 noxious effect Effects 0.000 description 2
- 238000007639 printing Methods 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 238000005728 strengthening Methods 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- FMMWHPNWAFZXNH-UHFFFAOYSA-N Benz[a]pyrene Chemical compound C1=C2C3=CC=CC=C3C=C(C=C3)C2=C2C3=CC=CC2=C1 FMMWHPNWAFZXNH-UHFFFAOYSA-N 0.000 description 1
- 230000004308 accommodation Effects 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 239000012267 brine Substances 0.000 description 1
- 238000004939 coking Methods 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 230000008030 elimination Effects 0.000 description 1
- 238000003379 elimination reaction Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000013505 freshwater Substances 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 125000005575 polycyclic aromatic hydrocarbon group Chemical group 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 230000035939 shock Effects 0.000 description 1
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 1
- NIAGBSSWEZDNMT-UHFFFAOYSA-M tetraoxidosulfate(.1-) Chemical compound [O]S([O-])(=O)=O NIAGBSSWEZDNMT-UHFFFAOYSA-M 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 238000004065 wastewater treatment 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
- C02F1/24—Treatment of water, waste water, or sewage by flotation
-
- 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
- C02F1/40—Devices for separating or removing fatty or oily substances or similar floating material
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/42—Treatment of water, waste water, or sewage by ion-exchange
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/44—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis
- C02F1/441—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis by reverse osmosis
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/44—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis
- C02F1/442—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
- C02F1/52—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
- C02F2001/5218—Crystallization
-
- 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
- C02F2305/023—Reactive oxygen species, singlet oxygen, OH radical
-
- 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
- C02F3/34—Biological treatment of water, waste water, or sewage characterised by the microorganisms used
-
- 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
Landscapes
- Separation Using Semi-Permeable Membranes (AREA)
- 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)
Abstract
Provided is a resource recycling and treatment system of high-concentration degradation-resistant salt-containing organic waste water.The system comprises a crystallizing defluorination reactor, a comprehensive waste water adjusting pool, a biochemical treatment system, an advanced oxidation unit, a filtering unit, an ultrafiltration device, a resin softening device, a reverse osmosis device, a concentrated electrodialysis device, a nanofiltration device, a first bipolar-membrane electrodialysis device and a second bipolar-membrane electrodialysis device.According to the resource recycling and treatment system of the high-concentration degradation-resistant salt-containing organic waste water, multiple process combinations are optimized, degradation-resistant organic matter and inorganic salts in the waste water can be removed step by step, and resource recycling of the high-concentration degradation-resistant salt-containing organic waste water is achieved on the basis of nearly zero emission; the recycling rate of produced water produced after the treatment process can reach 95% or above, and the produced water can be used as water for a production technology and replenishing water for circulating cooling water.The water quality requirement of biochemical reaction inlet water is guaranteed; the risk of organic matter contamination of a subsequent desalination system is effectively reduced by means of biochemical treatment and an advanced oxidation reaction.
Description
Technical field
The resource recycling that the present invention is a kind of high-concentration hardly-degradable salt-containing organic wastewater processes system and processes technique, belongs to field of waste water treatment.More particularly to a kind of for the physical treatment of this high-concentration hardly-degradable salt-containing organic wastewater, chemical treatment, biological treatment, film advanced treating integrated treatment process, it is intended to utilize this system realize on the basis of " near-zero release " high-concentration hardly-degradable salt-containing organic wastewater resource recycle.
Background technology
Sanitary sewage and industrial wastewater are the primary pollution source of China's water body.At present, sanitary sewage disposal technology has tended to ripe, and the process of industrial wastewater is also solved thoroughly, especially the treatment technology of the high-concentration hardly-degradable salt-containing organic wastewater that the industry such as petrochemical industry, Coal Chemical Industry, metallurgy, printing and dyeing, pharmacy, papermaking is discharged in process of production is still immature.This waste water quality feature is mainly manifested in the following aspects: (1) organic contamination substrate concentration is high, and general COD is more than 2000mg/L, it might even be possible to reach several ten thousand mg/litre；(2) difficult degradation, wastewater biodegradability is poor, and its ratio of BOD/COD will be generally less than 0.3, even lower；(3) salinity is high, and the salinity in usual waste water is higher than 3000mg/L；(4) pollutant component is complicated, usually contains the difficult degradation noxious substances such as aromatic compound, heterocyclic compound, sulfide, cyanide, heavy metal in organic wastewater；(5) colourity is high, there is abnormal flavour, and surrounding enviroment impact is bigger.
Owing in this kind of waste water, big and the material such as polycyclic aromatic hydrocarbon, benzopyrene the toxicity of hardly degraded organic substance content is big so that single biologic treating technique, physical chemistry treatment technology are difficulty with the qualified discharge of this kind of waste water.Investigation shows, the industry water consumptions such as petrochemical industry, Coal Chemical Industry, metallurgy, printing and dyeing, pharmacy, papermaking are big, if adopting advanced treatment process to recycle this kind of waste water, pollution on the environment can not only be alleviated, waste water can also be turned waste into wealth, recycle, and then decrease the consumption of fresh water, bring considerable economic benefit to enterprise.But the advanced treatment process running of routine is easily generated the Organic Pollution of membranous system and the problem of inorganic salt fouling so that this technique is difficult for long-term stable operation.Additionally, the response rate of the advanced treatment process waste water of routine Aquatic product amount low, dense is big, directly discharges if substantial amounts of pollutant are concentrated in dense water, serious environmental pollution can be caused.
Therefore, in order to realize the high-recovery of waste water, process system " near-zero release ", eliminate the pollution to environment of dense water, waste residue and waste water, it is proposed to a set of whole process, efficient resource recycle process system and process technique.
Summary of the invention
The resource recycling that it is an object of the invention to design a kind of novel high-concentration hardly-degradable salt-containing organic wastewater processes system, solves the problems referred to above.
To achieve these goals, the technical solution used in the present invention is as follows:
The resource recycling of a kind of high-concentration hardly-degradable salt-containing organic wastewater processes system, including:
Crystallization fluorine removal reactor: wherein add defluorinating agent and stir, for the fluorion in pending high-concentration hardly-degradable salt-containing organic wastewater is removed with sedimentary form, to reduce the fouling risk that subsequent film system produces because of calcium fluoride；
Comprehensive wastewater regulating reservoir: for uniform described crystallization fluorine removal reactor water outlet water quality, regulate the water yield of the water outlet of described crystallization fluorine removal reactor；
Biochemical treatment system: for the water outlet of described comprehensive wastewater regulating reservoir, realizes the degraded of COD under the effect of microorganism, synchronizes to realize the removal of nitrogen and phosphorus；
Advanced oxidation unit: for the water outlet of described biochemical treatment system, removes the Organic substance of difficult degradation in described biochemical treatment system, reduces follow-up desalination system and produces the risk of Organic Pollution；
Filter element: for the water outlet of described advanced oxidation unit being filtered, reduce delivery turbidity；
Ultrafiltration apparatus: for the float in the water outlet of described filter element, colloid, microorganism etc. are removed further；
Resin softening plant: for the water outlet of described ultrafiltration apparatus, removes calcium ion and magnesium ion, reduces the risk of follow-up desalination system inorganic salt fouling；The calcium chloride contained in the acid-basic regenerated waste liquids in water of described resin softening plant and magnesium chloride, be back to described crystallization fluorine removal reactor and use as defluorinating agent；
Reverse osmosis unit: for the product water of the water outlet of described resin softening plant and described concentrated type electrodialysis plant, reduce inorganic salt concentration therein, remove the Organic substance of residual simultaneously；The product water of described reverse osmosis unit is as product water reuse；
Concentrated type electrodialysis plant: for the dense water of described reverse osmosis unit is concentrated further；The product water of described concentrated type electrodialysis plant is back to described reverse osmosis unit and reclaims further；
Nanofiltration device: for sulfate ion in the dense water of described concentrated type electrodialysis plant is separated with chloride ion；
First bipolar membrane electrodialysis device: water is produced in the nanofiltration containing chloride ion for described nanofiltration device, and the saline solution based on NaCl is converted to hydrochloric acid solution and sodium hydroxide solution；
Second bipolar membrane electrodialysis device: contain the dense water of nanofiltration of sulfate ion for described nanofiltration device, will with Na2SO4The saline solution being main is converted to sulfuric acid solution and sodium hydroxide solution.
Preferably, also include oil interceptor and flotation tank, after pending high-concentration hardly-degradable salt-containing organic wastewater initially enters described oil interceptor and described flotation tank, enter back into described crystallization fluorine removal reactor.
Preferably, also including sludge-tank and sludge dewatering equipment, the precipitate in described flotation tank, described crystallization fluorine removal reactor and described biochemical treatment system enters described sludge-tank, after being then passed through described sludge dewatering equipment dehydration, is transported by mud.
Preferably, described filter element includes manganese sand filter or more medium filter or both combinations；
Described manganese sand filter is removed by aeration the iron ion in waste water and manganese ion, and the manganese sand filtering material in described manganese sand filter tentatively filters removal partial suspended thing；
Described more medium filter carries out fine filtering, equipped with quartz sand and ANTHRACITE FILTER MEDIA in described more medium filter, removes fine suspension and reduces delivery turbidity；
The particle diameter of the manganese sand filtering material in described manganese sand filter is 1-2mm；
In described more medium filter equipped with quartz sand and the particle diameter of ANTHRACITE FILTER MEDIA be 0.8-1.2mm.
Preferably, also including manganese sand discharge bay, the water outlet of described manganese sand filter first passes through described manganese sand discharge bay and then enters back into next device；
Also including multimedium discharge bay, the water outlet of described more medium filter first passes through described multimedium discharge bay and then enters back into next device；
Also including bio-chemical effluent pond, the water outlet of described biochemical treatment system first passes through described bio-chemical effluent pond and then enters back into next device；
Also including ultra-filtration water pond, the water outlet of described ultrafiltration apparatus first passes through described ultra-filtration water pond and then enters back into next device；
Also including softening discharge bay, the water outlet of described resin softening plant first passes through described softening discharge bay and then enters back into next device；
Also including reverse osmosis water outlet pond, the water outlet of described reverse osmosis unit first passes through described reverse osmosis water outlet pond and then enters back into next device.
Preferably, also including targeting catalyst oxidation reactor and fiber ball filter, the dense water of described reverse osmosis unit initially enters described targeting catalyst oxidation reactor, removes the hardly degraded organic substance of concentration in dense water；Enter back into fiber ball filter, carry out deep layer and cut dirt；Then enter back into described concentrated type electrodialysis plant to concentrate further.
Preferably, described crystallization fluorine removal reactor adds described defluorinating agent, and is sufficiently stirred for so that carrying out centrifugation after described high-concentration hardly-degradable salt-containing organic wastewater formation crystal, remove fluorion therein with solid forms；Described defluorinating agent is one or both in calcium chloride or magnesium chloride.
Preferably, described advanced oxidation unit comprises improvement Fenton oxidation response system and/or targeting catalytic oxidation system；
Described improvement Fenton oxidation response system adds ferrous sulfate and hydrogen peroxide when not acid adding, has contaminant degradation ability, also reduces reagent consumption amount and mud generation amount；
The filling needle catalyst to different quality feature in described targeting catalytic oxidation system, and pass into ozone, make ozone accelerated decomposition produce the hydroxyl radical free radical of strong oxidizing property by the inducing action of catalyst, the characteristic contamination in waste water is thoroughly decomposed.
Preferably, described resin softening plant adopts a kind of form in sodium form cation exchange resin, Hydrogen weak-acid cation-exchange resin or chelating resin；
Described nanofiltration device utilizes NF membrane that the selectivity of ion is retained, and sulfate ion and chloride ion is separated；
The hydrochloric acid solution produced in described first bipolar membrane electrodialysis device is for the regeneration of resin in described resin softening plant, and is used for including the Chemical cleaning of described ultrafiltration apparatus, concentrated type electrodialysis plant；
The adjustment of the system pH that the described second sulfuric acid solution producing to produce in bipolar membrane electrodialysis device is used in the resource recycling process technique of described high-concentration hardly-degradable salt-containing organic wastewater；
Described first bipolar membrane electrodialysis device and described second produces the sodium hydroxide solution that produces in bipolar membrane electrodialysis device and for the regeneration of resin in described resin softening plant and processes the adjustment of the system pH in technique for the resource recycling of described high-concentration hardly-degradable salt-containing organic wastewater, and for including the Chemical cleaning of described ultrafiltration apparatus, concentrated type electrodialysis plant.
Preferably, also including the cartridge filter of inflow requirement for meeting reverse osmosis unit, the water outlet of described resin softening plant, after described cartridge filter, enters back into described reverse osmosis unit；
Also include self-cleaning filter, after the water inlet of described ultrafiltration apparatus to first pass through described self-cleaning filter, enter back into described ultrafiltration apparatus.
In the present invention, so-called high-concentration hardly-degradable salt-containing organic wastewater refers to that organic contamination substrate concentration is high, and general COD is more than 2000mg/L, it might even be possible to reach several ten thousand mg/litre；Wastewater biodegradability is poor, and its ratio of BOD/COD will be generally less than 0.3, even lower；Salinity is high, and the salinity in usual waste water is higher than 3000mg/L；Pollutant component is complicated, usually contains the difficult degradation noxious substances such as aromatic compound, heterocyclic compound, sulfide, cyanide, heavy metal in organic wastewater；Colourity is high, there is abnormal flavour, the industrial wastewater that surrounding enviroment impact is bigger.
In the present invention, comprehensive wastewater regulating reservoir is mainly by pond appearance, pond structure (deflection plate, blender etc.) uniformly water quality, equilibrium water amount.
The present invention adopts the group technology of nanofiltration and bipolar membrane electrodialysis device dense water depth is processed, obtain by-product hydrochloric acid, sulphuric acid and sodium hydroxide solution.Hydrochloric acid solution can be used for resin regeneration and the Chemical cleaning of the device such as ultrafiltration, electrodialysis；Sulfuric acid solution can be used for system pH regulator；And sodium hydroxide solution cannot be only used for resin regeneration, the adjustment of system pH also can be directly used for the Chemical cleaning of ultrafiltration, electrodialysis plant, it is achieved that in system, the inner loop of dense water and resource are recycled.
Hydrochloric acid that in the present invention, bipolar membrane electrodialysis device produces and sodium hydroxide, for the regeneration of resin, can not only reach good regeneration effect, and the composition in its regenerated liquid is with CaCl2、MgCl2It is main, can be used as again the defluorinating agent in crystallization fluorine removal reactor, it is achieved that the inner loop of regeneration liquid waste and resource are recycled, and have reached the purpose of the treatment of wastes with processes of wastes against one another.
It is an object of the invention to optimize the coupling of multiple process technique form the resource recycling process system of high-concentration hardly-degradable salt-containing organic wastewater and process technique.Not external sewage effluent in whole flow process, produces water and can be back to different production unit as recirculated cooling water moisturizing and process water, and the scum silica frost of generation, mud form mud cake after dehydration, can be used as the raw material of the building materials such as light ceramic, eco-cement, brick.
The resource recycling of high-concentration hardly-degradable salt-containing organic wastewater processes the process technique of system and comprises the following steps:
(1) pretreating process: high-concentration hardly-degradable salt-containing organic wastewater initially enters oil interceptor, flotation tank, removes the oils in waste water and solid suspension.Flotation tank water outlet enters crystallization fluorine removal reactor, crystallization fluorine removal reactor adds defluorinating agent and is sufficiently stirred for, fluorion is removed with sedimentary form after forming the crystal that granule is bigger, to reduce the fouling risk that subsequent film system produces because of calcium fluoride, the water outlet of crystallization fluorine removal reactor enters comprehensive wastewater regulating reservoir and carries out the adjustment of water quality and quantity.
(2) biochemical processing process: comprehensive wastewater regulating reservoir water outlet is promoted to biochemical treatment system through pump, the degraded of most COD is realized under the effect of microorganism, in addition synchronizing to realize the removal of nitrogen, phosphorus in this process, biochemical treatment system water outlet is flowed in bio-chemical effluent pond.
(3) degree of depth pretreating process: the water outlet of bio-chemical effluent pond promotes through pump, enters advanced oxidation unit, removes the Organic substance being difficult to degrade in biochemical system, reduces the Organic Pollution risk that follow-up desalination system produces.Wherein advanced oxidation unit includes the one in improvement Fenton oxidation reaction, targeting catalytic oxidation.The feature of improvement Fenton oxidation technique is to add ferrous sulfate and hydrogen peroxide in the condition downhill reaction device of not acid adding, not only achieves stronger contaminant degradation ability, is also greatly reduced reagent consumption amount and mud generation amount.And the feature of targeting catalytic oxidation is the filling needle catalyst to specific water quality type selecting in reactor, and pass into ozone, make ozone accelerated decomposition produce the hydroxyl radical free radical of strong oxidizing property by the inducing action of catalyst, the characteristic contamination in waste water is thoroughly decomposed.
The water outlet of advanced oxidation unit enters manganese sand filter, removes the Fe and Mn in waste water by aeration, may also pass through the manganese sand filtering material that the particle diameter in manganese sand filter is 1-2mm in addition and tentatively filters removal partial suspended thing.Manganese sand filter water outlet is lifted into more medium filter fine filtering through pump, and more medium filter, equipped with the quartz sand that particle diameter is 0.8-1.2mm and ANTHRACITE FILTER MEDIA, is used for removing fine suspension, reduces delivery turbidity.
(4) advanced treatment process: more medium filter water outlet through self-cleaning filter remove further the pollutant such as float and colloid laggard enter ultrafiltration apparatus, float, colloid, microorganism etc. can almost all be removed by ultrafiltration apparatus.The water outlet of ultrafiltration apparatus enters resin softening plant, resin softening plant adopts a kind of form in sodium form cation exchange resin, Hydrogen weak-acid cation-exchange resin or chelating resin, most calcium, magnesium ion can be removed after resin softens, reduce the risk of follow-up desalination system inorganic salt fouling.Composition main in acid-basic regenerated waste liquids in water is calcium chloride and magnesium chloride, therefore, can be back in crystallization fluorine removal reactor directly as defluorinating agent and use.The water outlet of resin softening plant is promoted to cartridge filter through pump, to meet the inflow requirement of reverse osmosis unit, subsequently into reverse osmosis unit.Reverse osmosis unit can reduce inorganic salt concentration in waste water, removes the Organic substance of residual simultaneously, it is ensured that effluent quality meets quality of reused water requirement.Reverse osmosis unit produces water and enters reuse pool, as product water reuse.
(5) dense water treatment technology: the dense water of reverse osmosis unit enters reverse osmosis concentrated pond, is promoted to targeting catalyst oxidation reactor through pump, removes the hardly degraded organic substance of concentration in dense water.Water outlet enters fiber ball filter from top to bottom, carries out deep layer through fiber-ball filter media and cuts dirt.Fiber ball filter water outlet is promoted to concentrated type electrodialysis plant through pump and concentrates further.The product water of concentrated type electrodialysis plant is back to the water inlet of reverse osmosis unit and reclaims further, and dense water is after the pretreatment of front end, biochemical treatment and advanced treatment process, float, colloid and calcium, magnesium ion etc. are removed substantially, and main component is with Na2SO4It is main with inorganic salts such as NaCl.The dense water of concentrated type electrodialysis plant enters nanofiltration device, owing to the rejection of multivalent ion to be far longer than monovalention by NF membrane, therefore, can major part sulfate radical and chloride ion be separated.Nanofiltration containing chloride ion is produced water and is entered bipolar membrane electrodialysis device, through the centrifugation of Bipolar Membrane, the saline solution based on NaCl is converted to hydrochloric acid and sodium hydroxide solution；And the dense water of nanofiltration containing sulfate ion also passes through bipolar membrane electrodialysis device, will with Na2SO4The saline solution being main is converted to sulphuric acid and sodium hydroxide.The hydrochloric acid solution that bipolar membrane electrodialysis device produces can be used for resin regeneration and the Chemical cleaning of the device such as ultrafiltration, electrodialysis；The sulfuric acid solution produced can be used for the adjustment of system pH；The sodium hydroxide solution produced can be used for the Chemical cleaning of resin regeneration, the adjustment of system pH and ultrafiltration, electrodialysis plant.Simultaneously unnecessary acid, alkali can be sold to the producer that soda acid quality requirements is not high.
Beneficial effects of the present invention can be summarized as follows:
(1) the invention provides the resource recycling of a kind of high-concentration hardly-degradable salt-containing organic wastewater process system and process technique, the kinds of processes combination of this system optimization, can removing Organic substance and the inorganic salt of difficult degradation in waste water step by step, the resource realizing high-concentration hardly-degradable salt-containing organic wastewater on the basis of " near-zero release " is recycled.
(2) the product Water Sproading rate that present invention process produces after processing is up to more than 95%, can as the moisturizing with water and recirculated cooling water of production technology.
(3) float in waste water and part COD are removed in the pretreatment through front end of this system, it is ensured that biochemical reaction influent quality requirement；Through the elimination to fluorion of the crystallization fluorine removal reactor and the removal to calcium, magnesium ion of the resin softening plant, greatly reduce the risk of follow-up desalination system inorganic salt fouling；React through biochemical treatment and advanced oxidation, effectively reduce the risk of follow-up desalination system Organic Pollution.Combined treatment through process above unit, it is ensured that whole process system especially advanced treatment process long-term stability is run.
(4) dense water depth is processed by the present invention adopts nanofiltration and the group technology of bipolar membrane electrodialysis device, obtains by-product hydrochloric acid, sulphuric acid and sodium hydroxide solution.Hydrochloric acid solution can be used for resin regeneration and the Chemical cleaning of the device such as ultrafiltration, electrodialysis；Sulfuric acid solution can be used for system pH regulator；And sodium hydroxide solution cannot be only used for resin regeneration, the adjustment of system pH also can be directly used for the Chemical cleaning of ultrafiltration, electrodialysis plant, it is achieved that in system, the inner loop of dense water and resource are recycled.
(5) by-product hydrochloric acid and sodium hydroxide are for the regeneration of resin, can not only reach good regeneration effect, and the composition in its regenerated liquid is with CaCl2、MgCl2It is main, can be used as again the defluorinating agent in crystallization fluorine removal reactor, it is achieved that the inner loop of regeneration liquid waste and resource are recycled, and have reached the purpose of the treatment of wastes with processes of wastes against one another.
(6) advantage such as aggregation system of the present invention has high treating effect, stable, small accommodation area, shock-resistant ability is strong, automaticity is high, easy and simple to handle.
Accompanying drawing explanation
Fig. 1 is the flow chart of a kind of embodiment of the process technique of the resource recycling process system of high-concentration hardly-degradable salt-containing organic wastewater of the present invention.
Fig. 2 is the flow chart of the another kind of embodiment of the process technique of the resource recycling process system of high-concentration hardly-degradable salt-containing organic wastewater of the present invention.
Detailed description of the invention
In order to make technical problem solved by the invention, technical scheme and beneficial effect clearly understand, below in conjunction with drawings and Examples, the present invention is further elaborated.Should be appreciated that specific embodiment described herein is only in order to explain the present invention, is not intended to limit the present invention.
Resource recycling such as Fig. 1 to a kind of high-concentration hardly-degradable salt-containing organic wastewater shown in 2 processes system, including:
Crystallization fluorine removal reactor: wherein add defluorinating agent and stir, for the fluorion in pending high-concentration hardly-degradable salt-containing organic wastewater is removed with sedimentary form, to reduce the fouling risk that subsequent film system produces because of calcium fluoride；
Comprehensive wastewater regulating reservoir: for uniform described crystallization fluorine removal reactor water outlet water quality, regulate the water yield of the water outlet of described crystallization fluorine removal reactor；
Biochemical treatment system: for the water outlet of described comprehensive wastewater regulating reservoir, realizes the degraded of COD under the effect of microorganism, synchronizes to realize the removal of nitrogen and phosphorus；
Advanced oxidation unit: for the water outlet of described biochemical treatment system, removes the Organic substance of difficult degradation in described biochemical treatment system, reduces follow-up desalination system and produces the risk of Organic Pollution；
Filter element: for the water outlet of described advanced oxidation unit being filtered, reduce delivery turbidity；
Ultrafiltration apparatus: for the float in the water outlet of described filter element, colloid, microorganism etc. are removed further；
Resin softening plant: for the water outlet of described ultrafiltration apparatus, removes calcium ion and magnesium ion, reduces the risk of follow-up desalination system inorganic salt fouling；The calcium chloride contained in the acid-basic regenerated waste liquids in water of described resin softening plant and magnesium chloride, be back to described crystallization fluorine removal reactor and use as defluorinating agent；
Reverse osmosis unit: for the product water of the water outlet of described resin softening plant and described concentrated type electrodialysis plant, reduce inorganic salt concentration therein, remove the Organic substance of residual simultaneously；The product water of described reverse osmosis unit is as product water reuse；
Concentrated type electrodialysis plant: for the dense water of described reverse osmosis unit is concentrated further；The product water of described concentrated type electrodialysis plant is back to described reverse osmosis unit and reclaims further；
Nanofiltration device: for sulfate ion in the dense water of described concentrated type electrodialysis plant is separated with chloride ion；
First bipolar membrane electrodialysis device: water is produced in the nanofiltration containing chloride ion for described nanofiltration device, and the saline solution based on NaCl is converted to hydrochloric acid solution and sodium hydroxide solution；
Second bipolar membrane electrodialysis device: contain the dense water of nanofiltration of sulfate ion for described nanofiltration device, will with Na2SO4The saline solution being main is converted to sulfuric acid solution and sodium hydroxide solution.
Preferably, also include oil interceptor and flotation tank, after pending high-concentration hardly-degradable salt-containing organic wastewater initially enters described oil interceptor and described flotation tank, enter back into described crystallization fluorine removal reactor.
Preferably, also including sludge-tank and sludge dewatering equipment, the precipitate in described flotation tank, described crystallization fluorine removal reactor and described biochemical treatment system enters described sludge-tank, after being then passed through described sludge dewatering equipment dehydration, is transported by mud.
In embodiment more preferably, described filter element includes manganese sand filter or more medium filter or both combinations；
Described manganese sand filter is removed by aeration the iron ion in waste water and manganese ion, and the manganese sand filtering material in described manganese sand filter tentatively filters removal partial suspended thing；
Described more medium filter carries out fine filtering, equipped with quartz sand and ANTHRACITE FILTER MEDIA in described more medium filter, removes fine suspension and reduces delivery turbidity；
The particle diameter of the manganese sand filtering material in described manganese sand filter is 1-2mm；
In described more medium filter equipped with quartz sand and the particle diameter of ANTHRACITE FILTER MEDIA be 0.8-1.2mm.
In embodiment more preferably, also including manganese sand discharge bay, the water outlet of described manganese sand filter first passes through described manganese sand discharge bay and then enters back into next device；
Also including multimedium discharge bay, the water outlet of described more medium filter first passes through described multimedium discharge bay and then enters back into next device；
Also including bio-chemical effluent pond, the water outlet of described biochemical treatment system first passes through described bio-chemical effluent pond and then enters back into next device；
Also including ultra-filtration water pond, the water outlet of described ultrafiltration apparatus first passes through described ultra-filtration water pond and then enters back into next device；
Also including softening discharge bay, the water outlet of described resin softening plant first passes through described softening discharge bay and then enters back into next device；
Also including reverse osmosis water outlet pond, the water outlet of described reverse osmosis unit first passes through described reverse osmosis water outlet pond and then enters back into next device.
In embodiment more preferably, also including targeting catalyst oxidation reactor and fiber ball filter, the dense water of described reverse osmosis unit initially enters described targeting catalyst oxidation reactor, removes the hardly degraded organic substance of concentration in dense water；Enter back into fiber ball filter, carry out deep layer and cut dirt；Then enter back into described concentrated type electrodialysis plant to concentrate further.
In embodiment more preferably, described crystallization fluorine removal reactor adds described defluorinating agent, and is sufficiently stirred for so that carrying out centrifugation after described high-concentration hardly-degradable salt-containing organic wastewater formation crystal, remove fluorion therein with solid forms；Described defluorinating agent is one or both in calcium chloride or magnesium chloride.
In embodiment more preferably, described advanced oxidation unit comprises improvement Fenton oxidation response system and/or targeting catalytic oxidation system；
Described improvement Fenton oxidation response system adds ferrous sulfate and hydrogen peroxide when not acid adding, has contaminant degradation ability, also reduces reagent consumption amount and mud generation amount；
The filling needle catalyst to different quality feature in described targeting catalytic oxidation system, and pass into ozone, make ozone accelerated decomposition produce the hydroxyl radical free radical of strong oxidizing property by the inducing action of catalyst, the characteristic contamination in waste water is thoroughly decomposed.
In embodiment more preferably, described resin softening plant adopts a kind of form in sodium form cation exchange resin, Hydrogen weak-acid cation-exchange resin or chelating resin；
Described nanofiltration device utilizes NF membrane that the selectivity of ion is retained, and sulfate ion and chloride ion is separated；
The hydrochloric acid solution produced in described first bipolar membrane electrodialysis device is for the regeneration of resin in described resin softening plant, and is used for including the Chemical cleaning of described ultrafiltration apparatus, concentrated type electrodialysis plant；
The adjustment of the system pH that the described second sulfuric acid solution producing to produce in bipolar membrane electrodialysis device is used in the resource recycling process technique of described high-concentration hardly-degradable salt-containing organic wastewater；
Described first bipolar membrane electrodialysis device and described second produces the sodium hydroxide solution that produces in bipolar membrane electrodialysis device and for the regeneration of resin in described resin softening plant and processes the adjustment of the system pH in technique for the resource recycling of described high-concentration hardly-degradable salt-containing organic wastewater, and for including the Chemical cleaning of described ultrafiltration apparatus, concentrated type electrodialysis plant.
In embodiment more preferably, also including the cartridge filter of inflow requirement for meeting reverse osmosis unit, the water outlet of described resin softening plant, after described cartridge filter, enters back into described reverse osmosis unit；
Also include self-cleaning filter, after the water inlet of described ultrafiltration apparatus to first pass through described self-cleaning filter, enter back into described ultrafiltration apparatus.
Embodiment 1:
Adopting the integrated process flow in the inventive method accompanying drawing 1 that certain oil plant brine waste is processed, water quality index is as follows:
| Sequence number | Project | Unit | Influent quality |
| 1 | CODCr | mg/L | ≤2200 |
| 2 | NH3-N | mg/L | ≤120 |
| 3 | Chloride ion | mg/L | ≤550 |
| 4 | Turbidity | NTU | ≤200 |
| 5 | Total hardness is (with CaCO3Meter) | mg/L | ≤350 |
| 6 | Total dissolved solid (TDS) | mg/L | ≤5500 |
| 7 | pH | - | 6～9 |
This system comprises the following steps:
A, pretreating process
Waste water initially enters crystallization fluorine removal reactor and carries out pretreatment.Through pretreatment, remove part solid suspension, Organic substance and fluorion etc. in waste water.
Pretreatment water outlet: turbidity≤130NTU, COD≤1700mg/L, water outlet flows into comprehensive wastewater regulating reservoir and carries out the adjustment of water quality and quantity.
B, biochemical processing process
Biochemical processing process unit adopts anaerobic-anoxic-oxic (A2O) technique, carries out COD and the removal of nitrogen, phosphorus to waste water.
Through biochemical treatment unit, the COD≤170mg/L of waste water, ammonia nitrogen≤5mg/L.
C, degree of depth pretreating process
Biochemistry pool water outlet enters improvement Fenton oxidation reactor, after adding ferrous sulfate and hydrogen peroxide, oxidation reaction occurs, remove most hardly degraded organic substance in this reactor.After advanced oxidation reacts, COD≤60mg/L.Water outlet adds NaOH solution and regulates pH to about 7.5, enters more medium filter and is filtered.
After multi-medium filtering, turbidity≤5.0NTU in waste water.
D, advanced treatment process
More medium filter water outlet sequentially passes through ultrafiltration apparatus, resin softening plant and reverse osmosis unit and carries out advanced treating.Ultrafilter membrane adopts external pressing type hollow fibrous membrane element, intake pressure 0.3MPa, ultrafiltration apparatus delivery turbidity≤1NTU, SDI value≤3.Ultrafiltration apparatus water outlet enters resin softening plant, and this device adopts chelating resin, removes the calcium in waste water, magnesium ion reduction hardness of water, and to ensure the properly functioning of reverse osmosis membrane, it goes out the water hardness≤10mg/L.Reverse osmosis unit adopts anti-pollution reverse osmosis membrane, water inlet operation pressure 1.5MPa, the response rate 70%.
Reverse osmosis unit effluent quality is as follows: COD≤20mg/L, TDS≤220mg/L, chloride ion≤35mg/L, hardness≤2mg/L, ammonia nitrogen≤0.5mg/L, turbidity≤0.1NTU, pH value 7.2～7.5, and water quality index meets the requirement of " Code for design of industrial recirculating cooling water treatment " can reuse.
E, dense water treatment technology
The dense water water quality index of reverse osmosis unit is: COD≤160mg/L, electrical conductivity≤25730 μ S/cm, chloride ion≤1750mg/L, hardness≤29mg/L, turbidity≤0.1NTU.
The dense water of reverse osmosis unit enters concentrated type electrodialysis plant, the concentrated type electrodialysis plant adopted is vertical structure, intake pressure≤0.4MPa, after the concentrated type electrodialysis process of dense water, the response rate reaches 70%, salt rejection rate 75%, dense water conductivity≤70000 μ S/cm, produces water conductivity≤6400 μ S/cm.The product water of concentrated type electrodialysis plant is back to feed water by reverse osmosis mouth and reclaims further, as product water reuse after reverse osmosis membrane is desalinated.The dense water of this concentrated type electrodialysis plant enters nanofiltration device, utilizes NF membrane to retain the selectivity of ion so that in waste water, chloride ion and sulfate ion are separated, and the rejection of sulfate ion is reached more than 98% by this film.Nanofiltration containing chloride ion is produced water and is entered the first bipolar membrane electrodialysis device, and the saline solution based on NaCl converts to hydrochloric acid and sodium hydroxide solution, and conversion ratio reaches 95%；And the dense water of nanofiltration containing sulfate ion enters the second bipolar membrane electrodialysis device, will with Na2SO4Being that main saline solution converts sulphuric acid and sodium hydroxide solution to, conversion ratio is 93%.The hydrochloric acid that bipolar membrane electrodialysis device produces can be used for resin regeneration and the Chemical cleaning of the device such as ultrafiltration, electrodialysis；The sulphuric acid produced can be used for the adjustment of system pH；The sodium hydroxide solution produced can be used for the Chemical cleaning of resin regeneration, the adjustment of system pH and ultrafiltration, electrodialysis plant.Unnecessary hydrochloric acid solution, sulfuric acid solution and sodium hydroxide solution are for the not high soda acid purposes of quality requirements.
The scum silica frost, the mud that produce in this system form mud cake after dehydration, can be used as the raw material of the building materials such as light ceramic, eco-cement, brick.
Effluent quality index reaches the requirement of " Code for design of industrial recirculating cooling water treatment ", and concrete data are as follows:
| Sequence number | Project | Unit | Effluent quality | GB 50050-2007 design load |
| 1 | CODCr | mg/L | ≤20 | ≤30 |
| 2 | NH3-N | mg/L | ≤0.5 | ≤5 |
| 3 | Chloride ion | mg/L | ≤35 | ≤250 |
| 4 | Turbidity | NTU | ≤0.1 | ≤5 |
| 5 | Total hardness is (with CaCO3Meter) | mg/L | ≤2 | ≤250 |
| 6 | Dissolubility amounts to solid) body (TDS) | mg/L | ≤220 | ≤1000 |
| 7 | pH | - | 7.2～7.5 | 7.0～8.5 |
Note: GB50050-2007 is " Code for design of industrial recirculating cooling water treatment ".
Embodiment 2
Adopting the integrated process flow in the inventive method accompanying drawing 2 that certain Coking Plant Wastewater is processed, water quality index is as follows:
| Sequence number | Project | Unit | Influent quality |
| 1 | CODCr | mg/L | ≤3500 |
| 2 | NH3-N | mg/L | ≤140 |
| 3 | Chloride ion | mg/L | ≤500 |
| 4 | Turbidity | NTU | ≤240 9 --> |
| 5 | Total hardness is (with CaCO3Meter) | mg/L | ≤280 |
| 6 | Total dissolved solid (TDS) | mg/L | ≤3500 |
| 7 | pH | - | 6～9 |
This system comprises the following steps:
A, pretreating process
First waste water sequentially enter oil interceptor, flotation tank, crystallization fluorine removal reactor carry out pretreatment.Through pretreatment, remove the oils of part, solid suspension, fluorion and Organic substance etc. in waste water.
Pretreatment water outlet: turbidity≤30NTU, COD≤2400mg/L, water outlet flows into comprehensive wastewater regulating reservoir and carries out the adjustment of water quality and quantity.
B, biochemical processing process
Biochemical processing process unit adopts anaerobic-anoxic-oxic (A2O) technique, carries out COD and the removal of nitrogen, phosphorus to waste water.
Through biochemical treatment unit, the COD≤180mg/L of waste water, ammonia nitrogen≤3mg/L.
C, degree of depth pretreating process
Biochemistry pool water outlet promotes through pump, after adding ferrous sulfate and hydrogen peroxide, enters improvement Fenton oxidation reactor, oxidation reaction occurs, removes most hardly degraded organic substance.After improvement Fenton catalytic oxidation, COD≤60mg/L.Water outlet adds NaOH through pipe-line mixer and regulates pH to about 7.5, enters manganese sand filter, and manganese sand filter water outlet is lifted into more medium filter fine filtering through pump.
After manganese sand and multimedium double-filtration, turbidity≤1.0NTU in waste water, total ferrum≤0.3mg/L.
D, advanced treatment process
Multimedium water outlet sequentially passes through ultrafiltration apparatus, resin softening plant and reverse osmosis unit and carries out advanced treating.Ultrafilter membrane adopts external pressing type hollow fibrous membrane element, intake pressure 0.2MPa, ultra-filtration water turbidity≤0.1NTU, SDI value≤3.Ultra-filtration water enters resin softening plant, and this device adopts sodium form cation exchange resin, removes the calcium in waste water, magnesium ion reduction hardness of water, and to ensure the properly functioning of reverse osmosis membrane, it goes out the water hardness≤5mg/L.Reverse osmosis unit adopts anti-pollution reverse osmosis membrane, water inlet operation pressure 1.5MPa, the response rate 75%.
Reverse osmosis unit effluent quality is as follows: COD≤15mg/L, TDS≤100mg/L, chloride ion≤30mg/L, hardness≤0.5mg/L, ammonia nitrogen≤0.2mg/L, turbidity≤0.1NTU, pH value 7.0～7.5, and water quality index meets the requirement of " Code for design of industrial recirculating cooling water treatment " can reuse.
E, dense water treatment technology
The dense water water quality index of reverse osmosis unit is: COD≤210mg/L, electrical conductivity≤15000 μ S/cm, chloride ion≤1820mg/L, hardness≤25mg/L, turbidity≤0.1NTU.
The dense water of reverse osmosis unit is promoted to targeting catalyst oxidation reactor through pump, and the hardly degraded organic substance of concentration, water outlet COD≤58mg/L, turbidity≤7NTU in dense water are removed in strengthening.Flow into fiber ball filter afterwards from top to bottom, carry out deep layer and cut dirt, delivery turbidity value≤0.5NTU.The water inlet index request of concentrated type electrodialysis plant is reached through the effluent quality of targeting catalytic oxidation and fiber ball filter.The concentrated type electrodialysis plant adopted is vertical structure, intake pressure≤0.4MPa, and after the concentrated type electrodialysis process of dense water, the response rate reaches 79%, salt rejection rate 70%, dense water conductivity≤60000 μ S/cm, produces water conductivity≤4500 μ S/cm.The product water of concentrated type electrodialysis plant is back to feed water by reverse osmosis mouth and reclaims further, as product water reuse after reverse osmosis membrane is desalinated.The dense water of this electrodialysis plant enters nanofiltration device, utilizes NF membrane to retain the selectivity of ion so that in waste water, chloride ion and sulfate ion are separated, and the rejection of sulfate ion is reached more than 98% by this film.Nanofiltration containing chloride ion is produced water and is entered the first bipolar membrane electrodialysis device, and the saline solution based on NaCl converts to hydrochloric acid and sodium hydroxide solution, and conversion ratio reaches 95%；And the dense water of nanofiltration containing sulfate ion enters the second bipolar membrane electrodialysis device, will with Na2SO4Being that main saline solution converts sulphuric acid and sodium hydroxide solution to, conversion ratio is 93%.The hydrochloric acid that bipolar membrane electrodialysis device produces can be used for resin regeneration and the Chemical cleaning of the device such as ultrafiltration, electrodialysis；The sulphuric acid produced can be used for the adjustment of system pH；The sodium hydroxide solution produced can be used for the Chemical cleaning of resin regeneration, the adjustment of system pH and ultrafiltration, electrodialysis plant.
Unnecessary hydrochloric acid solution, sulfuric acid solution and sodium hydroxide solution are for the not high soda acid purposes of quality requirements.
The scum silica frost, the mud that produce in this system form mud cake after dehydration, can be used as the raw material of the building materials such as light ceramic, eco-cement, brick.
Effluent quality index reaches the requirement of " Code for design of industrial recirculating cooling water treatment ", and concrete data are as follows:
Note: GB50050-2007 is " Code for design of industrial recirculating cooling water treatment ".
Embodiment 3:
Adopt the integrated process flow in the inventive method accompanying drawing 2 that certain coal gas wastewater is processed.Water quality index is as follows:
| Sequence number | Project | Unit | Influent quality |
| 1 | CODCr | mg/L | ≤5200 |
| 2 | NH3-N | mg/L | ≤175 |
| 3 | Chloride ion | mg/L | ≤280 |
| 4 | Turbidity | NTU | ≤190 |
| 5 | Total hardness is (with CaCO3Meter) | mg/L | ≤330 |
| 6 | Total dissolved solid (TDS) | mg/L | ≤3000 |
| 7 | pH | - | 8.0～9.0 |
This system comprises the following steps:
A, pretreating process
First waste water sequentially enter oil interceptor, flotation tank, crystallization fluorine removal reactor carry out pretreatment.Through pretreatment, remove the oils of part, solid suspension, fluorion and Organic substance etc. in waste water.
Pretreatment water outlet: turbidity≤25NTU, COD≤3000mg/L, water outlet flows into comprehensive wastewater regulating reservoir and carries out the adjustment of water quality and quantity.
B, biochemical processing process
Biochemical processing process unit adopts anaerobic-anoxic-oxic (A2O) technique, carries out COD and the removal of nitrogen, phosphorus to waste water.
Biochemical treatment water outlet: COD≤200mg/L, ammonia nitrogen≤5mg/L.
C, degree of depth pretreating process
Biochemistry pool water outlet promotes through pump, enters targeting catalyst oxidation reactor.Targeting catalytic oxidation is the filling needle targeting catalyst to coal gas wastewater water quality characteristics in the reactor, and pass into ozone, ozone accelerated decomposition is made to produce the hydroxyl radical free radical of strong oxidizing property by the inducing action of catalyst, characteristic contamination in waste water is thoroughly decomposed, water outlet COD≤52mg/L, sequentially enters manganese sand filter and more medium filter.
After manganese sand and multimedium double-filtration, turbidity≤1.0NTU in waste water, total ferrum≤0.2mg/L.
D, advanced treatment process
Multimedium water outlet sequentially passes through ultrafiltration apparatus, resin softening plant and reverse osmosis unit and carries out advanced treating.Ultrafilter membrane adopts external pressing type hollow fibrous membrane element, intake pressure 0.2MPa, ultra-filtration water turbidity≤0.1NTU, SDI value≤3.Ultra-filtration water enters resin softening plant, and this device adopts Hydrogen weak-acid cation-exchange resin, removes the calcium in waste water, magnesium ion, reduces hardness of water, and to ensure the properly functioning of reverse osmosis membrane, it goes out the water hardness≤3mg/L.Reverse osmosis unit adopts anti-pollution reverse osmosis membrane, water inlet operation pressure 1.4MPa, the response rate 75%.
The effluent quality of reverse osmosis unit is as follows: COD≤20mg/L, TDS≤85mg/L, chloride ion≤20mg/L, hardness≤0.3mg/L, ammonia nitrogen≤0.5mg/L, turbidity≤0.1NTU, pH value 7.5～8.0, water quality index meets the requirement of " Code for design of industrial recirculating cooling water treatment " can reuse.
E, dense water treatment technology
The dense water water quality index of reverse osmosis unit is: COD≤178mg/L, electrical conductivity≤16750 μ S/cm, chloride ion≤1340mg/L, hardness≤11mg/L, turbidity≤0.1NTU.
The dense water of reverse osmosis unit is promoted to targeting catalyst oxidation reactor through pump, and the hardly degraded organic substance of concentration, water outlet COD≤44mg/L, turbidity≤5NTU in dense water are removed in strengthening.Flow into fiber ball filter afterwards from top to bottom to carry out deep layer and cut dirt, delivery turbidity value≤0.6NTU.The electrodialytic water inlet index request of concentrated type is reached through the effluent quality of targeting catalytic oxidation and fibre-ball filtration.The concentrated type electrodialysis adopted is vertical structure, and intake pressure 0.4MPa, after the concentrated type electrodialysis of dense water, the response rate is 85%, and salt rejection rate reaches 73%, dense water conductivity≤88000 μ S/cm, produce water conductivity≤4500 μ S/cm, as product water reuse after reverse osmosis membrane is desalinated.The dense water of this electrodialysis plant enters nanofiltration device, utilizes NF membrane to retain the selectivity of ion so that in waste water, chloride ion and sulfate ion are separated, and the rejection of sulfate ion is reached more than 98% by this film.Nanofiltration containing chloride ion is produced water and is entered the first bipolar membrane electrodialysis device, and the saline solution based on NaCl converts to hydrochloric acid and sodium hydroxide solution, and conversion ratio is 95%；And the dense water of nanofiltration containing sulfate ion enters the second bipolar membrane electrodialysis device, will with Na2SO4The saline solution being main converts sulphuric acid and sodium hydroxide solution to, and conversion ratio is 93%.The hydrochloric acid that bipolar membrane electrodialysis device produces can be used for resin regeneration and the Chemical cleaning of the device such as ultrafiltration, electrodialysis；The sulphuric acid produced can be used for the adjustment of system pH；The sodium hydroxide produced can be used for the Chemical cleaning of resin regeneration, the adjustment of system pH and ultrafiltration, electrodialysis plant.
Unnecessary hydrochloric acid solution, sulfuric acid solution and sodium hydroxide solution are for the not high soda acid purposes of quality requirements.
The scum silica frost, the mud that produce in this system form mud cake after dehydration, can be used as the raw material of the building materials such as light ceramic, eco-cement, brick.
Reach the requirement of " Code for design of industrial recirculating cooling water treatment " through advanced treating effluent quality index, can reuse, concrete data are as follows:
Note: GB50050-2007 is " Code for design of industrial recirculating cooling water treatment ".
Above by concrete and preferred embodiment detailed describe the present invention; but those skilled in the art should be understood that; the invention is not limited in embodiment described above; all within the spirit and principles in the present invention; the any amendment made, equivalent replacement etc., should be included within protection scope of the present invention.
Claims (10)
1. the resource recycling of a high-concentration hardly-degradable salt-containing organic wastewater processes system, it is characterised in that including:
Crystallization fluorine removal reactor: wherein add defluorinating agent and stir, for the fluorion in pending high-concentration hardly-degradable salt-containing organic wastewater is removed with sedimentary form, to reduce the fouling risk that subsequent film system produces because of calcium fluoride；
Comprehensive wastewater regulating reservoir: for uniform described crystallization fluorine removal reactor water outlet water quality, regulate the water yield of the water outlet of described crystallization fluorine removal reactor；
Biochemical treatment system: for the water outlet of described comprehensive wastewater regulating reservoir, realizes the degraded of COD under the effect of microorganism, synchronizes to realize the removal of nitrogen and phosphorus；
Advanced oxidation unit: for the water outlet of described biochemical treatment system, removes the Organic substance of difficult degradation in described biochemical treatment system, reduces follow-up desalination system and produces the risk of Organic Pollution；
Filter element: for the water outlet of described advanced oxidation unit being filtered, reduce delivery turbidity；
Ultrafiltration apparatus: for the float in the water outlet of described filter element, colloid, microorganism etc. are removed further；
Resin softening plant: for the water outlet of described ultrafiltration apparatus, removes calcium ion and magnesium ion, reduces the risk of follow-up desalination system inorganic salt fouling；The calcium chloride contained in the acid-basic regenerated waste liquids in water of described resin softening plant and magnesium chloride, be back to described crystallization fluorine removal reactor and use as defluorinating agent；
Reverse osmosis unit: for the product water of the water outlet of described resin softening plant and described concentrated type electrodialysis plant, reduce inorganic salt concentration therein, remove the Organic substance of residual simultaneously；The product water of described reverse osmosis unit is as product water reuse；
Concentrated type electrodialysis plant: for the dense water of described reverse osmosis unit is concentrated further；The product water of described concentrated type electrodialysis plant is back to described reverse osmosis unit and reclaims further；
Nanofiltration device: for sulfate ion in the dense water of described concentrated type electrodialysis plant is separated with chloride ion；
First bipolar membrane electrodialysis device: water is produced in the nanofiltration containing chloride ion for described nanofiltration device, and the saline solution based on NaCl is converted to hydrochloric acid solution and sodium hydroxide solution；
Second bipolar membrane electrodialysis device: contain the dense water of nanofiltration of sulfate ion for described nanofiltration device, will with Na2SO4The saline solution being main is converted to sulfuric acid solution and sodium hydroxide solution.
2. the resource recycling of high-concentration hardly-degradable salt-containing organic wastewater according to claim 1 processes system, it is characterized in that: also include oil interceptor and flotation tank, after pending high-concentration hardly-degradable salt-containing organic wastewater initially enters described oil interceptor and described flotation tank, enter back into described crystallization fluorine removal reactor.
3. the resource recycling of high-concentration hardly-degradable salt-containing organic wastewater according to claim 2 processes system, it is characterized in that: also include sludge-tank and sludge dewatering equipment, precipitate in described flotation tank, described crystallization fluorine removal reactor and described biochemical treatment system enters described sludge-tank, after being then passed through described sludge dewatering equipment dehydration, mud is transported.
4. the resource recycling of high-concentration hardly-degradable salt-containing organic wastewater according to claim 1 processes system, it is characterised in that: described filter element includes manganese sand filter or more medium filter or both combinations；
Described manganese sand filter is removed by aeration the iron ion in waste water and manganese ion, and the manganese sand filtering material in described manganese sand filter tentatively filters removal partial suspended thing；
Described more medium filter carries out fine filtering, equipped with quartz sand and ANTHRACITE FILTER MEDIA in described more medium filter, removes fine suspension and reduces delivery turbidity；
The particle diameter of the manganese sand filtering material in described manganese sand filter is 1-2mm；
In described more medium filter equipped with quartz sand and the particle diameter of ANTHRACITE FILTER MEDIA be 0.8-1.2mm.
5. the resource recycling of high-concentration hardly-degradable salt-containing organic wastewater according to claim 4 processes system, it is characterised in that: also including manganese sand discharge bay, the water outlet of described manganese sand filter first passes through described manganese sand discharge bay and then enters back into next device；
Also including multimedium discharge bay, the water outlet of described more medium filter first passes through described multimedium discharge bay and then enters back into next device；
Also including bio-chemical effluent pond, the water outlet of described biochemical treatment system first passes through described bio-chemical effluent pond and then enters back into next device；
Also including ultra-filtration water pond, the water outlet of described ultrafiltration apparatus first passes through described ultra-filtration water pond and then enters back into next device；
Also including softening discharge bay, the water outlet of described resin softening plant first passes through described softening discharge bay and then enters back into next device；
Also including reverse osmosis water outlet pond, the water outlet of described reverse osmosis unit first passes through described reverse osmosis water outlet pond and then enters back into next device.
6. the resource recycling of high-concentration hardly-degradable salt-containing organic wastewater according to claim 1 processes system, it is characterized in that: also include targeting catalyst oxidation reactor and fiber ball filter, the dense water of described reverse osmosis unit initially enters described targeting catalyst oxidation reactor, removes the hardly degraded organic substance of concentration in dense water；Enter back into fiber ball filter, carry out deep layer and cut dirt；Then enter back into described concentrated type electrodialysis plant to concentrate further.
7. the resource recycling of high-concentration hardly-degradable salt-containing organic wastewater according to claim 1 processes system, it is characterized in that: in described crystallization fluorine removal reactor, add described defluorinating agent, and be sufficiently stirred for so that carrying out centrifugation after described high-concentration hardly-degradable salt-containing organic wastewater formation crystal, remove fluorion therein with solid forms；Described defluorinating agent is one or both in calcium chloride or magnesium chloride.
8. the resource recycling of high-concentration hardly-degradable salt-containing organic wastewater according to claim 1 processes system, it is characterised in that: described advanced oxidation unit comprises improvement Fenton oxidation response system and/or targeting catalytic oxidation system；
Described improvement Fenton oxidation response system adds ferrous sulfate and hydrogen peroxide when not acid adding, has contaminant degradation ability, also reduces reagent consumption amount and mud generation amount；
The filling needle catalyst to different quality feature in described targeting catalytic oxidation system, and pass into ozone, make ozone accelerated decomposition produce the hydroxyl radical free radical of strong oxidizing property by the inducing action of catalyst, the characteristic contamination in waste water is thoroughly decomposed.
9. the resource recycling of high-concentration hardly-degradable salt-containing organic wastewater according to claim 1 processes system, it is characterised in that: described resin softening plant adopts a kind of form in sodium form cation exchange resin, Hydrogen weak-acid cation-exchange resin or chelating resin；
Described nanofiltration device utilizes NF membrane that the selectivity of ion is retained, and sulfate ion and chloride ion is separated；
The hydrochloric acid solution produced in described first bipolar membrane electrodialysis device is for the regeneration of resin in described resin softening plant, and is used for including the Chemical cleaning of described ultrafiltration apparatus, concentrated type electrodialysis plant；
The adjustment of the system pH that the described second sulfuric acid solution producing to produce in bipolar membrane electrodialysis device is used in the resource recycling process technique of described high-concentration hardly-degradable salt-containing organic wastewater；
Described first bipolar membrane electrodialysis device and described second produces the sodium hydroxide solution that produces in bipolar membrane electrodialysis device and for the regeneration of resin in described resin softening plant and processes the adjustment of the system pH in technique for the resource recycling of described high-concentration hardly-degradable salt-containing organic wastewater, and for including the Chemical cleaning of described ultrafiltration apparatus, concentrated type electrodialysis plant.
10. the resource recycling of high-concentration hardly-degradable salt-containing organic wastewater according to claim 1 processes system, it is characterized in that: also include the cartridge filter of inflow requirement for meeting reverse osmosis unit, the water outlet of described resin softening plant, after described cartridge filter, enters back into described reverse osmosis unit；
Also include self-cleaning filter, after the water inlet of described ultrafiltration apparatus to first pass through described self-cleaning filter, enter back into described ultrafiltration apparatus.
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