CN110451709A - The processing method of production of polysilicon wastewater zero discharge - Google Patents
The processing method of production of polysilicon wastewater zero discharge Download PDFInfo
- Publication number
- CN110451709A CN110451709A CN201910713557.2A CN201910713557A CN110451709A CN 110451709 A CN110451709 A CN 110451709A CN 201910713557 A CN201910713557 A CN 201910713557A CN 110451709 A CN110451709 A CN 110451709A
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- China
- Prior art keywords
- waste water
- liquid
- calcium
- production
- evaporator
- Prior art date
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Links
- 239000002351 wastewater Substances 0.000 title claims abstract description 106
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 44
- 229910021420 polycrystalline silicon Inorganic materials 0.000 title claims abstract description 43
- 229920005591 polysilicon Polymers 0.000 title claims abstract description 41
- 238000003672 processing method Methods 0.000 title claims abstract description 15
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 claims abstract description 78
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims abstract description 61
- 239000007788 liquid Substances 0.000 claims abstract description 61
- 238000001704 evaporation Methods 0.000 claims abstract description 55
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 54
- 239000013078 crystal Substances 0.000 claims abstract description 51
- 239000011780 sodium chloride Substances 0.000 claims abstract description 43
- 238000002425 crystallisation Methods 0.000 claims abstract description 41
- 230000008025 crystallization Effects 0.000 claims abstract description 37
- 230000008020 evaporation Effects 0.000 claims abstract description 33
- 238000004062 sedimentation Methods 0.000 claims abstract description 30
- 238000000926 separation method Methods 0.000 claims abstract description 21
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 claims abstract description 20
- 229910001424 calcium ion Inorganic materials 0.000 claims abstract description 20
- 238000006243 chemical reaction Methods 0.000 claims abstract description 18
- 239000007791 liquid phase Substances 0.000 claims abstract description 16
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims abstract description 15
- 239000002253 acid Substances 0.000 claims abstract description 15
- 238000005189 flocculation Methods 0.000 claims abstract description 15
- 230000016615 flocculation Effects 0.000 claims abstract description 15
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 claims abstract description 14
- 239000001110 calcium chloride Substances 0.000 claims abstract description 14
- 229910001628 calcium chloride Inorganic materials 0.000 claims abstract description 14
- 238000007872 degassing Methods 0.000 claims abstract description 13
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims abstract description 12
- 230000018044 dehydration Effects 0.000 claims abstract description 10
- 238000006297 dehydration reaction Methods 0.000 claims abstract description 10
- 238000001035 drying Methods 0.000 claims abstract description 10
- 239000006228 supernatant Substances 0.000 claims abstract description 10
- 239000000701 coagulant Substances 0.000 claims abstract description 9
- 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 claims abstract description 9
- 238000001556 precipitation Methods 0.000 claims abstract description 9
- 229910052602 gypsum Inorganic materials 0.000 claims abstract description 8
- 239000010440 gypsum Substances 0.000 claims abstract description 8
- 239000012535 impurity Substances 0.000 claims abstract description 8
- 239000000920 calcium hydroxide Substances 0.000 claims abstract description 7
- 229910052938 sodium sulfate Inorganic materials 0.000 claims abstract description 7
- 235000011152 sodium sulphate Nutrition 0.000 claims abstract description 6
- 235000011116 calcium hydroxide Nutrition 0.000 claims abstract description 5
- 239000013589 supplement Substances 0.000 claims abstract description 5
- 239000012141 concentrate Substances 0.000 claims abstract description 4
- 238000004064 recycling Methods 0.000 claims abstract description 4
- 239000007787 solid Substances 0.000 claims description 30
- 238000000034 method Methods 0.000 claims description 24
- 230000008569 process Effects 0.000 claims description 16
- 238000012545 processing Methods 0.000 claims description 16
- 239000010802 sludge Substances 0.000 claims description 16
- 238000000265 homogenisation Methods 0.000 claims description 15
- 230000003750 conditioning effect Effects 0.000 claims description 12
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 10
- 238000002156 mixing Methods 0.000 claims description 9
- 208000005156 Dehydration Diseases 0.000 claims description 8
- 238000010438 heat treatment Methods 0.000 claims description 8
- 230000008859 change Effects 0.000 claims description 7
- 230000000694 effects Effects 0.000 claims description 7
- 239000000463 material Substances 0.000 claims description 7
- 238000011084 recovery Methods 0.000 claims description 7
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 6
- 239000011575 calcium Substances 0.000 claims description 6
- 238000009826 distribution Methods 0.000 claims description 6
- 239000011552 falling film Substances 0.000 claims description 6
- 239000003973 paint Substances 0.000 claims description 6
- 239000000047 product Substances 0.000 claims description 6
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 5
- 238000009835 boiling Methods 0.000 claims description 5
- 239000000706 filtrate Substances 0.000 claims description 5
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 4
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 4
- 239000005864 Sulphur Substances 0.000 claims description 4
- 230000001680 brushing effect Effects 0.000 claims description 4
- 229910052791 calcium Inorganic materials 0.000 claims description 4
- 238000007701 flash-distillation Methods 0.000 claims description 4
- 229910001385 heavy metal Inorganic materials 0.000 claims description 4
- 230000008676 import Effects 0.000 claims description 4
- 238000002347 injection Methods 0.000 claims description 4
- 239000007924 injection Substances 0.000 claims description 4
- 150000002500 ions Chemical class 0.000 claims description 4
- 239000012452 mother liquor Substances 0.000 claims description 4
- 229920002401 polyacrylamide Polymers 0.000 claims description 4
- 239000002562 thickening agent Substances 0.000 claims description 4
- 238000010792 warming Methods 0.000 claims description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 3
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims description 3
- 239000006004 Quartz sand Substances 0.000 claims description 3
- 229910052799 carbon Inorganic materials 0.000 claims description 3
- 238000007906 compression Methods 0.000 claims description 3
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 3
- 238000012423 maintenance Methods 0.000 claims description 3
- 239000011150 reinforced concrete Substances 0.000 claims description 3
- 229910052710 silicon Inorganic materials 0.000 claims description 3
- 239000010703 silicon Substances 0.000 claims description 3
- 239000011343 solid material Substances 0.000 claims description 3
- 235000008733 Citrus aurantifolia Nutrition 0.000 claims description 2
- JLVVSXFLKOJNIY-UHFFFAOYSA-N Magnesium ion Chemical compound [Mg+2] JLVVSXFLKOJNIY-UHFFFAOYSA-N 0.000 claims description 2
- 235000011941 Tilia x europaea Nutrition 0.000 claims description 2
- 239000004411 aluminium Substances 0.000 claims description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical group [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 2
- 229910052782 aluminium Inorganic materials 0.000 claims description 2
- 239000003795 chemical substances by application Substances 0.000 claims description 2
- 230000003247 decreasing effect Effects 0.000 claims description 2
- 238000001914 filtration Methods 0.000 claims description 2
- 230000003311 flocculating effect Effects 0.000 claims description 2
- 239000004571 lime Substances 0.000 claims description 2
- 229910001425 magnesium ion Inorganic materials 0.000 claims description 2
- 229910021645 metal ion Inorganic materials 0.000 claims description 2
- 239000002245 particle Substances 0.000 claims description 2
- 239000002244 precipitate Substances 0.000 claims description 2
- 239000013049 sediment Substances 0.000 claims description 2
- 229910021655 trace metal ion Inorganic materials 0.000 claims description 2
- 229920000592 inorganic polymer Polymers 0.000 claims 2
- 238000010025 steaming Methods 0.000 claims 2
- 239000006071 cream Substances 0.000 claims 1
- 238000013327 media filtration Methods 0.000 claims 1
- 230000008929 regeneration Effects 0.000 abstract description 3
- 238000011069 regeneration method Methods 0.000 abstract description 3
- 239000007789 gas Substances 0.000 description 18
- 239000012267 brine Substances 0.000 description 13
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 13
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 12
- 150000003839 salts Chemical class 0.000 description 11
- 238000005516 engineering process Methods 0.000 description 9
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 7
- 239000002699 waste material Substances 0.000 description 7
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 6
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 6
- 238000005406 washing Methods 0.000 description 6
- 230000001376 precipitating effect Effects 0.000 description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 4
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 4
- 239000005046 Chlorosilane Substances 0.000 description 4
- 230000009471 action Effects 0.000 description 4
- 239000000460 chlorine Substances 0.000 description 4
- 229910052801 chlorine Inorganic materials 0.000 description 4
- KOPOQZFJUQMUML-UHFFFAOYSA-N chlorosilane Chemical compound Cl[SiH3] KOPOQZFJUQMUML-UHFFFAOYSA-N 0.000 description 4
- 229910052681 coesite Inorganic materials 0.000 description 4
- 229910052906 cristobalite Inorganic materials 0.000 description 4
- 238000010992 reflux Methods 0.000 description 4
- 239000010865 sewage Substances 0.000 description 4
- 239000000377 silicon dioxide Substances 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 229910052682 stishovite Inorganic materials 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 239000000725 suspension Substances 0.000 description 4
- 229910052905 tridymite Inorganic materials 0.000 description 4
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 3
- 238000005260 corrosion Methods 0.000 description 3
- 230000007797 corrosion Effects 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 238000005086 pumping Methods 0.000 description 3
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 3
- 239000002002 slurry Substances 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- 229910052708 sodium Inorganic materials 0.000 description 3
- 229910052911 sodium silicate Inorganic materials 0.000 description 3
- 229910052882 wollastonite Inorganic materials 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 229910000885 Dual-phase steel Inorganic materials 0.000 description 2
- 229910003910 SiCl4 Inorganic materials 0.000 description 2
- 229910003822 SiHCl3 Inorganic materials 0.000 description 2
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 2
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 2
- 230000006835 compression Effects 0.000 description 2
- 238000009833 condensation Methods 0.000 description 2
- 230000005494 condensation Effects 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000018109 developmental process Effects 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 239000010408 film Substances 0.000 description 2
- 238000011010 flushing procedure Methods 0.000 description 2
- 239000003595 mist Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- FDNAPBUWERUEDA-UHFFFAOYSA-N silicon tetrachloride Chemical compound Cl[Si](Cl)(Cl)Cl FDNAPBUWERUEDA-UHFFFAOYSA-N 0.000 description 2
- 239000002210 silicon-based material Substances 0.000 description 2
- WBHQBSYUUJJSRZ-UHFFFAOYSA-N sodium;sulfuric acid Chemical compound [H+].[H+].[Na+].[O-]S([O-])(=O)=O WBHQBSYUUJJSRZ-UHFFFAOYSA-N 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 238000005507 spraying Methods 0.000 description 2
- 239000004593 Epoxy Substances 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 239000007832 Na2SO4 Substances 0.000 description 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- 229910007156 Si(OH)4 Inorganic materials 0.000 description 1
- 229910003818 SiH2Cl2 Inorganic materials 0.000 description 1
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- HICCMIMHFYBSJX-UHFFFAOYSA-N [SiH4].[Cl] Chemical compound [SiH4].[Cl] HICCMIMHFYBSJX-UHFFFAOYSA-N 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 238000005273 aeration Methods 0.000 description 1
- 238000007605 air drying Methods 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 229910000963 austenitic stainless steel Inorganic materials 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000004566 building material Substances 0.000 description 1
- UBAZGMLMVVQSCD-UHFFFAOYSA-N carbon dioxide;molecular oxygen Chemical compound O=O.O=C=O UBAZGMLMVVQSCD-UHFFFAOYSA-N 0.000 description 1
- 238000005660 chlorination reaction Methods 0.000 description 1
- 238000005352 clarification Methods 0.000 description 1
- 238000005345 coagulation Methods 0.000 description 1
- 230000015271 coagulation Effects 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000006073 displacement reaction Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000010828 elution Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 125000003700 epoxy group Chemical group 0.000 description 1
- 239000012527 feed solution Substances 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 238000007667 floating Methods 0.000 description 1
- 239000003673 groundwater Substances 0.000 description 1
- 230000012010 growth Effects 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 239000010842 industrial wastewater Substances 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 238000005461 lubrication Methods 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- RECVMTHOQWMYFX-UHFFFAOYSA-N oxygen(1+) dihydride Chemical compound [OH2+] RECVMTHOQWMYFX-UHFFFAOYSA-N 0.000 description 1
- 230000008635 plant growth Effects 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 1
- 239000012286 potassium permanganate Substances 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000005201 scrubbing Methods 0.000 description 1
- 238000010956 selective crystallization Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- 239000011863 silicon-based powder Substances 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- NIAGBSSWEZDNMT-UHFFFAOYSA-M tetraoxidosulfate(.1-) Chemical compound [O]S([O-])(=O)=O NIAGBSSWEZDNMT-UHFFFAOYSA-M 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 230000008719 thickening Effects 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 238000011144 upstream manufacturing Methods 0.000 description 1
- 238000007740 vapor deposition Methods 0.000 description 1
- 238000009834 vaporization Methods 0.000 description 1
- 230000008016 vaporization Effects 0.000 description 1
- 239000002912 waste gas Substances 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
- C02F1/02—Treatment of water, waste water, or sewage by heating
- C02F1/04—Treatment of water, waste water, or sewage by heating by distillation or evaporation
- C02F1/06—Flash 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
- C02F1/02—Treatment of water, waste water, or sewage by heating
- C02F1/04—Treatment of water, waste water, or sewage by heating by distillation or evaporation
- C02F1/08—Thin film 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
- C02F1/20—Treatment of water, waste water, or sewage by degassing, i.e. liberation of dissolved gases
-
- 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
- C02F1/5245—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using inorganic agents using basic salts, e.g. of aluminium and iron
-
- 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
- C02F2001/007—Processes including a sedimentation step
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
- C02F2103/34—Nature of the water, waste water, sewage or sludge to be treated from industrial activities not provided for in groups C02F2103/12 - C02F2103/32
- C02F2103/40—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 or use of photosensitive materials
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2201/00—Apparatus for treatment of water, waste water or sewage
- C02F2201/002—Construction details of the apparatus
- C02F2201/007—Modular design
Abstract
The invention discloses a kind of processing methods of production of polysilicon wastewater zero discharge, include: salinity conversion: adding sodium sulphate in production of polysilicon waste water for the calcium chloride in waste water and be converted into calcium sulfate precipitation and sodium chloride, while calcium ion and sulfate ion content being made to reach the steady state of saturation Jie；Dosing removal of impurities: addition milk of lime, coagulant, flocculation aid carry out solid-liquid initial gross separation, supernatant liquid phase liquid after medium filter progress solid-liquid secondary separation must filter through efficient sedimentation tank；Crystal seed antiscale evaporative crystallization: liquid enters evaporator progress circulating and evaporating concentration after acid adding, degassing process after filter, is concentrated into supersaturated unstability and calcium sulfate crystallite is precipitated, calcium sulfate crystallite is adsorbed in calcium sulfate seed surface；Dope obtains gypsum mud through cyclonic separation and centrifugal dehydration after evaporation, is partly refluxed to evaporator as supplement crystal seed；Dope enters crystallizer concentrate crystallization, and it is main carnallite that sodium chloride is able to after centrifugal dehydration, drying；The regeneration of water is realized in evaporation, crystallization recycling water resource.
Description
Technical field
The invention belongs to wastewater zero discharge environmental technology fields, are related to a kind of processing side of production of polysilicon wastewater zero discharge
Method and device.
Background technique
Polycrystalline silicon material is most important photovoltaic material, and occupation rate of market is chiefly used in semiconductor and the sun 90% or more
It can battery.In general, polycrystalline silicon material can be divided into metallurgical grade (MG), solar level (SG) and electron level (EG) by purity, wherein electricity
Sub- grade generally requires 99.9999% or more > containing Si.Production of polysilicon technology is started late in China's development, and the current country is built up
The polysilicon enterprise gone into operation or built mostly uses external advanced production technology, such as Siemens Method, silane thermal decomposition process, fluidized bed
Method etc..Siemens Method is to produce column of polysilicon by vapor deposition mode, to improve raw material availability, on the basis of original process
It is improved Siemens using closed loop production technology, which accounts for the 80% of world's production capacity.Most domestic
Enterprise because scale and cost reason and be not implemented material full closed cycle, to chlorosilane low-boiling-point substance, hydrogen chloride, system tail gas and
After start-stop, maintenance displacement tail gas only carry out scrubbing tower elution operation, it is discharged into " three wastes " processing system together.
Production tail gas (exhaust gas) mainly contains a large amount of HCl, chlorosilane (SiHCl3、SiH2Cl2、SiCl4)、H2、N2, due to chlorine
Silane easily hydrolyzes, frequently with alkali liquid washing, such as dilute NaOH solution and milk of lime.Chlorosilane and hydrogen chloride occur in hydrolysis
With formation villaumite and silicate mixture.Hydrogen, nitrogen, vapor can be directly discharged in air, the chemistry that process is related to
Reaction mainly has:
SiHCl3+H2O→SiO2+HCl+H2
HCl+NaOH→NaCl+H2O
HCl+Ca(OH)2→CaCl2+H2O
SiCl4+NaOH→H4SiO4+NaCl
H4SiO4+NaOH→Na2SiO3+H2O
H4SiO4+Ca(OH)2→CaSiO3+H2O
Washing tail gas waste water is production of polysilicon waste water chief component, typically constitutes from 90% or more waste water total amount of production,
And changes with technology waste gas discharge amount, chlorosilane and hydrogen cloride concentration and change.Washing tail gas waste water and remaining polysilicon industry
On-site waste water (pure water sewerage, corrosion ejected wash water, silicon core processing and lubrication water, ground flushing water, sanitary sewage etc.) is in waste water
After conditioning tank of standing mixing, brine waste is formed.Brine waste salt content is higher, TDS variation range in 30000~60000mg/L,
Salinity is based on calcium chloride and sodium chloride；Simultaneous with a large amount of suspended solids, such as micro silicon powder, SiO2、CaSiO3、Na2SiO3、
Si(OH)4With Ca (OH)2Deng suspension content SS can reach 5000mg/L or more；Brine waste neutrality meta-alkalescence, containing micro
Organic matter and heavy metal, COD content is substantially in 150mg/L or less.
Currently, for the comprehensive industrial brine waste that polysilicon industry on-site generates, mixing dosing, more is generallyd use
Suspended matter in the techniques removal waste water such as grade precipitating, reduces useless Organic substance in water and content of beary metal, it is higher to obtain chloride ion content
Waste water, chloride ion content is in 10000~30000mg/L.Treated chlorine-contained wastewater drains into factory or place garden sewage at
Factory is managed, rear discharge up to standard is handled.As national awareness of environment protection is constantly reinforced, the related waste water environmental emission standard of country is also constantly mentioned
It is high.It requires to be discharged into urban wastewater treatment firm water quality chlorination as GB/T 31962-2015 sewage is discharged into town sewer water standard
Object content is less than 800mg/L.Meanwhile because in water salt content increase more adverse effect can be brought to water body, such as influence aquatic life
Object and plant growth influence field-crop growth etc..So in waste water chloride ion and containing salt component carry out processing be future
Development trend.
Evaporative crystallization technique is usually used in realizing the enrichment and removal of salinity in waste water, but chlorine in polysilicon industry production waste water
Change calcium accounts for total salt point ratio and is up to 40%~60%.Solubility is very big in water for calcium chloride, and waste water is boiled when crystallization terminal is concentrated
Point temperature rise is very high.If being precipitated salinity crystallization under excessively high evaporating temperature, equipment corrosion and fouling can be aggravated, easily cause to exchange heat
Pipe leakage.Meanwhile using high steam as heat source, device operation energy consumption is also significantly increased.Using calcium chloride in different temperatures
Lower dissolubility difference cools down operation, it can be achieved that salinity part is precipitated, but increases process complexity and operation behaviour using heating again
Make difficulty.Therefore near-zero release disposition is realized for polysilicon industry production waste water, it needs to select more economical rationality and operation is steady
Fixed processing technology routine.
Summary of the invention
Implement the effective and reasonable of zero-emission disposition for polysilicon industry production waste water the object of the present invention is to provide a kind of
Processing method and processing device.
The production of polysilicon waste water be the comprehensive waste water of polysilicon industry typical production, including washing tail gas waste water,
Corrode ejected wash water, ground flushing water, sanitary sewage etc., wherein washing tail gas waste water accounts for 90% or more waste water total amount.Described is more
Crystal silicon produces waste water salt content height, and TDS is 30000~60000mg/L, and based on calcium chloride and sodium chloride, calcium chloride accounts for salinity
The 40%~60% of total salinity；Contain a large amount of suspensions, gluey sundries, such as SiO2、CaSiO3、Na2SiO3With Ca (OH)2Deng outstanding
Floating object SS content reaches 5000mg/L or more；Waste water is in neutrality meta-alkalescence, and containing micro-content organism and heavy metal ion, COD contains
Amount is substantially in 150mg/L or less.
The purpose of the present invention is what is be achieved through the following technical solutions:
A kind of processing method of production of polysilicon wastewater zero discharge, production of polysilicon waste water successively pass through salinity conversion, add
After medicine removal of impurities, the processing of crystal seed antiscale evaporative crystallization, great lot of water resources regeneration is recycled, obtains gypsum mud, based on sodium chloride
Carnallite；The following steps are included:
Salinity conversion: sodium sulphate is added into the production of polysilicon waste water Jing Guo homogenization, by the calcium chloride in waste water
It is converted into calcium sulfate precipitation and sodium chloride, while calcium ion and sulfate ion content in waste water being made to reach the steady state of saturation Jie；
Dosing removal of impurities: milk of lime, coagulant, flocculation aid are added into the waste water after salinity conversion processing, through efficient
Sedimentation basin (i.e. potassium permanganate composites) carries out solid-liquid initial gross separation, and supernatant carries out solid-liquid secondary separation through medium filter and obtains
Liquid after filter, by being separated by solid-liquid separation trace metal ion, suspended particle and a small amount of organic components in removal waste water twice；
Crystal seed antiscale evaporative crystallization: after filter liquid successively through plus acid for adjusting pH to 5~6, degassing process after enter evaporator into
Row circulating and evaporating is concentrated, and calcium ion and sulfate ion concentration are concentrated into supersaturated unstability in waste water in circulating and evaporating concentration process
Calcium sulfate crystallite is precipitated, calcium sulfate crystallite is adsorbed in adds calcium sulfate seed surface and life in evaporator saline slot in advance
It is long, it is constantly recycled with feed liquid；Dope is after cyclone separation device after evaporation, partially containing solid turbid conduct after centrifugal dehydration treatment
Gypsum mud outlet, it is 10g/L~15g/L that remaining part, which maintains calcium sulfate seed count as supplement crystal seed re-injection evaporator,；It follows
Ring, which is concentrated by evaporation to dope TDS in evaporator, reaches 15~20%, into crystallizer in be further concentrated into TDS reach 30~
40%, product is precipitated crystal, through centrifugal dehydration, is dried to obtain with sodium chloride as main carnallite.
The processing method of production of polysilicon wastewater zero discharge of the present invention, specifically includes the following steps:
Step (1), homogenization: all kinds of polysilicon industry production waste water enter conditioning tank, carry out under blender effect
Homogenization, after homogenization, calcium ion content is greater than 4000mg/L, sulfate ion content≤1000mg/L；
Step (2), salinity conversion: the waste water after homogenization enters dosing pond, and sodium sulphate is added, in waste water calcium ion and
Sulfate ion concentration converts calcium sulfate precipitation and chlorine for calcium chloride in waste water more than calcium sulfate precipitation is formed after solubility product
Change sodium, so that calcium ion content in waste water is decreased to less than 1000mg/L, calcium ion and sulfate ion are in the steady state of saturation Jie, chlorine
Change sodium and accounts for the 80%~90% of total salinity；
Step (3), dosing removal of impurities: in dosing pond, into the waste water Jing Guo salinity conversion processing, feeding lime is newborn, and gives up
Micro Magnesium in the Ground Water ion and heavy metal ion (such as Pb2+、Hg2+、Cd2+、Cr6+、Cr3+、As3+、Fe2+、Fe3+、Cu2+、Zn2+、Ni2+)
In conjunction with generation sediment；The waste water in dosing pond is discharged into efficient sedimentation tank again, coagulant and flocculation aid, stirring action is added
Gluey granulated is suspended in lower waste water into larger alumen ustum, rapid subsidence, while can also adsorb a small amount of organic components together, via
Efficient sedimentation tank flocculating setting realizes solid-liquid initial gross separation；Supernatant enters medium filter progress solid-liquid two in efficient sedimentation tank
Liquid after secondary isolated filter；High-rate sedimentation bottom of pond portion 30~50% is back to dosing pond containing solid liquid phase, and more after homogenization
Crystal silicon produces waste water mixing, and water inlet suspended matter flocculation is promoted to grow up；Residue is containing solid liquid phase successively through sludge concentration tank concentrate, filters pressing
Machine compresses to obtain moisture content in 20% mud cake below；
Step (4), crystal seed antiscale evaporative crystallization: liquid enters the head tank of crystal seed antiscale evaporation and crystallization system after filter, adds sulphur
Acid for adjusting pH eliminates basicity in waste water, then be pumped into degasser, carries out degasification operation for steam using outer, remove molten to 5~6
Oxygen, carbon dioxide and fixed gas in waste water slow down the generation of back segment crystallizing evaporator corrosion phenomenon, improve evaporative crystallization
System thermal efficiency and stability；Waste water after degassing enters progress circulating and evaporating concentration in evaporator, concentrated in circulating and evaporating
Cheng Zhong, calcium ion and sulfate ion concentration progressively reach supersaturation, and system is changed from metasable state to unstability state, and calcium sulfate is precipitated
Crystallite, according to " selective crystallization " mechanism, Preferential adsorption is in calcium sulfate seed surface and grows, and is not easy to be formed in heated metal face
Calcium sulfate scaling influences heat transfer property；Meanwhile crystal seed recycles in evaporator with waste water, washes away tube wall, wall, plays inhibition
Dirt is formed and the effect on adhesiving metal surface；Dope part enters cyclone separator after evaporation, (is rich in calcium sulfate containing solid liquid phase
Crystal slurries) partially via crystal seed recovery pipe Returning evaporimeter as supplement crystal seed, maintenance calcium sulfate seed count is 10g/L
~15g/L, residue are used as gypsum mud outlet containing solid liquid phase after centrifugal dehydrator is handled, and outer lithoexpulsium paste mud can be handled through deep processing
As building materials export trade；Dope is concentrated into TDS and reaches 15%~20% in device to be evaporated, continues to be concentrated into TDS into crystallizer and reaches
To 30%~40%, product is precipitated crystal, when solid content reaches 10%~30%, through centrifugal dehydration, is dried and obtains with chlorine
Change sodium is main carnallite, can be used as deicing salt export trade.
The sodium sulphate is preferably Na2SO4The thenardite of mass fraction >=90%, thenardite are cheap.
The coagulant selects aluminium polychloride (PAC) or poly-ferric chloride (PFC), dosage be 10mg/L~
30mg/L；The flocculation aid selects polyacrylamide (PAM), and dosage is 1mg/L~5mg/L.Part coagulant and help it is solidifying
Agent can also be by being added system into configuring pipes mixer before efficient sedimentation tank in advance.
The ss suspended solid content of the supernatant is less than 50mg/L, and COD content is less than 60mg/L.
The ss suspended solid content of liquid is less than 10mg/L after the filter, and COD content is less than 30mg/L.
It is a further object to provide a kind of processing units of production of polysilicon wastewater zero discharge, comprising: adjusts
Pond, dosing pond, efficient sedimentation tank, sludge concentration tank, filter press, medium filter, crystal seed antiscale evaporation and crystallization system；Described
Crystal seed antiscale evaporation and crystallization system includes head tank, degasser, evaporator, vortex separation system, crystal system connection；Described
The main function of conditioning tank is production waste water supplied materials homogeneous and measures that the outlet of conditioning tank is connect with the import in dosing pond, dosing
Pond provides salinity conversion and a small amount of metal ion reacts precipitation position, the outlet in the dosing pond and the import of efficient sedimentation tank
Connection, the top water outlet of efficient sedimentation tank and the water inlet of medium filter connect supernatant being sent into medium filter, are situated between
The water outlet of mass filter is successively connect with head tank, the degasser of crystal seed antiscale evaporation and crystallization system, the water outlet of degasser
It is connect with the water inlet of evaporator, the outlet of evaporator is connect with vortex separation system, crystal system respectively, the eddy flow point
Include sequentially connected cyclone separator and centrifugal dehydrator from system, is additionally provided with crystal seed in the cyclone separator outlet and returns
Closed tube road connect the re-injection containing solid liquid phase by part containing calcium sulfate crystal seed with evaporator to evaporator；The crystal system packet
Sequentially connected crystallization heater, crystallizer, centrifugal dehydrator are included, secondary steam outlet and the condenser of the crystallizer connect
It connects for recycle-water, thickener is equipped between crystallizer water outlet and centrifugal dehydrator, the water outlet of centrifugal dehydrator connects
Strong brine tank, then crystallized circulation line are connect after mixing centrifuge mother liquor with evaporation dope again with crystallization heater inlet ductwork
Secondary feeding crystallization heater heat exchange is warming up to boiling point, is sent into crystallizer flash distillation；Centrifugal dehydrator contains solid outlet and drying equipment
Connection will be centrifuged wet solid material and be sent into drying equipment drying.
The conditioning tank is round or rectangular reinforced concrete structure pond body, since waste water contains high concentration chloride, is adjusted
Save pond inner and outer surfaces brushing anticorrosive paint；Blender is provided in the conditioning tank.
The dosing pond inner and outer surfaces brushing anticorrosive paint, dosing pond are stirred equipped with Full-automatic agent-feeding device and dosing
Machine, the dosing blender can select vertical or submersible type blender, the effect of blender: on the one hand accelerate Ar ion mixing
Reaction precipitating, sinks to the bottom suspended particulate substance not and is pumped into efficient sedimentation tank.
The anticorrosive paint is polyurethanes or epoxies anticorrosive paint.
The efficient sedimentation tank is integral reinforced concrete structures, as collection dosing, flocculation, precipitating, exiting water process
What is be integrated removes the place of suspended solid, gluey sundries；Efficient sedimentation tank is general type, and inside is divided into coagulation by barricade
Pond, flocculation basin, sedimentation basin, it is compact-sized, clear water gathering ground is made of above sedimentation basin inclined plate, is returned below sedimentation basin equipped with sludge
Head piece and mud discharging mouth, the sludge reflux mouth of efficient sedimentation tank, which is connect through sludge reflux pipeline with dosing pond, contains precipitating bottom of pond portion admittedly
Liquid phase part conveys through sludge reflux pipeline and returns to dosing pond, mixes with water inlet, and water inlet suspended matter flocculation is promoted to grow up；Mud discharging mouth
It is connect through mud line with sludge concentration tank and remainder is entered into sludge concentration tank concentrate, sludge concentration tank and pressure containing solid liquid phase
Filter connection, is disposed via transporting outward after filter press boil down to mud cake.The filter press uses plate and frame type filter-press, and dehydration rate exists
80% or more.
The medium filter selects one of quartz sand, potsherd, active carbon etc. or a variety of filtrates to stack conduct
Filtering layer, the partial size of the filtrate is in 0.5mm~2mm.
The head tank is temporary with the place acid adding tune pH as feeding liquid, sulfuric acid pumps by acid adding, by pipeline be added into
In batch can, online pH meter is equipped in head tank, equipped with auxiliary rinse-system.
Water drenching disc type or material filling type degasser can be selected in the degasser.The degasser uses tower structure, interior
Component includes salt water even distribution device, such as water spraying tray, and strong brine flows after being evenly distributed with via water spraying tray to tower bottom, heats steam by tower bottom
Into upwards with strong brine contact heat-exchanging；Exhaust-valve is equipped at the top of degasser, removing gas and a small amount of emptying steam drain into atmosphere.
The evaporator be vertical tube falling film evaporator (202610066 U of CN), comprising catch box, liquid distribution trough,
Heat exchanger tube, saline slot, saline slot periphery gas chamber, demister, circulating pump, circulating line, top is catch box, and feed liquid is by circulating pump
It send to catch box, after liquid distribution trough is uniformly distributed, into the vertical heat-exchanging tube bundle in lower section, brine waste is walked in pipe, in realization
Wall surface descending manner liquid film evaporation, steam walks shell side, as heat source；Brine waste after vertical heat-exchanging tube bundle heating evaporation,
Into in the saline slot of lower end, the secondary steam of generation is gathered by saline slot periphery gas chamber, carries the secondary steam of strong brine secretly through gas
The demister being equipped with below room removes drop, discharge system.Saline slot outlet at bottom is connect through circulating line with catch box, salt water
Evaporation dope is delivered to catch box through circulating line in the case where recycling pumping action again in slot.Shell side heats steam exothermic condensation into liquid
Body is collected in distillation flow container.Evaporation feed liquor liquid can be exchanged heat with high temperature distillation liquid by plate heat exchanger, be heated in advance
Heating.
Function of mechanical steam recompression (MVR) or multiple-effect evaporation technology can be used, improve secondary steam enthalpy utilization rate.According to machine
Tool vapor recompression (MVR) technology then enters outside secondary steam discharge system after compressor increasing temperature and pressure mentions enthalpy, is back to shell side
It is re-used as heat source；It is according to multiple-effect evaporation technology, then rear outside secondary steam discharge system to enter next effect evaporator shell
Cheng Zuowei heat source；Saline slot outlet at bottom connect through pipeline with the catch box of lower 1st effective evaporator will be evaporated in saline slot it is dense
Liquid is delivered to lower 1st effective evaporator catch box.
The circulating and evaporating concentration process are as follows: liquid is delivered to vertical tube by circulating pump after acid adding, degassing process after filter
The catch box on falling film evaporator top, waste water is after liquid distribution trough is distributed, and into vertical heat-exchanging tube bundle, waste water walks tube side, steams
Vapour walks shell side；Waste water is after the heating concentration of vertical heat-exchanging tube bundle, and into the saline slot of lower end, the secondary steam of generation is by saline slot
Periphery gas chamber gathers, and removes drop, discharge system through the demister below gas chamber；Evaporation dope is in evaporative recirculation pump in saline slot
Export pipeline is mixed with liquid after the filter after acid adding, degassing process, is delivered to catch box again, realizes that circulating and evaporating is concentrated
Journey；Calcium ion and sulfate ion concentration are concentrated into supersaturated unstability that calcium sulfate is precipitated are micro- in waste water in circulating and evaporating concentration process
Crystalline substance, calcium sulfate crystallite are adsorbed in calcium sulfate seed surface and grow, and constantly recycle with feed liquid.
Start-up adds 10g/L~15g/L calcium sulfate crystal seed into evaporator saline slot, in circulating and evaporating concentration process
Maintaining calcium sulfate seed count in evaporator saline slot is 10g/L~15g/L, can realize that evaporated crystallization device nonincrusting is continuous
Operating.
The crystallizer is using outer circulation crystallizer is forced, and dope is pumped into crystallisation cycle pump discharge pipeline after evaporation, with
Enter crystallization heater after feed liquid mixing in crystallisation cycle pipeline, is heated for steam as heat source by outer, recycle feed liquid
Heat exchange is warming up to boiling point, is sent into crystallizer flash distillation, and the secondary steam of generation enters condenser, is condensed into distillate；Salt slurry reaches
Supersaturation, be precipitated salt crystal, be discharged by crystalliser feet, send to thickener thickening after enter centrifugal dehydrator, centrifuge mother liquor into
Enter strong brine tank, conveying is pumped by strong brine and returns to crystal system；It is centrifuged wet solid material and such as shakes fluidized bed, hot wind via drying equipment
After drying, baling press is packaged to obtain finished product carnallite.
High-grade stainless steel material is selected with highly concentrated saline contacts pipeline, equipment in crystal seed antiscale evaporation and crystallization system.
The evaporator saline slot selects dual phase steel 2207,2507, heat exchanger tube material selection titanium, crystallizer and crystallization heater choosing
With dual phase steel or austenitic stainless steel 6%Mo.The secondary steam that evaporator and crystallizer generate is respectively via high efficiency demister (silk
Net or folded plate), thermal recovery unit (heat exchanger), be condensed into liquid water and recycled.Water quality reaches regeneration water quality standard, can reuse
Each water ring section in production.Final realization wastewater zero discharge, water resource effective recycling, the rate of recovery are up to 90%.
Detailed description of the invention
Fig. 1 is the flow chart of invention production of polysilicon wastewater zero emission treatment method.
Fig. 2 is the structural schematic diagram of vertical tube falling film evaporator.
Specific embodiment
Technical solution of the present invention is described further combined with specific embodiments below.
Embodiment 1
Certain production of polysilicon enterprise is mixed to get production of polysilicon waste water by washing tail gas waste water and full factory's industrial wastewater
25m3/ h, total dissolved solidss TDS content is about 50000mg/L, wherein Na+、Ca2+、Mg2+Content respectively may be about 10000mg/L,
8000mg/L, 300mg/L, SO4 2-、Cl-Content respectively may be about 1000mg/L, 30000mg/L；Total suspended solid SS content is about
15000mg/L, wherein SiO2Content is about 200mg/L；COD content is about 50mg/L.
As shown in Figure 1, a kind of processing method of production of polysilicon wastewater zero discharge, steps are as follows:
Homogenization: aeration effect is uniformly mixed production of polysilicon waste water in agitated device and pond in conditioning tank；
Salinity conversion: the waste water by homogenization is pumped by waste water lifting to dosing pond, and anhydrous awns is added into waste water
The calcium chloride in waste water is converted calcium sulfate precipitation and sodium chloride by nitre, after salinity conversion, Ca2+Content is about 950mg/L, Na+
About 18000mg/L, sodium chloride account for total salinity about 90%, and calcium ion and sulfate ion content reach saturation in waste water at this time
Be situated between steady state；
Dosing removal of impurities: in dosing pond, milk of lime is added into the waste water by salinity conversion, reaction is sufficiently stirred, contains
Suspended matter muddiness waste water enters efficient sedimentation tank and carries out solid-liquid initial gross separation: poly-ferric chloride conduct being added in efficient sedimentation tank
Polyacrylamide is added as flocculation aid (adding concentration is 5mg/L) in coagulant (adding concentration is 20mg/L), and waste water is precipitating
It is sufficiently reacted in pond with coagulant, flocculation aid, forms larger flocculation alumen ustum, fall to bottom；High-rate sedimentation bottom of pond portion 30-50%
Sludge is back to dosing pond under sludge circulation pumping action, through sludge reflux pipeline, mixes with the water inlet Jing Guo homogenization, energy
It is enough that water inlet suspended matter flocculation is promoted to grow up；Excess sludge is sent dense again to sludge concentration tank under spoil disposal pumping action through mud line
Contracting, then form dry mud cake of the moisture content less than 10% through plate and frame filter press compression dehydration and transport outward.Efficient sedimentation tank supernatant is through oblique
Plate clarification and effluent, suspension content are about 45mg/L, and COD content is about 50mg/L, and being pumped into medium filter, (filtrate is using quartz
Sand and two layers of active carbon stacking) realize solid-liquid secondary separation, suspension content about 10mg/L in liquid, COD 20mg/L after filter.
Crystal seed antiscale evaporative crystallization: liquid enters the head tank of crystal seed antiscale evaporation and crystallization system after filter, adds sulphur acid for adjusting pH
To 6 or so, plate heat exchanger is pumped to by charging and back segment crystal seed antiscale evaporation and crystallization system output distillate exchanges heat, temperature connects
Nearly solution boiling point；It is sent into degasser after liquid heating after filter, is in contact through nozzles spray and with upstream steam, removal dissolution
Oxygen and other fixed gases drain into atmosphere with a small amount of emptying steam.Liquid and evaporator cyclic salt after filter after adjusting acid, degassing process
Enter vertical tube falling film evaporator (Fig. 2) after water mixing and carry out circulating and evaporating concentration: feed liquid is sent to catch box 1 at the top of evaporator,
It is evenly distributed in every vertical heat exchanger tube 3 through liquid distribution trough 2, realizes that inner wall descending manner liquid film evaporation, steam walk shell side,
As heat source；The secondary steam of generation is gathered by saline slot periphery gas chamber, by entering both vapor compression after mesh mist eliminator 4
Enter evaporator shell journey after machine increasing temperature and pressure and be used as heat source, enters distillate tank after steam exothermic condensation, distillate and through toning
Enter water producing tank after liquid heat exchange after filter after acid, as recycle-water.Waste water is after the heating concentration of vertical heat-exchanging tube bundle, into lower end
In saline slot 5, evaporation dope is discharged from bottom in saline slot, in evaporative recirculation pump export pipeline and after acid adding, degassing process
Filter after liquid mix, be delivered to catch box 1 again, realize circulating and evaporating concentration process.Start-up is into evaporator saline slot
10g/L~15g/L calcium sulfate crystal seed is added, in vaporization cycle concentration process, sulfate radical and calcium ion concentration cross Jie in feed liquid
Stable state generates calcium sulfate crystallite, and Preferential adsorption is in the calcium sulfate seed surface in dosing system and grows.According to sulphur in evaporator
Sour calcium seed count adjusts the dope amount for entering cyclone separator, contains solid liquid phase through cyclone separator is isolated, a part by
It is 10g/L~15g/L that crystal seed recovery pipe, which returns in evaporator and maintains calcium sulfate seed count in evaporator saline slot, is remained
It is remaining handled by centrifugal dehydrator containing solid liquid phase after, obtain the outward transport of gypsum mud.It is about 15% that circulating and evaporating, which is concentrated into dope TDS, is steamed
The crystallized charging of dope is pumped at crystallisation cycle pump discharge after hair, and crystallization is entered after mixing with the feed liquid in crystallisation cycle pipeline
Heater is warming up to boiling point, is sent into crystallizer flash distillation, and the secondary steam of generation is condensed into after mesh mist eliminator into condenser
Distillate, distillate are used to preheat liquid after the filter after toning acid；Crystallizer feed solution TDS reaches about 40%, precipitates crystal, when solid
Content reaches about 30%, and slurries enter centrifugal dehydrator after exporting to thickener, and centrifuge mother liquor enters strong brine tank, crystallized to follow
Ring Pipeline transport mixes with dope after evaporation and is again introduced into crystallization heater, continues to participate in crystallization.Dewatered solids carnallite is through dry
After dry device heated-air drying, deicing salt export trade can be used as.
The secondary steam that evaporator is generated with crystallizer is separately recovered, and the rate of recovery is up to 90%, final to realize waste water zero-emission
It puts, recycle-water reaches " Standard of reclaimed water SL368-2006 ".
Claims (10)
1. a kind of processing method of production of polysilicon wastewater zero discharge, it is characterised in that production of polysilicon waste water successively turns through salinity
After change, dosing removal of impurities, the processing of crystal seed antiscale evaporative crystallization, water resource is recycled, obtains gypsum mud, the carnallite based on sodium chloride；Packet
Include following steps:
Salinity conversion: adding sodium sulphate into the production of polysilicon waste water Jing Guo homogenization, and the calcium chloride in waste water is converted
For calcium sulfate precipitation and sodium chloride, while so that calcium ion and sulfate ion content is reached saturation and being situated between steady state；
Dosing removal of impurities: milk of lime, coagulant, flocculation aid are added into the waste water after salinity conversion processing, through High-rate sedimentation
Pond carries out solid-liquid initial gross separation, and supernatant liquid phase carries out liquid after solid-liquid secondary separation is filtered through medium filter, by solid twice
Liquid separation, removes trace metal ion, suspended particle and a small amount of organic components in waste water；
Crystal seed antiscale evaporative crystallization: liquid successively enters evaporator progress circulating and evaporating concentration after acid adding, degassing process after filter, follows
Calcium ion and sulfate ion concentration are concentrated into supersaturated unstability and calcium sulfate crystallite, sulphur are precipitated in waste water in ring evaporating concentration process
Sour calcium crystallite is adsorbed in calcium sulfate seed surface and grows, and constantly recycles with feed liquid；Dope is after cyclone separation device after evaporation,
Part is used as gypsum mud outlet containing solid turbid after centrifugal dehydration treatment, and remaining part is maintained as supplement crystal seed re-injection evaporator
Calcium sulfate seed count is 10g/L~15g/L；Circulating and evaporating is concentrated into dope TDS in evaporator and reaches 15~20%, into knot
It is further concentrated into TDS in brilliant device and reaches 30~40%, precipitates crystal product, through centrifugal dehydration, is dried to obtain and is with sodium chloride
Main carnallite.
2. the processing method of production of polysilicon wastewater zero discharge according to claim 1, it is characterised in that including following step
It is rapid:
Step (1), homogenization: polysilicon industry production waste water enters conditioning tank and carries out homogenization, after homogenization, calcium
Ion concentration is greater than 4000mg/L, sulfate ion content≤1000mg/L；
Step (2), salinity conversion: the waste water after homogenization enters dosing pond, and sodium sulphate is added and converts calcium chloride in waste water
For calcium sulfate precipitation and sodium chloride, calcium ion and sulfate ion are in the steady state of saturation Jie；
Step (3), dosing removal of impurities: in dosing pond, the feeding lime cream into the waste water Jing Guo salinity conversion processing, in waste water
Micro magnesium ion and heavy metal ion, which combine, generates sediment；The waste water in dosing pond is discharged into efficient sedimentation tank again, is added
Coagulant and flocculation aid realize solid-liquid initial gross separation via efficient sedimentation tank flocculating setting；Supernatant enters in efficient sedimentation tank
Medium filter carries out liquid after solid-liquid secondary separation is filtered；High-rate sedimentation bottom of pond portion 30~50% is back to dosing containing solid liquid phase
Pond is mixed with the production of polysilicon waste water after homogenization, and residue is containing solid liquid phase successively through sludge concentration tank concentrate, filter press pressure
Contracting obtains moisture content in 20% mud cake below；
Step (4), crystal seed antiscale evaporative crystallization: liquid enters the head tank of crystal seed antiscale evaporation and crystallization system after filter, adds sulfuric acid tune
PH to 5~6 is saved, then is pumped into degasification in degasser；Waste water after degassing enters progress circulating and evaporating concentration in evaporator, is recycling
In evaporating concentration process, calcium ion and sulfate ion concentration progressively reach supersaturation, and system is changed from metasable state to unstability state,
Calcium sulfate crystallite is precipitated, is adsorbed in calcium sulfate seed surface and grows；Dope part after evaporation enters cyclone separator, obtains
Part containing solid liquid phase via crystal seed recovery pipe Returning evaporimeter as supplement crystal seed, maintenances calcium sulfate seed count be 10g/
L~15g/L, residue are used as gypsum mud outlet containing solid liquid phase after centrifugal dehydrator is handled；Dope is concentrated into TDS in device to be evaporated
Reach 15%~20%, continue to be concentrated into TDS into crystallizer and reach 30%~40%, product is precipitated crystal, when solid content reaches
To 10%~30%, obtain through centrifugal dehydration, drying process with sodium chloride as main carnallite.
3. the processing method of production of polysilicon wastewater zero discharge according to claim 1 or 2, it is characterised in that described is more
The TDS that crystal silicon produces waste water is 30000~60000mg/L, and for salinity based on sodium chloride and calcium chloride, calcium chloride accounts for total salinity
40%~60%；Ss suspended solid content is greater than 5000mg/L, and COD content is less than 150mg/L.
4. the processing method of production of polysilicon wastewater zero discharge according to claim 1 or 2, it is characterised in that turn through salinity
Change calcium ion content in treated waste water and be decreased to less than 1000mg/L, sodium chloride accounts for total salinity 80%~90%.
5. the processing method of production of polysilicon wastewater zero discharge according to claim 1 or 2, it is characterised in that described is mixed
Solidifying agent is inorganic polymer, and the inorganic polymer is aluminium polychloride or poly-ferric chloride, dosage be 10mg/L~
30mg/L；The flocculation aid is polyacrylamide, and dosage is 1mg/L~5mg/L.
6. the processing method of production of polysilicon wastewater zero discharge according to claim 1 or 2, it is characterised in that the height
Ss suspended solid content is less than 50mg/L in supernatant in effect sedimentation basin, and COD content is less than 60mg/L；The medium filter filter
Liquid ss suspended solid content≤10mg/L afterwards, COD content are less than 30mg/L.
7. the processing method of production of polysilicon wastewater zero discharge according to claim 1 or 2, it is characterised in that the steaming
Hair device is vertical tube falling film evaporator, circulating and evaporating concentration process are as follows: liquid is defeated by circulating pump after acid adding, degassing process after filter
It send to the catch box on vertical tube falling film evaporator top, waste water is after liquid distribution trough is distributed, into vertical heat-exchanging tube bundle, waste water
Tube side is walked, steam walks shell side；Waste water is after the heating concentration of vertical heat-exchanging tube bundle, into the saline slot of lower end, the secondary steaming of generation
Vapour is gathered by saline slot periphery gas chamber, removes drop, discharge system through the demister below gas chamber；Evaporation dope exists in saline slot
Circulating-pump outlet pipeline is mixed with liquid after the filter after acid adding, degassing process, is delivered to catch box again, realizes that circulating and evaporating is dense
Compression process；Calcium ion and sulfate ion concentration are concentrated into supersaturated unstability and sulfuric acid are precipitated in waste water in circulating and evaporating concentration process
Calcium crystallite, calcium sulfate crystallite are adsorbed in calcium sulfate seed surface and grow, and constantly recycle with feed liquid.
8. the processing method of production of polysilicon wastewater zero discharge according to claim 7, it is characterised in that start-up to
10g/L~15g/L calcium sulfate crystal seed is added in evaporator saline slot, is maintained in evaporator saline slot in circulating and evaporating concentration process
Calcium sulfate seed count is 10g/L~15g/L.
9. a kind of processing unit for production of polysilicon wastewater zero discharge described in claim 1, characterized by comprising: adjust
Save pond, dosing pond, efficient sedimentation tank, sludge concentration tank, filter press, medium filter, crystal seed antiscale evaporation and crystallization system；It is described
Crystal seed antiscale evaporation and crystallization system include head tank, degasser, evaporator, vortex separation system, crystal system connection；It is described
Conditioning tank for producing waste water supplied materials homogeneous and measure, the outlet of conditioning tank is connect with the import in dosing pond, the offer of dosing pond
Salinity conversion and a small amount of metal ion react precipitation position, and the outlet in the dosing pond and the import of efficient sedimentation tank connect,
The top water outlet of efficient sedimentation tank and the water inlet of medium filter connect supernatant being sent into medium filter, media filtration
The water outlet of device is successively connect with head tank, the degasser of crystal seed antiscale evaporation and crystallization system, the water outlet of degasser and evaporation
The water inlet of device connects, and the outlet of evaporator is connect with vortex separation system, crystal system respectively, the vortex separation system
Including sequentially connected cyclone separator and centrifugal dehydrator, crystal seed recovery pipe is additionally provided in the cyclone separator outlet
It is connect with evaporator by part re-injection containing solid liquid phase to evaporator；The crystal system includes sequentially connected crystallization heating
The secondary steam outlet of device, crystallizer, centrifugal dehydrator, the crystallizer is connect for recycle-water with condenser, is being crystallized
Thickener is equipped between device water outlet and centrifugal dehydrator, the crystallized circulation line of the water outlet of centrifugal dehydrator and crystallization are heated
The connection of device inlet ductwork is fed again into crystallization heater heat exchange and is warming up to boiling point after mixing centrifuge mother liquor with dope after evaporation, send
Enter crystallizer flash distillation；Connecting containing solid outlet with drying equipment for centrifugal dehydrator will be centrifuged wet solid material feeding drying equipment drying.
10. the processing unit of production of polysilicon wastewater zero discharge according to claim 9, it is characterised in that the adjusting
Pond is round or rectangular reinforced concrete structure pond body, conditioning tank inner and outer surfaces brushing anticorrosive paint；In the conditioning tank
It is provided with blender；
The dosing pond inner and outer surfaces brushing anticorrosive paint, dosing pond are furnished with Full-automatic agent-feeding device and dosing blender；
The medium filter selects one of quartz sand, potsherd, active carbon etc. or a variety of filtrates to stack and is used as filtering layer,
The partial size of the filtrate is in 0.5mm~2mm；
The crystallizer is using pressure outer circulation crystallizer.
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