CN106565045A - Complete equipment for stainless steel pickling wastewater treatment and resource recycling and treatment process - Google Patents
Complete equipment for stainless steel pickling wastewater treatment and resource recycling and treatment process Download PDFInfo
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- 238000000034 method Methods 0.000 title claims abstract description 65
- 230000008569 process Effects 0.000 title claims abstract description 58
- 229910001220 stainless steel Inorganic materials 0.000 title claims abstract description 30
- 239000010935 stainless steel Substances 0.000 title claims abstract description 30
- 238000004065 wastewater treatment Methods 0.000 title claims abstract description 19
- 238000004064 recycling Methods 0.000 title claims abstract description 14
- 238000005554 pickling Methods 0.000 title claims abstract description 11
- 238000001223 reverse osmosis Methods 0.000 claims abstract description 86
- 239000002351 wastewater Substances 0.000 claims abstract description 84
- 238000000108 ultra-filtration Methods 0.000 claims abstract description 72
- 238000001704 evaporation Methods 0.000 claims abstract description 63
- 230000008020 evaporation Effects 0.000 claims abstract description 62
- 238000003860 storage Methods 0.000 claims abstract description 51
- 239000012528 membrane Substances 0.000 claims abstract description 36
- 239000002253 acid Substances 0.000 claims abstract description 35
- 239000010802 sludge Substances 0.000 claims abstract description 32
- 238000002425 crystallisation Methods 0.000 claims abstract description 29
- 230000008025 crystallization Effects 0.000 claims abstract description 29
- 230000001105 regulatory effect Effects 0.000 claims abstract description 27
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 26
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims abstract description 20
- 150000003839 salts Chemical class 0.000 claims abstract description 18
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims abstract description 12
- 229910052938 sodium sulfate Inorganic materials 0.000 claims abstract description 12
- 235000011152 sodium sulphate Nutrition 0.000 claims abstract description 12
- 239000000126 substance Substances 0.000 claims abstract description 12
- 239000011780 sodium chloride Substances 0.000 claims abstract description 10
- 238000000926 separation method Methods 0.000 claims abstract description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 117
- 238000004140 cleaning Methods 0.000 claims description 84
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 76
- 239000000243 solution Substances 0.000 claims description 64
- 239000013078 crystal Substances 0.000 claims description 49
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims description 32
- 239000011737 fluorine Substances 0.000 claims description 32
- 229910052731 fluorine Inorganic materials 0.000 claims description 32
- 238000007710 freezing Methods 0.000 claims description 32
- 230000008014 freezing Effects 0.000 claims description 32
- 230000008676 import Effects 0.000 claims description 29
- 239000012452 mother liquor Substances 0.000 claims description 27
- 238000006386 neutralization reaction Methods 0.000 claims description 27
- 239000010413 mother solution Substances 0.000 claims description 23
- 238000011084 recovery Methods 0.000 claims description 22
- 239000002244 precipitate Substances 0.000 claims description 20
- 239000003814 drug Substances 0.000 claims description 19
- 238000005189 flocculation Methods 0.000 claims description 19
- 230000016615 flocculation Effects 0.000 claims description 19
- 238000006243 chemical reaction Methods 0.000 claims description 18
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 18
- 239000000047 product Substances 0.000 claims description 14
- 238000004062 sedimentation Methods 0.000 claims description 14
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 12
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 claims description 10
- 235000008733 Citrus aurantifolia Nutrition 0.000 claims description 10
- 239000005708 Sodium hypochlorite Substances 0.000 claims description 10
- 235000011941 Tilia x europaea Nutrition 0.000 claims description 10
- 239000001110 calcium chloride Substances 0.000 claims description 10
- 229910001628 calcium chloride Inorganic materials 0.000 claims description 10
- 239000000701 coagulant Substances 0.000 claims description 10
- 238000001914 filtration Methods 0.000 claims description 10
- 239000004571 lime Substances 0.000 claims description 10
- 238000004519 manufacturing process Methods 0.000 claims description 10
- 229920000642 polymer Polymers 0.000 claims description 10
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 claims description 10
- 238000005119 centrifugation Methods 0.000 claims description 9
- 238000005273 aeration Methods 0.000 claims description 8
- 238000005276 aerator Methods 0.000 claims description 8
- ODINCKMPIJJUCX-UHFFFAOYSA-N Calcium oxide Chemical compound [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 claims description 7
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 7
- 239000013505 freshwater Substances 0.000 claims description 7
- 238000010438 heat treatment Methods 0.000 claims description 7
- 239000011734 sodium Substances 0.000 claims description 7
- 229910052708 sodium Inorganic materials 0.000 claims description 7
- 238000005406 washing Methods 0.000 claims description 7
- 239000004902 Softening Agent Substances 0.000 claims description 6
- 239000003513 alkali Substances 0.000 claims description 6
- 239000004411 aluminium Substances 0.000 claims description 6
- 229910052782 aluminium Inorganic materials 0.000 claims description 6
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 6
- 239000003795 chemical substances by application Substances 0.000 claims description 6
- 239000000498 cooling water Substances 0.000 claims description 6
- 150000002500 ions Chemical class 0.000 claims description 6
- 229910021645 metal ion Inorganic materials 0.000 claims description 6
- 239000002455 scale inhibitor Substances 0.000 claims description 6
- 239000013049 sediment Substances 0.000 claims description 6
- 239000007787 solid Substances 0.000 claims description 6
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 5
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 claims description 5
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 claims description 5
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 5
- 230000000844 anti-bacterial effect Effects 0.000 claims description 5
- 229910052791 calcium Inorganic materials 0.000 claims description 5
- 239000011575 calcium Substances 0.000 claims description 5
- 229910001424 calcium ion Inorganic materials 0.000 claims description 5
- 238000003682 fluorination reaction Methods 0.000 claims description 5
- 229910052749 magnesium Inorganic materials 0.000 claims description 5
- 239000011777 magnesium Substances 0.000 claims description 5
- GTTYPHLDORACJW-UHFFFAOYSA-N nitric acid;sodium Chemical compound [Na].O[N+]([O-])=O GTTYPHLDORACJW-UHFFFAOYSA-N 0.000 claims description 5
- 239000002699 waste material Substances 0.000 claims description 5
- 239000012141 concentrate Substances 0.000 claims description 4
- 239000002826 coolant Substances 0.000 claims description 4
- 238000001816 cooling Methods 0.000 claims description 4
- 230000003311 flocculating effect Effects 0.000 claims description 4
- 239000006228 supernatant Substances 0.000 claims description 4
- 230000015572 biosynthetic process Effects 0.000 claims description 3
- 230000000903 blocking effect Effects 0.000 claims description 3
- 150000001768 cations Chemical class 0.000 claims description 3
- 239000003638 chemical reducing agent Substances 0.000 claims description 3
- 230000006835 compression Effects 0.000 claims description 3
- 238000007906 compression Methods 0.000 claims description 3
- 238000010612 desalination reaction Methods 0.000 claims description 3
- 239000000835 fiber Substances 0.000 claims description 3
- 238000009292 forward osmosis Methods 0.000 claims description 3
- 235000000396 iron Nutrition 0.000 claims description 3
- 229920002521 macromolecule Polymers 0.000 claims description 3
- 238000001471 micro-filtration Methods 0.000 claims description 3
- 238000001728 nano-filtration Methods 0.000 claims description 3
- 238000002203 pretreatment Methods 0.000 claims description 3
- 238000009287 sand filtration Methods 0.000 claims description 3
- 230000026676 system process Effects 0.000 claims description 3
- 239000006200 vaporizer Substances 0.000 claims description 3
- 239000002918 waste heat Substances 0.000 claims description 3
- 101100341609 Drosophila melanogaster jing gene Proteins 0.000 claims 13
- 238000005204 segregation Methods 0.000 claims 3
- 102000005393 Sodium-Potassium-Exchanging ATPase Human genes 0.000 claims 1
- 108010006431 Sodium-Potassium-Exchanging ATPase Proteins 0.000 claims 1
- 239000000463 material Substances 0.000 claims 1
- 238000007781 pre-processing Methods 0.000 claims 1
- 238000010025 steaming Methods 0.000 claims 1
- PUZPDOWCWNUUKD-UHFFFAOYSA-M sodium fluoride Chemical compound [F-].[Na+] PUZPDOWCWNUUKD-UHFFFAOYSA-M 0.000 abstract description 24
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 abstract description 14
- 238000001556 precipitation Methods 0.000 abstract description 12
- 239000011775 sodium fluoride Substances 0.000 abstract description 12
- 235000013024 sodium fluoride Nutrition 0.000 abstract description 12
- 239000004317 sodium nitrate Substances 0.000 abstract description 7
- 235000010344 sodium nitrate Nutrition 0.000 abstract description 7
- 229910017053 inorganic salt Inorganic materials 0.000 abstract description 2
- 230000003247 decreasing effect Effects 0.000 abstract 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- QDOXWKRWXJOMAK-UHFFFAOYSA-N dichromium trioxide Chemical compound O=[Cr]O[Cr]=O QDOXWKRWXJOMAK-UHFFFAOYSA-N 0.000 description 6
- 230000004907 flux Effects 0.000 description 6
- 239000000203 mixture Substances 0.000 description 5
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 5
- 238000006396 nitration reaction Methods 0.000 description 5
- 229910052742 iron Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 230000003647 oxidation Effects 0.000 description 4
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical compound [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 3
- LDHBWEYLDHLIBQ-UHFFFAOYSA-M iron(3+);oxygen(2-);hydroxide;hydrate Chemical compound O.[OH-].[O-2].[Fe+3] LDHBWEYLDHLIBQ-UHFFFAOYSA-M 0.000 description 3
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 230000007935 neutral effect Effects 0.000 description 3
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 2
- 229910000831 Steel Inorganic materials 0.000 description 2
- 230000003851 biochemical process Effects 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- ZCDOYSPFYFSLEW-UHFFFAOYSA-N chromate(2-) Chemical compound [O-][Cr]([O-])(=O)=O ZCDOYSPFYFSLEW-UHFFFAOYSA-N 0.000 description 2
- 239000011651 chromium Substances 0.000 description 2
- 238000005345 coagulation Methods 0.000 description 2
- 230000015271 coagulation Effects 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- SZVJSHCCFOBDDC-UHFFFAOYSA-N ferrosoferric oxide Chemical compound O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 description 2
- 239000012467 final product Substances 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- 244000005700 microbiome Species 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 229910017604 nitric acid Inorganic materials 0.000 description 2
- 238000006213 oxygenation reaction Methods 0.000 description 2
- 235000010265 sodium sulphite Nutrition 0.000 description 2
- AKHNMLFCWUSKQB-UHFFFAOYSA-L sodium thiosulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=S AKHNMLFCWUSKQB-UHFFFAOYSA-L 0.000 description 2
- 235000019345 sodium thiosulphate Nutrition 0.000 description 2
- 239000010959 steel Substances 0.000 description 2
- 230000032258 transport Effects 0.000 description 2
- 241000894006 Bacteria Species 0.000 description 1
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 description 1
- 229910021543 Nickel dioxide Inorganic materials 0.000 description 1
- 239000006004 Quartz sand Substances 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
- MMDJDBSEMBIJBB-UHFFFAOYSA-N [O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[NH6+3] Chemical compound [O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[NH6+3] MMDJDBSEMBIJBB-UHFFFAOYSA-N 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 238000000137 annealing Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 description 1
- WUKWITHWXAAZEY-UHFFFAOYSA-L calcium difluoride Chemical compound [F-].[F-].[Ca+2] WUKWITHWXAAZEY-UHFFFAOYSA-L 0.000 description 1
- 229910001634 calcium fluoride Inorganic materials 0.000 description 1
- VQWFNAGFNGABOH-UHFFFAOYSA-K chromium(iii) hydroxide Chemical compound [OH-].[OH-].[OH-].[Cr+3] VQWFNAGFNGABOH-UHFFFAOYSA-K 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 239000006071 cream Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 229960004887 ferric hydroxide Drugs 0.000 description 1
- 229910001448 ferrous ion Inorganic materials 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 239000008103 glucose Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- -1 iron ion Chemical class 0.000 description 1
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 description 1
- IEECXTSVVFWGSE-UHFFFAOYSA-M iron(3+);oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Fe+3] IEECXTSVVFWGSE-UHFFFAOYSA-M 0.000 description 1
- 239000010808 liquid waste Substances 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 238000009285 membrane fouling Methods 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 238000005498 polishing Methods 0.000 description 1
- 238000011112 process operation Methods 0.000 description 1
- 238000005086 pumping Methods 0.000 description 1
- 238000010926 purge Methods 0.000 description 1
- 238000010791 quenching Methods 0.000 description 1
- 230000000171 quenching effect Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000006722 reduction reaction Methods 0.000 description 1
- 238000010591 solubility diagram Methods 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 239000001117 sulphuric acid Substances 0.000 description 1
- 235000011149 sulphuric acid Nutrition 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 238000003466 welding Methods 0.000 description 1
Abstract
Complete equipment for stainless steel pickling wastewater treatment and resource recycling and a treatment process are disclosed. A pretreatment section, a membrane treatment section and a quality-based crystallization section are involved. The invention is characterized in that a storage regulating basin, a neutralization-oxidation reaction tank, a flocculent precipitation tank, a filter, an ultrafiltration and reverse osmosis system, a membrane concentration system and an evaporation and concentration and quality-based crystallization system are mutually connected end to end through pipelines. Each dosage device is respectively arranged on corresponding section. According to the order of the pretreatment section, the membrane treatment section and the quality-based crystallization section, thirteen steps are included for the operation. By the treatment process of chemical reactive precipitation, membrane separation concentration and evaporation and quality-based crystallization, various acid wastewaters mainly containing acid and inorganic salt can be treated to realize recycling of wastewater. After crystallization of salt, sodium sulfate (and sodium chloride), sodium nitrate, sodium fluoride and other products can be recycled, and zero-discharge resource utilization of stainless steel pickling wastewater is realized. Meanwhile, system sludge yield is greatly reduced such that the burden of sludge treatment is decreased.
Description
Technical field
The present invention relates to a kind of environmental protection equipment, complexes and technique that more particularly to a kind of stainless steel acid cleaning waste water Treatment and recovery is reclaimed.
Background technology
Rustless steel is widely used because of its excellent corrosion resistance and good outward appearance.In process of production, inevitably through courses of processing such as annealing, normalizing, quenching, welding, surface can produce the iron scale of black to rustless steel often.Oxide skin not only affects stainless presentation quality, and also the following process of product can be had a negative impact, therefore must be removed using surface treatment methods such as pickling, polishings before following process.
It is FeO, Fe that stainless steel surfaces can produce iron scale, its main component2O3、NiO2、Cr2O3、Fe3O4、FeO·Cr2O3、Ni·Fe2O3、FeO·Cr2O3·Fe2O3Deng dense form oxide.The basic adhesive force of these oxides is strong, adopting ball blast, in the handling process of group technology such as high temperature alkaline etching, molten-salt electrolysis, nitration mixture pickling, multistage rinsing, the multiply pickling-rinsing waste water such as neutral salt waste water, acid-bearing wastewater, fluorine-containing nitration mixture waste water are inevitably discharged.
During acid-washing stainless steel, be typically that the iron scale for going to surface is removed with sulphuric acid pre-sour first, then pickling carried out with 90-160g/L nitric acid and 50-60g/L Fluohydric acid .s nitration mixture.Metal and metal oxide can be generated Cr by the nitric acid with strong oxidizing property3+、Fe3+And Ni2+Ion, these metal ions (especially Cr3+And Fe3+) and Fluohydric acid. form stable complex.In multistage rinse cycle, above-mentioned acid solution and metal ion are entered in washings, form pickling waste waterss.
Stainless steel waste water is mostly divided into two classes by stainless steel enterprises both at home and abroad：Containing Cr6+Neutral salt waste water and nitration mixture waste water.The former Jing electronations will wherein overwhelming majority Cr6+It is converted into Cr3+Afterwards, then plus alkali (typically sodium hydroxide), generate chromium hydroxide precipitation, waste water enters nitration mixture wastewater equalization pond again, adds alkali (typically Calx) to be neutralized reaction, make Cr in waste water3+Water-fast hydroxide deposit is generated with the ferrum in waste water, nickel.This method is simple to operate, is conventional process method for waste water.
By neutralization precipitation, sludge condensation and dehydration, final to mud cake russet.This method processes stainless steel acid cleaning waste water, although neutralization, reduction, precipitation process have been carried out to waste water, but in the day-to-day operation at each enterprise wastewater station, to guarantee standard water discharge, lime cream is usually excessively added, and is thereby resulted in mud cake amount and is greatly increased.And containing harmful substances such as a large amount of nickel, fluorine in these sludge, with very big harm, it is necessary to safe disposal.And it is increasingly strict current to environmental requirement in society, Treatment of Sludge expense is more and more expensive.
Furthermore, with the requirement more and more higher of people's environmental pollution, new requirement be there has also been to discharging the total nitrogen in water, originally only through neutralization precipitation can qualified discharge waste water, because the nitrate anion containing very high concentration in waste water, qualified discharge has been unable to it, it is necessary to which the nitrogen to containing in waste water carries out denitrogenation processing.
At present, conventional denitrification treatment process is biochemical process, using the Denitrification of denitrifying bacterium, the nitrate nitrogen for containing is changed into nitrogen discharge from water in waste water.This process must be carried out on the premise of carbon source abundance, and in pickling waste waterss, it is generally deficient of Organic substance carbon source, a large amount of methanol, glucose etc. must be additionally added during biochemical treatment as the carbon source of microorganism denitrification process, simultaneously, as the nitrogen in nitrate anion is removed, the pH of water is stepped up, and is the pH environment for maintaining growth of microorganism to need, it is necessary to add acid and be neutralized.Therefore, biochemical process denitrification operation is costly, constrains the purified treatment of pickling waste waterss.
The content of the invention
The purpose of the present invention is, for defect present in prior art, to provide the complexes that a kind of stainless steel acid cleaning waste water Treatment and recovery is reclaimed.Patent of the present invention is adopted with chemical neutralization precipitation as pretreatment, film process recycle-water, sub-prime crystallization reclaim salt based on wastewater treatment and resource recovery system, the salt contained in waste water is reclaimed as resource, and reclaim Water circulation production.Patent of the present invention is directed to stainless steel acid cleaning waste water, using the process of three segment process, realizes wastewater zero discharge, and salt resource is reclaimed.Processing stage the present invention includes three segment process:First paragraph pretreatment process, predominantly chemical reaction, neutralization precipitation and filtration；Second segment film process operation, mainly using membrane separation technique, the salt in waste water is removed, and reclaims fresh water reuse, and the concentrated water that membranous system is produced is enriched the salt of high concentration, can be further processed in back segment operation；3rd section of sub-prime Crystallization Procedure, low-temperature evaporation condensing crystallizing is adopted mainly, salt bearing liquid wastes are further concentrated, and the difference by salt therein (such as sodium fluoride, sodium sulfate etc.) according to its dissolubility at a certain temperature, various salt are made to crystallize respectively, freezing and crystallizing technology is adopted again, the temperature of concentrated solution is reduced, and the sodium nitrate in concentrated solution is reduced as solubility with temperature is reduced and is produced crystallization.
Pretreatment section includes：Storage regulating reservoir, neutralization oxidation reaction groove, flocculation reaction groove, stillpot, filter, intermediate pool, sludge dewatering unit, regulating reservoir elevator pump, aerator, sodium hydroxide throwing device, high polymer coagulant throwing device, aluminium polychlorid throwing device.
Film process section includes：Self-cleaning filter, ultrafiltration apparatus, ultra-filtration water groove, cartridge filter, reverse osmosis unit, reverse osmosis concentrated tank, film softening plant, concentration film intake chamber, concentration film device, reuse tank, ultrafiltration intake pump, feed water by reverse osmosis pump, reverse osmosis high-pressure pump, film softens feed pump, concentration film feed pump, concentration film high-pressure pump, ultrafiltration apparatus cleaning pump, air compressor machine, chemically-cleaning device, sodium hypochlorite throwing device, softening agent throwing device, scale inhibitor feeding device, citric acid throwing device.
Sub-prime crystallized region includes：Concentrated solution storage tank, heat exchanger, evaporation concentrator, concentrated solution fluorine removal groove, crystallizing evaporator, freezing and crystallizing device, magma subsider, centrifugal separator, centrifuge mother liquor groove, crystal storage tank, evaporation and concentration feed pump, evaporation and concentration circulating pump, evaporative crystallization feed pump, freezing and crystallizing feed pump, crystalline mother solution efflux pump, centrifugal separator feed pump, centrifuge mother liquor pump.
It is characterized in that：In pretreatment section, stainless steel acid cleaning waste water is stored in storage regulating reservoir, stores regulating reservoir outlet and is connected with the water inlet of neutralization oxidation reaction groove by pipeline and regulating reservoir elevator pump, and storage regulating tank is provided with aerator, the oxygenation into pond.Neutralization oxidation reaction groove is provided with oxygenate apparatus and sodium hydroxide throwing device, adds sodium hydroxide and is neutralized.Neutralization oxidation trough outlet is connected with flocculation reaction groove by pipeline, and flocculation reaction groove is provided with high polymer coagulant throwing device.Flocculation reaction groove outlet is connected with stillpot water inlet by pipeline.Stillpot outlet is connected by pipe-and-filter water inlet, and filter is provided with aluminium polychlorid throwing device, carries out coagulation and filtration.Filter outlet is connected with intermediate pool water inlet by pipeline, and intermediate pool outlet is connected to film process section by pipeline.The mud mouth of stillpot passes through pipeline and pump is connected with sludge dewatering unit.
In film process section, the intermediate pool outlet of pretreatment section is connected with self-cleaning filter water inlet by pipeline and ultrafiltration intake pump, is provided with sodium hypochlorite throwing device, for adding sodium hypochlorite antibacterial before self-cleaning filter water inlet.The outlet of self-cleaning filter is connected with the water inlet of ultrafiltration apparatus by pipeline.Ultrafiltration apparatus outlet is connected with the water inlet of ultra-filtration water groove by pipeline.The outlet of chemically-cleaning device is cleaned interface with the medicament of ultrafiltration apparatus by pipeline and is connected, and the washing outlet of ultrafiltration apparatus is connected by pipeline with the import of chemically-cleaning device.The air inlet of ultrafiltration apparatus is connected with air compressor machine by pipeline.Ultrafiltration is gone out an outlet of groove and is connected with the water inlet of cartridge filter by pipeline and feed water by reverse osmosis pump, another outlet passes through pipeline and ultrafiltration apparatus cleaning pump is connected with the Butterworth Hatch of ultrafiltration apparatus, and its pipeline is provided with sodium hypochlorite throwing device and citric acid throwing device.The outlet of cartridge filter passes through pipeline and reverse osmosis high-pressure pump is connected with the water inlet of reverse osmosis unit, and reverse osmosis unit front end is provided with scale inhibitor feeding device.The clean water outlet of reverse osmosis unit is connected with the water inlet of reuse tank by pipeline, and concentrated water outlet is connected with the water inlet of reverse osmosis concentrated tank by pipeline, and the cleaning of reverse osmosis unit is imported and exported and is connected with the export and import of chemically-cleaning device by pipeline respectively.Reverse osmosis concentrated tank import is provided with softening agent throwing device, the outlet of reverse osmosis concentrated tank passes through pipeline and film is softened feed pump and is connected with the water inlet of film softening plant, the outlet of film softening plant is connected with the water inlet of concentration film intake chamber by pipeline, the outlet of concentration film intake chamber passes through pipeline and concentration film feed pump is connected with cartridge filter, and cartridge filter outlet is passed through pipeline and concentration film high-pressure pump and is connected with the water inlet of concentration film device.The clean water outlet of concentration film device is connected with reuse tank by pipeline, the dope outlet of concentration film device is connected to the water inlet of the concentrated solution storage tank of hypomere operation by pipeline, and the cleaning inlet and outlet connectors for concentrating film device connect the export and import of chemically-cleaning device respectively by pipeline.
In sub-prime crystallized region, the dope outlet of the concentration film device of film process section is connected with the import of concentrated solution storage tank by pipeline, the outlet of concentrated solution storage tank is connected with the cold side import of heat exchanger by pipeline and evaporation and concentration feed pump, the cold side outlet port of heat exchanger is connected with another vapor heat exchanger, the coolant side outlet of vapor heat exchanger is connected with the import of evaporation concentrator by pipeline, concentrated water after membrance concentration is first preheated before evaporation concentrator is entered, the indirect steam that the thermal source of preheating is first discharged using sub-prime crystallized region, make full use of waste heat, insufficient section is again using raw steam heating.The concentrated solution outlet of evaporation concentrator passes through pipeline and evaporation and concentration circulating pump is connected with the import of concentrated solution fluorine removal groove, and the outlet of evaporation and concentration circulating pump takes back the import of evaporation concentrator by an other pipeline, is flowed back.The crystalline solid outlet of evaporation concentrator is connected with the import of the magma subsider of the operation by pipeline, the outlet of the magma subsider is connected with centrifugal separator import by the centrifugal separator feed pump of pipeline and the operation, the fluorination sodium crystal that centrifugal separator is separated falls into crystal (sodium fluoride) storage tank, the mother solution separated is connected to centrifuge mother liquor groove by pipeline, then takes back concentrated solution storage tank by pipeline and centrifuge mother liquor pump.Evaporation concentrator rear end is provided with fluorine removal groove, and the fluorine for remaining in concentrated solution is removed, to ensure the purity of sodium nitrate, sodium sulfate product.The outlet of concentrated solution fluorine removal groove is connected with the import of crystallizing evaporator by pipeline and evaporative crystallization feed pump.Concentrated solution fluorine removal groove is provided with lime throwing device, and the sediment outlet of concentrated solution fluorine removal groove enters sludge dewatering unit by pipeline.The outlet of crystallizing evaporator is connected with the import of freezing and crystallizing device by pipeline and freezing and crystallizing feed pump, the crystalline solid outlet of crystallizing evaporator is connected with the import of the magma subsider of the operation by pipeline, the outlet of the magma subsider is connected with centrifugal separator import by the centrifugal separator feed pump of pipeline and the operation, sodium sulfate (or Sodium Chloride) crystal that centrifugal separator is separated falls into crystal (sodium sulfate or Sodium Chloride) storage tank, the mother solution separated is connected to centrifuge mother liquor groove by pipeline, concentrated solution fluorine removal groove is taken back by pipeline and centrifuge mother liquor pump again.The outlet of freezing and crystallizing device takes back the storage regulating reservoir of pretreatment section by pipeline and crystalline mother solution efflux pump, and the outlet of crystalline mother solution efflux pump is additionally provided with pipeline, will arrange outside remaining crystalline mother solution.The crystalline solid outlet of freezing and crystallizing device is connected with the import of the magma subsider of the operation by pipeline, the outlet of the magma subsider is connected with centrifugal separator import by the centrifugal separator feed pump of pipeline and the operation, the nitric acid sodium crystal that centrifugal separator is separated falls into crystal (sodium nitrate) storage tank, the mother solution separated is connected to centrifuge mother liquor groove, then the import that freezing and crystallizing device is taken back by pipeline and centrifuge mother liquor pump by pipeline.The cooling water outlet and inlet of freezing and crystallizing device connects the import and export of recirculated cooling water respectively by pipeline.
Aeration tube is provided with the storage regulating reservoir, with blower unit into aerator, the ferrous salt for containing can be oxidized to ferric iron, then removed by adding sodium hydroxide production ferric hydroxide precipitate in waste water, meanwhile, in waste water, other contained metal ions are also together removed.Filter is sand filtration, multi-medium filtering or fiber filter device.
The concentration film device is high pressure reverse osmosiss rolled film or high pressure reverse osmosiss disc type film or vibrating diaphragm or forward osmosis membrane.
The evaporation concentrator is mechanical compress vaporizer (MVR) or multi-effect evaporator, and crystallizing evaporator is mechanical compression evaporation crystallizer or Multi-effect evaporation crystallizer.
The concentration film device is provided with the waste-heat recovery device that membrane flux is improved for the operating temperature for improving membranous system, and preheating is into the indirect steam that the thermal source of the concentrated water of evaporation concentrator is that sub-prime crystallized region is discharged.
Present invention also offers the handling process of stainless steel acid cleaning waste water is processed with stainless steel acid cleaning waste water Treatment and recovery recovery apparatus set, including with the following steps：
Pretreatment section：
(1) stainless steel acid cleaning waste water enters into storage regulating reservoir and carries out water quality and quantity regulation, and carries out aeration, the ferrous irons in oxidized waste water；
(2) the adjusted pond elevator pump of waste water that step (1) is processed is promoted to neutralization oxidation reaction groove, in reactive tank, on the one hand proceed oxidation reaction, on the one hand add sodium hydroxide, the metal ions such as the ferrum in waste water are converted into hydrate precipitate；
(3) waste water that step (2) is processed enters back into flocculation sediment groove, under the flocculation of high polymer coagulant, forms big flocculating body, and the precipitate and separate in sedimentation tank；
(4) waste water that step (3) is processed enters into filter and is filtered, and removes oil removal, is being stored to intermediate pool；
(5) the sludge Jing sludge pumps that Jing steps (3) precipitate are lifted and carry out sludge dewatering to sludge dewatering unit；
Film process section：
(6) pretreated waste water Jing ultrafiltration intake pump lifts ultrafiltration apparatus, in ultrafiltration apparatus, the float contained in water, macromolecular substances are separated, waste water is stored into ultra-filtration water groove, before waste water enters ultrafilter membrane, antibacterial is added, and Jing self-cleaning filters are filtered, prevent film blocking, pollution, self-cleaning filter can be cleaned to film, when seriously polluted, Chemical cleaning can be carried out, the concentrated water of generation returns to pretreatment system process；
(7) the waste water Jing feed water by reverse osmosis pumps that step (6) is processed are lifted into reverse osmosis unit; waste water enters reverse osmosis unit after cartridge filter filtration after the pressurization of reverse osmosis high-pressure pump; the fresh water of reverse osmosis unit production enters reuse tank and stores reuse; concentrated water is stored into reverse osmosis concentrated tank; waste water adds antisludging agent, reducing agent protecting film before into reverse osmosis unit; and it is provided with chemically-cleaning device, film capable of washing；
(8) concentrated water that step (7) is processed, film softening plant is entered Jing after pump is lifted, soften medicament addition device and add medicament, the incrustation ions such as the calcium and magnesium in removal waste water, the precipitate of formation is separated by the tubular ultra-filtration membrane of film softening plant, water outlet enters concentration film intake chamber, and concentrated water returns to pretreatment section；
(9) concentrated water that step (8) is processed, concentration film device is entered through concentrating film feed pump, further concentrated water is concentrated, concentration film device is provided with cartridge filter and chemically-cleaning device, fresh water enters reuse tank reuse, and concentrated solution enters hypomere operation；
Sub-prime crystallized region：
(10) the concentrated solution Jing evaporation and concentration feed pump for entering into concentrated solution storage tank is lifted, heated into heat exchanger, dope after heating enters evaporation concentrator, is evaporated concentration under negative pressure, and the fluorination sodium crystal of generation is after sedimentation, centrifugation as Product recycling；
(11) concentrated solution that step (10) is processed, into concentration fluorine removal groove, feeding lime or calcium chloride, go fluorine removal, precipitate Jing transports to the sludge dewatering unit of pretreatment section, supernatant Jing evaporative crystallization feed pumps are promoted to crystallizing evaporator, and sodium sulfate that evaporative crystallization is produced and (or) sodium chloride crystal are after sedimentation, centrifugation as Product recycling；
(12) serosity that step (11) is processed, chilled crystallization feed pump are promoted to freezing and crystallizing device, the cooling down in freezing and crystallizing device, crystallize out nitric acid sodium crystal, and crystal is after sedimentation, centrifugation as Product recycling；
(13) disposal is arranged outside the crystallized mother solution efflux pump of remaining crystalline mother solution that step (12) is processed, or returns pretreatment section and processed.
Neutralization alkali liquor in the step (2) is sodium hydroxide or sodium hydroxide+calcium chloride (or Calx), need after the pre-treatment, enter film process before set up medicament softening plant, the calcium ion in waste water is removed.When adding sodium hydroxide, the final product for reclaiming has sodium fluoride, and adding sodium hydroxide+calcium chloride (or Calx) final products does not have a sodium fluoride, and after filtration, set up medicament softening plant before film process section, the calcium ion gone in eliminating water.The chromate waste water that discharges in production, neutral salt waste water, after pretreatment, (plus sodium sulfite or sodium thiosulfate oxidoreduction, hydro-oxidation sodium neutralization precipitation) can be mixed into above-mentioned Waste Water Treatment and process together.
In the step (6), arrange by the content of the bivalence in water and above ion or be not provided with before reverse osmosis unit, setting up Weak-acid cation switch.
In the film process section of step (6)～(9), ultrafiltration+reverse osmosis process carries out desalination, the concentrated water that reverse osmosiss are produced is again after medicament softens, tubular ultra-filtration membrane (film softening plant) is separated, enter back into concentration film device further to concentrate, when the hardness in waste water is higher, stillpot and filter can be set up before tubular ultra-filtration membrane or stillpot is only set, NF membrane is set up when divalent salts comparision contents are high or microfiltration+nanofiltration+reverse osmosiss combination is set.
It is an advantage of the invention that using chemical reaction precipitation, membrane separation concentration, and evaporation sub-prime crystallization process handling process, can process various containing acid, the acid waste water based on inorganic salt, realize waste water recycling, after salt is crystallized, the product such as recyclable sodium sulfate (and Sodium Chloride), sodium nitrate, sodium fluoride, realizes stainless steel acid cleaning waste water zero-emission recycling.Simultaneity factor sludge yield is substantially reduced, and alleviates the burden of sludge treatment.
Description of the drawings
The process flow diagram of Fig. 1 present invention；
The structural representation of Fig. 2 present invention.
In figure：Pretreatment section：101 storage regulating reservoirs, in 102 and oxidation reaction groove, 103 flocculation reaction grooves, heavy 104 shallow lake grooves, 105 filters, 106 intermediate pools, 107 sludge dewatering units, 108 regulating reservoir elevator pumps, 109 aerators, 110 sodium hydroxide throwing devices, 111 high polymer coagulant throwing devices, 112 aluminium polychlorid throwing devices；
Film process section：201 self-cleaning filters, 202 ultrafiltration apparatus, 203 ultra-filtration water grooves, 204 cartridge filters, 205 reverse osmosis units, 206 reverse osmosis concentrated tanks, 207 film softening plants, 208 concentration film intake chambers, 209 concentration film devices, 210 reuse tanks, 211 ultrafiltration intake pumps, 212 feed water by reverse osmosis pumps, 213 reverse osmosis high-pressure pumps, 214 films soften feed pump, 215 concentration film feed pumps, 216 concentration film high-pressure pumps, 217 ultrafiltration apparatus cleaning pumps, 219 air compressor machines, 220 chemically-cleaning devices, 221 sodium hypochlorite throwing devices, 222 softening agent throwing devices, 223 scale inhibitor feeding devices, 224 citric acid throwing devices；
Sub-prime crystallized region：301 concentrated solution storage tanks, 302 heat exchangers, 303 evaporation concentrators, 304 concentrated solution fluorine removal grooves, 305 crystallizing evaporators, 306 freezing and crystallizing devices, 307 magma subsiders, 308 centrifugal separators, 309 centrifuge mother liquor grooves, 310 crystal storage tanks, 311 evaporation and concentration feed pumps, 312 evaporation and concentration circulating pumps, 313 evaporative crystallization feed pumps, 314 freezing and crystallizing feed pumps, 315 crystalline mother solution efflux pumps, 316 centrifugal separator feed pumps, 317 centrifuge mother liquor pumps, 319 lime throwing devices.
Specific embodiment
Embodiment one
Embodiments of the invention are further illustrated below in conjunction with the accompanying drawings：
Referring to Fig. 1, Fig. 2, the present embodiment is made up of pretreatment section, film process section, sub-prime crystallized region.
Pretreatment section includes：Storage regulating reservoir 101, neutralization oxidation reaction groove 102, flocculation reaction groove 103, stillpot 104, filter 105, intermediate pool 106, sludge dewatering unit 107, regulating reservoir elevator pump 108, aerator 109, sodium hydroxide throwing device 110, high polymer coagulant throwing device 111, aluminium polychlorid throwing device 112.
Film process section includes：Self-cleaning filter 201, ultrafiltration apparatus 202, ultra-filtration water groove 203, cartridge filter 204, reverse osmosis unit 205, reverse osmosis concentrated tank 206, film softening plant 207, concentration film intake chamber 208, concentration film device 209, reuse tank 210, ultrafiltration intake pump 211, feed water by reverse osmosis pump 212, reverse osmosis high-pressure pump 213, film softens feed pump 214, concentration film feed pump 215, concentration film high-pressure pump 216, ultrafiltration apparatus cleaning pump 217, air compressor machine 219, chemically-cleaning device 220, sodium hypochlorite throwing device 221, softening agent throwing device 222, scale inhibitor feeding device 223, citric acid throwing device 224.
Sub-prime crystallized region includes：Concentrated solution storage tank 301, heat exchanger 302, evaporation concentrator 303, concentrated solution fluorine removal groove 304, crystallizing evaporator 305, freezing and crystallizing device 306, magma subsider 307, centrifugal separator 308, centrifuge mother liquor groove 309, crystal storage tank 310, evaporation and concentration feed pump 311, evaporation and concentration circulating pump 312, evaporative crystallization feed pump 313, freezing and crystallizing feed pump 314, crystalline mother solution efflux pump 315, centrifugal separator feed pump 316, centrifuge mother liquor pump 317, lime throwing device 319.
In pretreatment section, stainless steel acid cleaning waste water is stored in storage regulating reservoir 101 and carries out water quality and quantity regulation, storage regulating reservoir outlet is passed through pipeline and regulating reservoir elevator pump 108 and is connected with the water inlet of neutralization oxidation reaction groove 102, storage regulating tank 101 is provided with aerator, aeration tube is provided with storage regulating reservoir 101, with blower unit into aerator to oxygenation in pond, the ferrous ions contained in making waste water are into iron ion；Neutralization oxidation reaction groove 102 is provided with oxygenate apparatus and sodium hydroxide throwing device 110, adds sodium hydroxide and is neutralized, while further by precipitated metals such as the ferrous oxidation of residual, production hydrated ferric oxide .s under the Oxidation of oxygen；Neutralization 102 outlet of oxidation trough is connected to flocculation reaction groove 103 by pipeline, and flocculation reaction groove 103 is provided with high polymer coagulant throwing device 111, adds high polymer coagulant, makes the metal precipitates such as the hydrated ferric oxide. in water be condensed into big flocculating body so as to subsequent sedimentation；103 outlet of flocculation reaction groove is connected with stillpot 104 by pipeline；The metal flco such as hydrated ferric oxide. is settled in stillpot, and supernatant enters filter 105 by 104 outlet of stillpot, and filter 105 is quartz sand filtration equipment.Filter 105 is provided with aluminium polychlorid throwing device 112, carries out coagulation and filtration；105 water outlet of filter enters intermediate pool 106 by pipeline, and 106 outlet of intermediate pool is connected to film process section by pipeline.The mud mouth Jing pumpings that precipitate in stillpot 104 passes through are processed to sludge treating block 107.
In film process section, 106 outlet of intermediate pool of pretreatment section is connected to by self-cleaning filter 201 by pipeline and ultrafiltration intake pump 211, sodium hypochlorite throwing device 221 is provided with before self-cleaning filter 201, for adding sodium hypochlorite antibacterial；The outlet of self-cleaning filter 201 is connected to the water inlet of ultrafiltration apparatus 202 by pipeline, and after Ultra filtration membrane, float in waste water etc. is removed waste water, and outlet is connected to ultra-filtration water groove 203 by pipeline；Ultrafiltration apparatus 202 are provided with chemically-cleaning device 220, and when film is contaminated serious, for cleaning ultrafilter membrane, cleaning medicinal liquid is back to that chemically-cleaning device 220 is reusable, arranges outside the cleanout fluid of failure；The air inlet of ultrafiltration apparatus 202 is connected with air compressor machine 219 by pipeline, can carry out air purge to ultrafiltration apparatus；One outlet of ultra-filtration water groove 203 passes through pipeline and feed water by reverse osmosis pump 212 is connected with the water inlet of cartridge filter 204, another outlet passes through pipeline and ultrafiltration apparatus cleaning pump 217 is connected with the Butterworth Hatch of ultrafiltration apparatus 202, its pipeline is provided with sodium hypochlorite throwing device 221 and citric acid throwing device 224, can carry out daily cleaning to ultrafilter membrane；The outlet of cartridge filter 204 is connected with the water inlet of reverse osmosis unit 205 by pipeline and reverse osmosis high-pressure pump 213, water is after reverse osmosis membrane separation, salt in waste water can be concentrated in concentrated water, reverse osmosis unit is provided with scale inhibitor feeding device 223, antisludging agent can be added and slow down film fouling；Reverse osmosis produced water is demineralized water, is connected to reuse tank 210 by pipeline by the clean water outlet of reverse osmosis unit 205, and concentrated water is then connected to reverse osmosis concentrated tank 206 by pipeline；The cleaning of reverse osmosis unit 205 is imported and exported and is connected with the export and import of chemically-cleaning device 220 by pipeline respectively, after reverse osmosis membrane is contaminated, can carry out Chemical cleaning.Reverse osmosis concentrated tank 206 is provided with softening agent throwing device 222, can add softening medicament, and the calcium and magnesium plasma in concentrated water is formed precipitate；The water outlet of reverse osmosis concentrated tank 206 passes through pipeline and film softens feed pump 214 and enters film softening plant 207, and in film softening plant, the precipitate such as calcium and magnesium is separated removal.The outlet of film softening plant 207 enters concentration film intake chamber 208 by pipeline, the outlet of concentration film intake chamber 208 passes through pipeline and concentration film feed pump 215 is connected with cartridge filter 204,204 outlet of cartridge filter passes through pipeline and concentration film high-pressure pump 216 is connected with the water inlet of concentration film device 209, concentration film device 209 is high pressure reverse osmosiss rolled film, in concentration film device, by membrance separation, the salinity in concentrated water is further concentrated；The fresh water that concentration film device 209 is produced enters reuse tank 210 by pipeline by the clean water outlet for concentrating film device, the dope that concentration film device 209 is produced is connected to the concentrated solution storage tank 301 of hypomere operation by pipeline, the cleaning of concentration film device 209 is provided with chemically-cleaning device 220, and Chemical cleaning can be carried out after film is contaminated.
In sub-prime crystallized region, the concentrated solution of the concentration film device 209 of film process section is stored into concentrated solution storage tank 301 by pipeline, the outlet of concentrated solution storage tank 301 passes through pipeline and evaporation and concentration feed pump 311 enters the cold side of heat exchanger 302, the indirect steam produced with this section is exchanged heat, preheat concentrated solution, enter back into another vapor heat exchanger 302, supplementary heating is carried out using steam-out (SO), concentrated solution after heating from the coolant side outlet of vapor heat exchanger 302 out, evaporation concentrator 303 is entered by pipeline, low-temperature evaporation concentration is carried out under vacuo, evaporation concentrator 303 is mechanical compress vaporizer (MVR).Simultaneously, the sodium fluoride contained in concentrated solution forms crystal, the concentrated solution of evaporation concentrator 303 passes through pipeline and evaporation and concentration circulating pump 312 enters concentrated solution fluorine removal groove 304, the fluorine removal groove 304 is provided with lime throwing device 319, can feeding lime, the fluorion production calcium fluoride remained in making concentrated solution is deposited and removes, and the sediment of concentrated solution fluorine removal groove 304 enters sludge dewatering unit 107 by pipeline；The concentrated solution that evaporation concentrator 303 is produced is taken back the import of evaporation concentrator 303 by an other pipeline for the outlet of evaporation and concentration circulating pump 312, is flowed back；The crystal serosity that evaporation concentrator 303 is produced enters the magma subsider 307 of the operation by pipeline, in magma subsider, crystal settles down, the crystal that the magma subsider 307 settles down is separated into centrifugal separator 308 by the centrifugal separator feed pump 316 of pipeline and the operation, the fluorination sodium crystal that centrifugal separator 308 is separated falls into crystal (sodium fluoride) storage tank 310, the mother solution separated is connected to centrifuge mother liquor groove 309 by pipeline, then takes back concentrated solution storage tank 301 by pipeline and centrifuge mother liquor pump 317.The concentrated solution of concentrated solution fluorine removal groove 304 passes through pipeline and evaporative crystallization feed pump 313 enters crystallizing evaporator 305, and crystallizing evaporator is mechanical compression evaporation crystallizer.Further evaporative crystallization, produces sodium sulfate (or Sodium Chloride) crystal under vacuo；The crystal serosity of crystallizing evaporator 305 is settled into the magma subsider 307 of the operation by pipeline, the crystal that the magma subsider 307 settles down is centrifuged into centrifugal separator 308 by the centrifugal separator feed pump 316 of pipeline and the operation, sodium sulfate (or Sodium Chloride) crystal separated falls into crystal (sodium sulfate or Sodium Chloride) storage tank 310, the mother solution separated is connected to centrifuge mother liquor groove 309 by pipeline, then takes back concentrated solution fluorine removal groove 304 by pipeline and centrifuge mother liquor pump 317.The concentrated solution out of crystallizing evaporator 305 passes through pipeline and freezing and crystallizing feed pump 314 enters freezing and crystallizing device 306, carrying out cooling reduces temperature, the sodium nitrate crystallization contained in making concentrated solution, the crystal serosity that cooler crystallizer 306 is produced enters the magma subsider 307 of the operation by pipeline, settled in magma groove, crystal after sedimentation is centrifuged into centrifugal separator 308 by the centrifugal separator feed pump 316 of pipeline and the operation, the nitric acid sodium crystal that centrifugal separator 308 is separated falls into crystal (sodium nitrate) storage tank 310, the mother solution separated is connected to centrifuge mother liquor groove 309 by pipeline, pass through pipeline again and centrifuge mother liquor pump 317 takes back the import of cooler crystallizer 306；The dope of the remnants of freezing and crystallizing device 306 passes through pipeline and crystalline mother solution efflux pump 315 takes back the storage regulating reservoir 101 of pretreatment section, and the outlet of crystalline mother solution efflux pump 315 is additionally provided with pipeline, will arrange outside remaining crystalline mother solution；The cooling water outlet and inlet of cooler crystallizer connects the import and export of recirculated cooling water respectively by pipeline.
During aforesaid operations, the following parameter of control is should be noted：
Pretreatment section：The time of staying of storage regulating tank 101 and aeration rate, the aeration rate and pH of neutralization oxidation reaction groove 110, the dosage of flocculant in flocculation reaction groove 103, the time of staying of stillpot 104 and hydraulic surface loading, the turbidity of the rate of filtration, filter area and water outlet of filter element 106.
Film process section：The membrane flux of ultrafiltration apparatus 202, the membrane flux of reverse osmosis unit 205, the membrane flux of film softening plant 207, the dosage of the softening medicament in reverse osmosis concentrated tank 206, the membrane flux of concentration film device 209, the membrane flux of above-mentioned various films will have different values with different raw water qualities.Each section of film to also be controlled and go out electrical conductivity of water, the SDI (index of membrane fouling) of 202 water outlet of ultrafiltration apparatus, species and consumption, cleaning frequency of various film chemical cleaning medicaments etc. also change with the change of raw water in addition.
Sub-prime crystallized region：Evaporation concentrator 303, the operation vacuum of crystallizing evaporator 305, temperature and forced circulation amount, the operation temperature and forced circulation amount of freezing and crystallizing device 306, the rotating speed of each centrifugal separator 308, the Lime-Injecting amount of fluorine removal groove 304.
The present embodiment is included with following process steps：Referring to Fig. 1.
Pretreatment section：
(1) stainless steel acid cleaning waste water enters into storage regulating reservoir 101 and carries out water quality and quantity regulation, and carries out aeration, the ferrous irons in oxidized waste water；
(2) the adjusted pond elevator pump of waste water that step (1) is processed is promoted to neutralization oxidation reaction groove 102, in reactive tank, on the one hand proceed oxidation reaction, on the one hand add sodium hydroxide, the metal ions such as the ferrum in waste water are converted into hydrate precipitate；
(3) (2 waste water for processing enter back into flocculation sediment groove 103 to step, under the flocculation of high polymer coagulant, form big flocculating body, and the precipitate and separate in sedimentation tank；
(4) waste water that step (3) is processed enters into filter 105 and is filtered, and removes oil removal, is being stored to intermediate pool；
(5) the sludge Jing sludge pumps that step (3) precipitates are lifted and carry out sludge dewatering to sludge dewatering unit 107；
Film process section：
(6) pretreated waste water Jing ultrafiltration intake pump 211 lifts ultrafiltration apparatus 202, in ultrafiltration apparatus 202, the float contained in water, macromolecular substances are separated, water outlet is stored into ultra-filtration water groove, before waste water enters ultrafilter membrane, antibacterial is added, and Jing self-cleaning filters are filtered, prevent film blocking, pollution, self-cleaning filter can be cleaned to film, when seriously polluted, Chemical cleaning can be carried out, the concentrated water of generation returns to pretreatment system process；
(7) the waste water Jing feed water by reverse osmosis pump 212 that step (6) is processed is lifted into reverse osmosis unit 205; waste water enters reverse osmosis unit 205 after the filtration of cartridge filter 204 after reverse osmosis high-pressure pump 213 pressurizes; the clear water of the production of reverse osmosis unit 205 enters reuse tank 210 and stores reuse; concentrated water is stored into reverse osmosis concentrated tank 206; waste water adds antisludging agent, reducing agent protecting film before into reverse osmosis unit 205; and it is provided with chemically-cleaning device, film capable of washing；
(8) concentrated water that step (7) is processed, soften after feed pump 214 is lifted Jing film and enter film softening plant 207, soften medicament addition device and add medicament, the incrustation ions such as the calcium and magnesium in removal waste water, the precipitate of formation is separated by the tubular ultra-filtration membrane of film softening plant 207, water outlet enters concentration film intake chamber 208, and concentrated water returns to pretreatment section；
(9) concentrated water that step (8) is processed, concentration film device 209 is entered through concentrating film feed pump 215, further concentrated water is concentrated, concentration film device 209 is provided with cartridge filter 204 and chemically-cleaning device 220, fresh water enters 210 reuse of reuse tank, and concentrated solution enters hypomere operation；
Sub-prime crystallized region：
(10) the concentrated solution Jing evaporation and concentration feed pump 311 for entering into concentrated solution storage tank 301 is lifted, heated into heat exchanger 302, dope after heating enters evaporation concentrator 303, it is evaporated concentration under negative pressure, the fluorination sodium crystal of generation is after sedimentation, centrifugation as Product recycling；
(11) concentrated solution that step (10) is processed, into concentration fluorine removal groove, feeding lime or calcium chloride, go fluorine removal, precipitate Jing transports to the sludge dewatering unit 107 of pretreatment section, supernatant Jing evaporative crystallizations feed pump 313 is promoted to crystallizing evaporator 305, and sodium sulfate that evaporative crystallization is produced and (or) sodium chloride crystal are after sedimentation, centrifugation as Product recycling；
(12) serosity that step (11) is processed, chilled crystallization feed pump 314 are promoted to freezing and crystallizing device 306, the cooling down in freezing and crystallizing device, crystallize out nitric acid sodium crystal, and crystal is after sedimentation, centrifugation as Product recycling；
(13) the crystallized 315 outer row of mother solution efflux pump of remaining crystalline mother solution that step (12) is processed disposes, or returns pretreatment section process.
Neutralization alkali liquor in step (2) is sodium hydroxide or sodium hydroxide+calcium chloride (or Calx), need after the pre-treatment, enter film process before set up medicament softening plant, the calcium ion in waste water is removed.When adding sodium hydroxide, the final product for reclaiming has sodium fluoride, and adding sodium hydroxide+calcium chloride (or Calx) final products does not have a sodium fluoride, and after filtration, set up medicament softening plant before film process section, the calcium ion gone in eliminating water.The chromate waste water that discharges in production, neutral salt waste water, after pretreatment, (plus sodium sulfite or sodium thiosulfate oxidoreduction, hydro-oxidation sodium neutralization precipitation) can be mixed into above-mentioned Waste Water Treatment and process together.
In the film process section of step (6)～(9), ultrafiltration+reverse osmosis process carries out desalination, the concentrated water that reverse osmosiss are produced is again after medicament softens, tubular ultra-filtration membrane (film softening plant) is separated, enter back into concentration film device further to concentrate, when the hardness in waste water is higher, stillpot and filter can be set up before tubular ultra-filtration membrane or stillpot is only set, NF membrane is set up when divalent salts comparision contents are high or microfiltration+nanofiltration+reverse osmosiss combination is set.
Alkali liquor (sodium hydroxide) throwing device, pH instrument are provided with neutralization oxidation reaction groove, transmissometer is provided with intermediate pool, each section of film device outlet of film processing system is provided with conductivity meter, thermometer, the Chemical cleaning cycle of each section of film and pharmacy variety and concentration, can be determined by test adjustment according to actual water quality situation；The operation vacuum of every section of evaporating, concentrating and crystallizing device of sub-prime crystal system, temperature, concentration and evaporation amount can be determined according to the concentration of each salt in feed liquid and phase-solubility diagrams.
Embodiment two
Embodiment two is identical with embodiment one, except that filter 105 is more medium filter or fibre turntable filter plant.Concentration film device 209 is high pressure reverse osmosiss disc type film or vibrating diaphragm or forward osmosis membrane high-pressure membrane.It is precipitation+ultrafiltration that film softening plant 207 is.Evaporation concentrator 303 is concentrated for multiple-effect evaporation.Crystallizing evaporator 305 is Multi-effect evaporation crystallizer.The defluorinating agent of fluorine removal groove 304 is calcium chloride.
Embodiment three
The present embodiment is identical with embodiment one, except that sodium hydroxide throwing device 110 is sodium hydroxide+calcium chloride (or Calx) throwing device in pretreatment, medicament is set up after the intermediate pool 106 of pretreatment section and softens throwing device and reaction settling basin, cancel the crystal piece-rate system (containing sodium fluoride magma subsider, centrifugal separator feed pump, centrifugal separator, centrifuge mother liquor groove, crystal storage tank) of sodium fluoride.Weak-acid cation switch is set up before reverse osmosis unit.
Claims (10)
1. the complexes that a kind of stainless steel acid cleaning waste water Treatment and recovery is reclaimed, including：Pretreatment section,
Film process section, sub-prime crystallized region, pretreatment section include store regulating reservoir, neutralization oxidation reaction groove,
Flocculation reaction groove, stillpot, filter, intermediate pool, sludge dewatering unit；Film process section bag
Include self-cleaning filter, ultrafiltration apparatus, ultra-filtration water groove, cartridge filter, reverse osmosis unit,
Reverse osmosis concentrated tank, film softening plant, concentration film intake chamber, concentration film device, reuse tank；
Sub-prime crystallized region includes concentrated solution storage tank, heat exchanger, evaporation concentrator, concentrated solution fluorine removal groove, steaming
Send out crystallizer, freezing and crystallizing device, crystal segregation apparatuss, it is characterised in that pretreatment section：Storage is adjusted
Section pond is connected with neutralization oxidation reaction groove, and neutralization oxidation reaction groove is connected with flocculation reaction groove, is flocculated
Reactive tank is connected with stillpot, and stillpot is connected with filter, and filter is connected with intermediate pool；
Film process section：Intermediate pool is connected with self-cleaning filter, and self-cleaning filter is connected with ultrafiltration apparatus
Connect, ultrafiltration apparatus are connected with ultra-filtration water groove, chemically-cleaning device is cleaned with the medicament of ultrafiltration apparatus
Interface connects, and the washing outlet of ultrafiltration apparatus is connected with the import Jing pipelines of chemically-cleaning device, surpasses
The air inlet of filter device is connected with air compressor machine, an outlet of ultra-filtration water groove and cartridge filter
It is connected, another outlet is connected with the Butterworth Hatch of ultrafiltration apparatus, cartridge filter is filled with reverse osmosiss
Connection is put, the clean water outlet of reverse osmosis unit is connected with reuse tank, concentrated water is exported and reverse osmosis concentrated water
Groove connects, the cleaning of reverse osmosis unit import and export Jing pipelines respectively with the outlet of chemically-cleaning device and
Import be connected, the outlet of reverse osmosis concentrated tank is connected with film softening plant, film softening plant with
The intake chamber connection of concentration film, concentration film intake chamber are connected with concentration film device, concentrate the clear of film device
The mouth of a river is connected with reuse tank；Sub-prime crystallized region：Dope outlet and the concentrated solution of concentration film device is store
Groove connects, and concentrated solution storage tank is connected with the coolant side-entrance of heat exchanger, heat exchanger and another steam
Heat exchanger is connected, and the coolant side outlet of vapor heat exchanger is connected with evaporation concentrator, evaporation concentrator
Concentrated solution outlet be connected with concentrated solution fluorine removal groove, the outlet of the crystalline solid of evaporation concentrator and crystal point
Be connected from device, the centrifuge mother liquor after crystal is separated takes back concentrated solution storage tank, concentrated solution fluorine removal groove with
Crystallizing evaporator connects, and the sediment outlet of concentrated solution fluorine removal groove is connected with sludge dewatering unit, is evaporated
Crystallizer is connected with freezing and crystallizing device, crystalline solid outlet and the crystal segregation apparatuss phase of crystallizing evaporator
Even, the centrifuge mother liquor after crystal is separated takes back concentrated solution fluorine removal groove, the outlet Jing of freezing and crystallizing device
Pipeline takes back the storage regulating reservoir of pretreatment section, and the crystalline solid outlet of freezing and crystallizing device is separated with crystal
Device is connected, the import of the centrifuge mother liquor tieback freezing and crystallizing device after crystal separation.
2. stainless steel acid cleaning waste water Treatment and recovery according to claim 1 reclaim into suit
Put, it is characterised in that the outlet of the storage regulating reservoir is provided with regulating reservoir elevator pump, and storage is adjusted
Section is provided with aeration tube in pond, and with blower unit into aerator, neutralization oxidation reaction groove is provided with
Sodium hydroxide throwing device, flocculation reaction groove are provided with high polymer coagulant throwing device, filter
Device is provided with aluminium polychlorid throwing device, and filter is sand filtration, multi-medium filtering or fiber mistake
Filter equipment, the mud mouth of stillpot are connected with sludge dewatering unit.
3. stainless steel acid cleaning waste water Treatment and recovery according to claim 1 reclaim into suit
Put, it is characterised in that the self-cleaning filter water inlet is provided with ultrafiltration intake pump, reverse osmosiss dress
Put front end and be provided with feed water by reverse osmosis pump, scale inhibitor feeding device and reverse osmosis high-pressure pump, film softens
Device front end is provided with film and softens feed pump, and concentration film device front end is provided with concentration film feed pump, dense
It is provided with ultrafiltration apparatus cleaning pump, sodium hypochlorite to throw before contracting film high-pressure pump, the Butterworth Hatch of ultrafiltration apparatus
Feeder apparatus, citric acid throwing device, the water inlet of reverse osmosis concentrated tank are provided with softening agent and add dress
Put, concentration film device be high pressure reverse osmosiss rolled film or high pressure reverse osmosiss disc type film or vibrating diaphragm or
Forward osmosis membrane.
4. the complexes that stainless steel acid cleaning waste water Treatment and recovery according to claim 1 is reclaimed,
It is characterized in that the outlet of the concentrated solution storage tank is provided with evaporation and concentration feed pump, evaporation concentrator
Concentrated solution outlet be provided with evaporation and concentration circulating pump, the outlet of concentrated solution fluorine removal groove is provided with evaporation and concentration
Circulating pump, the outlet of crystallizing evaporator are provided with evaporative crystallization feed pump, and the outlet of crystallizing evaporator sets
The outlet for having freezing and crystallizing feed pump, freezing and crystallizing device is provided with crystalline mother solution efflux pump, sub-prime crystallization
The import of the centrifugal separator of section is provided with centrifugal separator feed pump, and the outlet of centrifuge mother liquor groove is provided with
Centrifuge mother liquor pump, concentrated solution fluorine removal groove are provided with lime throwing device.
5. the complexes that stainless steel acid cleaning waste water Treatment and recovery according to claim 1 is reclaimed,
It is characterized in that the concentration film device is provided with waste-heat recovery device, preheating is into evaporation concentrator
The thermal source of concentrated water is the indirect steam that sub-prime crystallized region is discharged, and the evaporation concentrator is mechanical compress
Vaporizer or multi-effect evaporator, crystallizing evaporator are that mechanical compression evaporation crystallizer or multiple-effect evaporation are tied
Brilliant device, the cooling water outlet and inlet of freezing and crystallizing device connect the import and export of recirculated cooling water respectively by pipeline.
6. the complexes that stainless steel acid cleaning waste water Treatment and recovery according to claim 1 is reclaimed,
It is characterized in that the crystal segregation apparatuss are provided with magma subsider, centrifugal separator, centrifuge mother liquor
Groove, crystal storage tank, the magma that evaporation and concentration (evaporative crystallization, freezing and crystallizing) is produced enter magma
Subsider, the magma subsider are connected with centrifugal separator, crystal outlet and the crystalline substance of centrifugal separator
Body storage tank connects, and the mother solution Jing pipelines after separation are connected with centrifuge mother liquor groove, the outlet of centrifuge mother liquor groove
The front end of Jing pipeline tieback evaporation and concentration (evaporative crystallization, freezing and crystallizing).
7. the pickling waste waterss of the stainless steel acid cleaning waste water Treatment and recovery recovery apparatus set of claim 1 are used
Handling process, including with the following steps：
Pretreatment section：
(1) stainless steel acid cleaning waste water enters into storage regulating reservoir and carries out water quality and quantity regulation, and carries out aeration,
Ferrous irons in oxidized waste water；
(2) the adjusted pond elevator pump of waste water that step (1) is processed is promoted to neutralization oxidation reaction groove, in reaction
In groove, on the one hand proceed oxidation reaction, on the one hand add sodium hydroxide, by waste water
The metal ions such as ferrum convert hydrate precipitate；
(3) waste water that step (2) is processed enters back into flocculation sediment groove, under the flocculation of high polymer coagulant,
Form big flocculating body, and the precipitate and separate in sedimentation tank；
(4) waste water that step (3) is processed enters into filter and is filtered, and removes oil removal, is being stored to
Intermediate pool；
(5) the sludge Jing sludge pumps that step (3) precipitates are lifted and carry out sludge dewatering to sludge dewatering unit；
Film process section：
(6) pretreated waste water Jing ultrafiltration intake pump lifts ultrafiltration apparatus, in ultrafiltration apparatus, by water
In the float that contains, macromolecular substances separate, water outlet is stored into ultra-filtration water groove, is given up
Before water enters ultrafilter membrane, antibacterial is added, and Jing self-cleaning filters are filtered, prevent film from blocking,
Pollution, self-cleaning filter can be cleaned to film, when seriously polluted, can carry out Chemical cleaning,
The concentrated water of generation returns to pretreatment system process；
(7) the waste water Jing feed water by reverse osmosis pumps that step (6) is processed are lifted into reverse osmosis unit, waste water Jing
Cross reverse osmosis unit, reverse osmosis are entered after the pressurization of reverse osmosis high-pressure pump after cartridge filter is filtered
The fresh water of device production enters reuse tank and stores reuse thoroughly, and concentrated water is store into reverse osmosis concentrated tank
Deposit, waste water adds antisludging agent, reducing agent protecting film, and being provided with before into reverse osmosis unit
Learn cleaning device, film capable of washing；
(8) concentrated water that step (7) is processed, enters film softening plant Jing after pump is lifted, and softens adding of agent dress
Put and add medicament, the incrustation ion such as calcium and magnesium in removal waste water, the precipitate of formation are soft by film
The tubular ultra-filtration membrane that makeup is put is separated, and water outlet enters concentration film intake chamber, and concentrated water returns to pretreatment
Section；
(9) concentrated water that step (8) is processed, enters concentration film device through concentrating film feed pump, further will
Concentrated water is concentrated, and concentration film device is provided with cartridge filter and chemically-cleaning device, and fresh water is entered back
Tank reuse, concentrated solution is used to enter hypomere operation；
Sub-prime crystallized region：
(10) the concentrated solution Jing evaporation and concentration feed pump for entering into concentrated solution storage tank is lifted, and is carried out into heat exchanger
Heating, the dope after heating enter evaporation concentrator, are evaporated concentration under negative pressure, produce
Fluorination sodium crystal through sedimentation, after centrifugation as Product recycling；
(11) concentrated solution that step (10) is processed, into concentration fluorine removal groove, feeding lime or calcium chloride, goes
Fluorine removal, precipitate Jing transport to the sludge dewatering unit of pretreatment section, and supernatant Jing evaporative crystallizations are given
Material pump is promoted to crystallizing evaporator, sodium sulfate and (or) sodium chloride crystal that evaporative crystallization is produced
As Product recycling after sedimentation, centrifugation；
(12) serosity that step (11) is processed, chilled crystallization feed pump is promoted to freezing and crystallizing device, cold
Freeze cooling down in crystallizer, crystallize out nitric acid sodium crystal, crystal is through sedimentation, centrifugation
Afterwards as Product recycling；
(13) disposal is arranged outside the crystallized mother solution efflux pump of remaining crystalline mother solution that step (12) is processed, or is returned pre-
Processing section process.
8. use stainless steel acid cleaning waste water Treatment and recovery recovery apparatus set according to claim 7
Pickling waste waterss handling process, it is characterised in that the neutralization alkali liquor in the step (2) is hydroxide
Sodium or sodium hydroxide+calcium chloride or Calx, need after the pre-treatment, enter film process before to set up medicament soft
Makeup is put, and the calcium ion in waste water is removed.
9. the work of stainless steel acid cleaning waste water Treatment and recovery recovery apparatus set according to claim 7
Skill, it is characterised in that in the step (6), is arranged by the content of the bivalence in water and above ion
Or before being not provided with reverse osmosis unit, set up Weak-acid cation switch.
10. the work of stainless steel acid cleaning waste water Treatment and recovery recovery apparatus set according to claim 7
Skill, it is characterised in that ultrafiltration+reverse osmosis process enters in the film process section of step (6)～(9)
Row desalination, the concentrated water that reverse osmosiss are produced is again through medicament softening, tubular ultra-filtration membrane (film softening plant)
After separation, enter back into concentration film device and further concentrate, when the hardness in waste water is higher, can
Stillpot and filter are set up before tubular ultra-filtration membrane or stillpot is only set, when divalent salts comparision contents
NF membrane is set up when high or microfiltration+nanofiltration+reverse osmosiss combination is set.
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