CN116835833A - Resource utilization method of heavy metal sodium sulfate-containing wastewater - Google Patents
Resource utilization method of heavy metal sodium sulfate-containing wastewater Download PDFInfo
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- CN116835833A CN116835833A CN202311073177.XA CN202311073177A CN116835833A CN 116835833 A CN116835833 A CN 116835833A CN 202311073177 A CN202311073177 A CN 202311073177A CN 116835833 A CN116835833 A CN 116835833A
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- sodium sulfate
- concentration
- sodium
- wastewater
- sulfate
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- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 title claims abstract description 98
- 229910052938 sodium sulfate Inorganic materials 0.000 title claims abstract description 96
- 235000011152 sodium sulphate Nutrition 0.000 title claims abstract description 96
- 239000002351 wastewater Substances 0.000 title claims abstract description 74
- 238000000034 method Methods 0.000 title claims abstract description 59
- 229910001385 heavy metal Inorganic materials 0.000 title claims abstract description 50
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims abstract description 68
- 229910052921 ammonium sulfate Inorganic materials 0.000 claims abstract description 59
- 235000011130 ammonium sulphate Nutrition 0.000 claims abstract description 59
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 claims abstract description 58
- 238000001704 evaporation Methods 0.000 claims abstract description 52
- 229910000030 sodium bicarbonate Inorganic materials 0.000 claims abstract description 34
- 235000017557 sodium bicarbonate Nutrition 0.000 claims abstract description 34
- 238000000354 decomposition reaction Methods 0.000 claims abstract description 32
- 239000003124 biologic agent Substances 0.000 claims abstract description 31
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 24
- 239000011574 phosphorus Substances 0.000 claims abstract description 24
- 239000012535 impurity Substances 0.000 claims abstract description 15
- 238000004064 recycling Methods 0.000 claims abstract description 13
- 150000002500 ions Chemical class 0.000 claims abstract description 12
- 229910001415 sodium ion Inorganic materials 0.000 claims abstract description 10
- 238000001556 precipitation Methods 0.000 claims abstract description 9
- 230000002195 synergetic effect Effects 0.000 claims abstract description 9
- 239000007800 oxidant agent Substances 0.000 claims abstract description 7
- 230000001590 oxidative effect Effects 0.000 claims abstract description 7
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims abstract description 4
- 239000002207 metabolite Substances 0.000 claims abstract description 4
- 230000008020 evaporation Effects 0.000 claims description 35
- 239000012452 mother liquor Substances 0.000 claims description 35
- 239000000243 solution Substances 0.000 claims description 35
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 claims description 34
- 229910000013 Ammonium bicarbonate Inorganic materials 0.000 claims description 32
- 235000012538 ammonium bicarbonate Nutrition 0.000 claims description 32
- 239000001099 ammonium carbonate Substances 0.000 claims description 32
- 239000013078 crystal Substances 0.000 claims description 30
- 239000007788 liquid Substances 0.000 claims description 27
- 238000001816 cooling Methods 0.000 claims description 26
- 238000005406 washing Methods 0.000 claims description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 18
- IMQLKJBTEOYOSI-GPIVLXJGSA-N Inositol-hexakisphosphate Chemical compound OP(O)(=O)O[C@H]1[C@H](OP(O)(O)=O)[C@@H](OP(O)(O)=O)[C@H](OP(O)(O)=O)[C@H](OP(O)(O)=O)[C@@H]1OP(O)(O)=O IMQLKJBTEOYOSI-GPIVLXJGSA-N 0.000 claims description 17
- IMQLKJBTEOYOSI-UHFFFAOYSA-N Phytic acid Natural products OP(O)(=O)OC1C(OP(O)(O)=O)C(OP(O)(O)=O)C(OP(O)(O)=O)C(OP(O)(O)=O)C1OP(O)(O)=O IMQLKJBTEOYOSI-UHFFFAOYSA-N 0.000 claims description 16
- 229940068041 phytic acid Drugs 0.000 claims description 16
- 235000002949 phytic acid Nutrition 0.000 claims description 16
- 239000000467 phytic acid Substances 0.000 claims description 16
- 239000007787 solid Substances 0.000 claims description 15
- 238000006243 chemical reaction Methods 0.000 claims description 13
- 238000001914 filtration Methods 0.000 claims description 13
- 239000010413 mother solution Substances 0.000 claims description 11
- 238000000926 separation method Methods 0.000 claims description 11
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 10
- 230000001580 bacterial effect Effects 0.000 claims description 10
- 238000012258 culturing Methods 0.000 claims description 10
- 238000002360 preparation method Methods 0.000 claims description 10
- 244000005700 microbiome Species 0.000 claims description 7
- 238000003756 stirring Methods 0.000 claims description 7
- 238000003723 Smelting Methods 0.000 claims description 6
- 238000004140 cleaning Methods 0.000 claims description 6
- 238000009833 condensation Methods 0.000 claims description 5
- 230000005494 condensation Effects 0.000 claims description 5
- 238000002425 crystallisation Methods 0.000 claims description 5
- 230000008025 crystallization Effects 0.000 claims description 5
- 239000001963 growth medium Substances 0.000 claims description 5
- 239000008394 flocculating agent Substances 0.000 claims description 4
- 238000005189 flocculation Methods 0.000 claims description 4
- 230000016615 flocculation Effects 0.000 claims description 4
- 230000003647 oxidation Effects 0.000 claims description 4
- 238000007254 oxidation reaction Methods 0.000 claims description 4
- 241000605272 Acidithiobacillus thiooxidans Species 0.000 claims description 3
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 claims description 3
- 239000002131 composite material Substances 0.000 claims description 3
- 229910052751 metal Inorganic materials 0.000 claims description 3
- 239000002184 metal Substances 0.000 claims description 3
- 241000605222 Acidithiobacillus ferrooxidans Species 0.000 claims description 2
- 239000005708 Sodium hypochlorite Substances 0.000 claims description 2
- UMPKMCDVBZFQOK-UHFFFAOYSA-N potassium;iron(3+);oxygen(2-) Chemical compound [O-2].[O-2].[K+].[Fe+3] UMPKMCDVBZFQOK-UHFFFAOYSA-N 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 claims description 2
- 239000000126 substance Substances 0.000 claims description 2
- 230000000813 microbial effect Effects 0.000 claims 1
- 238000011084 recovery Methods 0.000 claims 1
- XKMRRTOUMJRJIA-UHFFFAOYSA-N ammonia nh3 Chemical compound N.N XKMRRTOUMJRJIA-UHFFFAOYSA-N 0.000 abstract description 14
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 abstract description 2
- 239000000047 product Substances 0.000 description 17
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 10
- 239000002253 acid Substances 0.000 description 9
- 239000011701 zinc Substances 0.000 description 9
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 8
- 239000011133 lead Substances 0.000 description 8
- BNIILDVGGAEEIG-UHFFFAOYSA-L disodium hydrogen phosphate Chemical compound [Na+].[Na+].OP([O-])([O-])=O BNIILDVGGAEEIG-UHFFFAOYSA-L 0.000 description 7
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 239000012528 membrane Substances 0.000 description 5
- 230000008901 benefit Effects 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 229910052759 nickel Inorganic materials 0.000 description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 4
- 229910052725 zinc Inorganic materials 0.000 description 4
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 3
- 229910019142 PO4 Inorganic materials 0.000 description 3
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 3
- 235000011114 ammonium hydroxide Nutrition 0.000 description 3
- 238000000909 electrodialysis Methods 0.000 description 3
- 239000002609 medium Substances 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 238000001728 nano-filtration Methods 0.000 description 3
- 239000010452 phosphate Substances 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 239000002699 waste material Substances 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 241000605118 Thiobacillus Species 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 229910017052 cobalt Inorganic materials 0.000 description 2
- 239000010941 cobalt Substances 0.000 description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 2
- 239000012141 concentrate Substances 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 239000007857 degradation product Substances 0.000 description 2
- 230000008014 freezing Effects 0.000 description 2
- 238000007710 freezing Methods 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 159000000000 sodium salts Chemical class 0.000 description 2
- 108010011619 6-Phytase Proteins 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 1
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- 229920000298 Cellophane Polymers 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-L Phosphate ion(2-) Chemical compound OP([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-L 0.000 description 1
- 229920000297 Rayon Polymers 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- JTXJZBMXQMTSQN-UHFFFAOYSA-N amino hydrogen carbonate Chemical compound NOC(O)=O JTXJZBMXQMTSQN-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 229910052793 cadmium Inorganic materials 0.000 description 1
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 239000012295 chemical reaction liquid Substances 0.000 description 1
- NVIVJPRCKQTWLY-UHFFFAOYSA-N cobalt nickel Chemical compound [Co][Ni][Co] NVIVJPRCKQTWLY-UHFFFAOYSA-N 0.000 description 1
- 230000000536 complexating effect Effects 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 238000006477 desulfuration reaction Methods 0.000 description 1
- 230000023556 desulfurization Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000002848 electrochemical method Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000003546 flue gas Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 150000002484 inorganic compounds Chemical class 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 description 1
- 229910052808 lithium carbonate Inorganic materials 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 230000004060 metabolic process Effects 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 238000005649 metathesis reaction Methods 0.000 description 1
- 239000010446 mirabilite Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 229940085991 phosphate ion Drugs 0.000 description 1
- 229940085127 phytase Drugs 0.000 description 1
- -1 phytic acid Chemical compound 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 239000012047 saturated solution Substances 0.000 description 1
- 239000013049 sediment Substances 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- VQBIMXHWYSRDLF-UHFFFAOYSA-M sodium;azane;hydrogen carbonate Chemical compound [NH4+].[Na+].[O-]C([O-])=O VQBIMXHWYSRDLF-UHFFFAOYSA-M 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 239000011550 stock solution Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 125000003396 thiol group Chemical group [H]S* 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
- C01—INORGANIC CHEMISTRY
- C01C—AMMONIA; CYANOGEN; COMPOUNDS THEREOF
- C01C1/00—Ammonia; Compounds thereof
- C01C1/24—Sulfates of ammonium
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01D—COMPOUNDS OF ALKALI METALS, i.e. LITHIUM, SODIUM, POTASSIUM, RUBIDIUM, CAESIUM, OR FRANCIUM
- C01D7/00—Carbonates of sodium, potassium or alkali metals in general
- C01D7/02—Preparation by double decomposition
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01D—COMPOUNDS OF ALKALI METALS, i.e. LITHIUM, SODIUM, POTASSIUM, RUBIDIUM, CAESIUM, OR FRANCIUM
- C01D7/00—Carbonates of sodium, potassium or alkali metals in general
- C01D7/12—Preparation of carbonates from bicarbonates or bicarbonate-containing product
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F3/00—Biological treatment of water, waste water, or sewage
- C02F3/34—Biological treatment of water, waste water, or sewage characterised by the microorganisms used
- C02F3/345—Biological treatment of water, waste water, or sewage characterised by the microorganisms used for biological oxidation or reduction of sulfur compounds
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F3/00—Biological treatment of water, waste water, or sewage
- C02F3/34—Biological treatment of water, waste water, or sewage characterised by the microorganisms used
- C02F3/348—Biological treatment of water, waste water, or sewage characterised by the microorganisms used characterised by the way or the form in which the microorganisms are added or dosed
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/001—Processes for the treatment of water whereby the filtration technique is of importance
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/02—Treatment of water, waste water, or sewage by heating
- C02F1/04—Treatment of water, waste water, or sewage by heating by distillation or evaporation
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/52—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
- C02F1/54—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using organic material
- C02F1/56—Macromolecular compounds
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/66—Treatment of water, waste water, or sewage by neutralisation; pH adjustment
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/722—Oxidation by peroxides
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/76—Treatment of water, waste water, or sewage by oxidation with halogens or compounds of halogens
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/101—Sulfur compounds
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/20—Heavy metals or heavy metal compounds
-
- 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
- C02F2103/16—Nature of the water, waste water, sewage or sludge to be treated from metallurgical processes, i.e. from the production, refining or treatment of metals, e.g. galvanic wastes
Abstract
The invention provides a method for recycling sodium sulfate wastewater containing heavy metals, which comprises the steps of firstly removing heavy metal impurities in high-concentration sodium sulfate wastewater through a high-phosphorus biological agent, wherein the volume mass ratio of the high-phosphorus biological agent to the heavy metal ions in the sodium sulfate wastewater is 1-30 ml:1g, and then adding a synergistic oxidant by 0.1-1.0 times of the volume of the high-phosphorus biological agent; and then evaporating and concentrating the wastewater, wherein the mass concentration of sodium sulfate after the evaporating and concentrating is 400-460 g/L, adding sodium bicarbonate for double decomposition reaction, and then evaporating and concentrating to co-produce ammonium sulfate. The invention utilizes the metabolite in the high-phosphorus biological agent to improve the purity and the yield of the ammonium sulfate, the flow is simple, the cost is low, the purity of the sodium bicarbonate is more than 90 percent, the ammonia nitrogen precipitation rate is more than 60 percent, the purity of the ammonium sulfate product meets the requirements of GB535-1995, the sodium ion utilization rate is more than 97 percent, and the sulfate ion utilization rate is more than 95 percent.
Description
Technical Field
The invention relates to the field of environmental protection treatment of waste acid and wastewater in nonferrous metal smelting industry, in particular to a resource utilization method of high-concentration sodium sulfate wastewater containing heavy metals.
Background
The waste water produced in the nonferrous smelting industry mainly comprises concentrated water produced by a membrane treatment method and part of hydrometallurgical waste water, and the two types of waste water often contain a large amount of heavy metal ions such as copper, iron, aluminum, zinc, cobalt, nickel and the like, and the direct discharge can seriously affect the ecological environment, so that heavy metal pollution is caused, and deep purification treatment is needed.
The biological agent is a polymer which is formed by compounding a metabolite formed by large-scale culture of a complex specific functional bacterial colony taking thiobacillus as a main component and a certain inorganic compound under the unbalanced growth condition and has a large number of functional groups such as hydroxyl, sulfhydryl, carboxyl, amino and the like. Multifunctional group rich in biological agent and Cu 2+ 、Pb 2+ 、Zn 2+ 、Hg 2+ 、Cd 2+ The equivalent heavy metal ions form bonds to form a biological complex, so that various heavy metals in the wastewater can be effectively removed.
The other characteristic of the waste water in the nonferrous smelting industry is that the waste water contains a large amount of inorganic salts such as sodium sulfate, sodium chloride and the like, the concentration is as high as 120-239 g/L, and the concentration of sodium sulfate in part of the process can even reach saturation. Because the salinity of the wastewater is too high, even if heavy metals are removed, direct discharge can lead to salinization of the soil, so that sodium sulfate salts in the wastewater still need to be treated properly.
At present, the yield of sodium sulfate in China reaches more than 1000 ten thousand tons, and the income of preparing sodium sulfate by evaporation and crystallization is far lower than the cost, so that a large burden is brought to enterprises. Therefore, the sodium sulfate is converted into other products with economic value, so that the pressure of sodium sulfate treatment can be relieved, economic benefits can be brought to enterprises, and the method has wide application prospect.
The main current process is to prepare sodium bicarbonate and co-produce ammonium sulfate by the metathesis reaction of sodium sulfate and ammonium bicarbonate. Sodium bicarbonate is prepared by double decomposition reaction of sodium sulfate and ammonium bicarbonate, and ammonium sulfate is co-produced by the mother liquor after reaction in an evaporation concentration mode, but the raw materials in the method are high-purity sodium sulfate prepared by separation and purification, the problem of heavy metal impurities in sodium sulfate wastewater is not considered, and a large amount of sodium ions remained in a system are doped in the form of sodium sulfate to be separated out in the ammonium sulfate during evaporation concentration, so that the purity of the obtained ammonium sulfate is low, the nitrogen content is low, the obtained ammonium sulfate cannot be effectively utilized as a product, and the cost after industrialization is high.
CN216808418U discloses a method for producing ammonium sulfate by adding ammonium bicarbonate to sodium sulfate wastewater to produce sodium bicarbonate, and then freezing at low temperature; the method is based on a mirabilite alkali preparation method to enable sodium sulfate and ammonium bicarbonate to react to generate sodium carbonate and ammonium sulfate, but the method does not consider the problem of impurities in wastewater, and the purity of sodium bicarbonate and ammonium sulfate produced when the components of sodium sulfate stock solution are complex is difficult to reach the standard.
CN102241448A discloses a method for treating sodium sulfate wastewater by electrochemical method, which comprises pretreating sodium sulfate wastewater, adding into an electrolytic tank for electrolytic reaction, finally obtaining sodium hydroxide in a cathode chamber, and obtaining sulfuric acid product containing part of sodium sulfate in an anode chamber, wherein the method has the advantages of short flow, simple equipment, and direct recycling of the product to generate certain economic benefit; however, the method has higher requirements on the quality of the electrode, the electrode has larger loss in strong acid and strong alkali environment after sodium hydroxide and sulfuric acid are prepared, the electrode needs to be replaced frequently, and higher maintenance cost is also brought.
CN112209575a discloses a combined process of denitrification treatment, biochemical treatment, electrodialysis treatment and MVR evaporation concentration, which firstly removes organic impurities therein through biochemical treatment and denitrification treatment, then uses electrodialysis method to concentrate the organic impurities, and finally the treated wastewater enters an evaporation concentration device to prepare sodium sulfate product; the combined process treats the wastewater by various means, but under the high-salt condition of sodium sulfate wastewater, the metabolism of microorganisms is greatly inhibited, the efficiency of treating the organic matters in the wastewater is extremely low and even the organic matters cannot grow normally, and a large amount of organic matters which are difficult to remove are introduced in the same process of treatment, so that the concentrated water entering the evaporation concentration equipment after electrodialysis treatment is difficult to meet the requirements.
In CN114702046a, a method for preparing sodium carbonate and co-producing ammonium sulfate by using sodium sulfate is disclosed, and the method uses nanofiltration membrane to purify and separate mother liquor after double decomposition reaction, which is favorable for filtering system impurities and improving the utilization rate of sodium sulfate at the same time, but mother liquor after sodium sulfate and ammonium bicarbonate reaction is close to saturated solution, and under the condition, the nanofiltration membrane needs extremely high pressure, and crystallization of salt is easy to separate out on the membrane, so that the mother liquor cannot be used, and the nanofiltration membrane is extremely difficult to separate and concentrate the mother liquor normally.
CN108046295a discloses a method that ammonia gas and carbon dioxide are absorbed by sodium sulfate solution, and then mixed with ammonia bicarbonate for reaction, sodium bicarbonate is prepared after freezing, and then the frozen mother solution is subjected to acid adjustment and evaporation concentration to obtain ammonium sulfate; the sodium sulfate solution in the patent is derived from waste liquid generated by flue gas desulfurization, sodium sulfate-containing byproducts generated by a lithium carbonate production process or waste liquid generated by manufacturing viscose fiber, cellophane and pigment, the patent considers the problem of impurities in waste water before carrying out double decomposition reaction, and the waste water is pretreated by using an oxidant, but the problem of heavy metals in the waste water is not solved, and the process still cannot guarantee the quality of ammonium sulfate like the conventional process.
The above studies show that the existing sodium sulfate wastewater treatment mainly has the following problems: the front end heavy metal impurity is not treated in place, and the purity of the co-produced ammonium sulfate product is lower.
Disclosure of Invention
The invention aims to provide a treatment method for high-concentration sodium sulfate wastewater containing heavy metals, which is characterized in that heavy metal ions in the wastewater are treated by adding a specific high-phosphate biological agent, and then double decomposition reaction is carried out by adding ammonium bicarbonate to obtain sodium bicarbonate and co-produce ammonium sulfate.
The invention introduces phytic acid in the culture process of the biological preparation to obtain the high-phosphorus biological preparation, the phytic acid, namely phytic acid, has extremely strong complexing effect and oxidation resistance with metal ions, and the phytic acid is added in the culture process of microorganisms, so that the synthesis and oxidation resistance of microorganisms can be promoted, the growth of the microorganisms can be accelerated, the culture period of the microorganisms can be shortened, and in addition, the removal of zinc, lead, cobalt, nickel and other heavy metal ions in wastewater by the biological preparation can be enhanced by utilizing extremely strong chelating performance of the phytic acid and the heavy metal, the consumption of the biological preparation in the process of removing heavy metal is reduced, heavy metal impurities brought in the process of producing sodium bicarbonate by double decomposition reaction are reduced, the accumulation of heavy metal impurities in the circulation process of a system is avoided, and the purity of sodium bicarbonate products is improved. In addition, a large amount of phytase is produced in the culture process of the biological agent, and a large amount of degradation products are introduced into the system after the phytic acid is degraded, and the main component of the degradation products is phosphate, so that the subsequent evaporation concentration process is facilitated.
After the double decomposition reaction is finished, a large amount of sodium ions remained in the system are not converted into sodium bicarbonate, and part of the sodium ions exist in the system in the form of sodium sulfate for circulation, but during evaporation concentration, because the water content of the system is greatly reduced, the dissolution amount of sodium sulfate and ammonium sulfate can be reduced, and because the concentration of ammonium sulfate in the system is far higher than that of sulfate radical, ammonium sulfate can be separated out in preference to sodium sulfate, but when the evaporation amount reaches about 35%, sodium sulfate can still be separated out to influence the purity of ammonium sulfate, so that the evaporation amount is controlled to be an important parameter in the co-production of ammonium sulfate; after the phosphate ions are introduced into the system, the phosphate ions mostly exist in the form of hydrogen phosphate under the condition of pH=4-4.5, and the ions are combined with sodium ions to form disodium hydrogen phosphate, so that the disodium hydrogen phosphate has higher solubility than sodium sulfate, and therefore, the evaporation capacity can be further increased without precipitation of sodium sulfate during evaporation concentration, on one hand, the purity of ammonium sulfate is improved, on the other hand, the yield of ammonium sulfate is increased, the ammonia nitrogen conversion rate is improved, the system circulation quantity is reduced, and the running cost of the system is reduced. The solubility of sodium sulfate, ammonium sulfate, disodium hydrogen phosphate at 80℃is shown in Table 1.
Table 1: solubility contrast of sodium sulfate, ammonium sulfate, disodium hydrogen phosphate at 80 ℃ (unit: g/100ml h2 o):
the high-phosphorus biological agent is realized by adopting the following technical scheme:
a preparation method of biological agent comprises culturing domesticated composite bacterial colony of Thiobacillus ferrooxidans and Thiobacillus thiooxidans in 9K culture medium, adding FeSO per liter 4 ·7H 2 And (3) adding 10-150 g of O, then adding 5-20 g of phytic acid, culturing at the temperature of 30-38 ℃ and the pH of 3.5-5 for 3-5 hours, and performing solid-liquid separation after culturing, so as to remove solid impurities in the solid-liquid separation, thereby obtaining the high-phosphorus biological agent for wastewater.
Preferably, in the preparation method of the biological agent, the addition amount of the phytic acid is 5-15 g/L.
The technical scheme of the invention comprises the following steps:
(1) According to the preparation method of the biological agent, the high-phosphorus biological agent is prepared;
(2) Adding the high-phosphorus biological agent and the synergistic oxidant into sodium sulfate wastewater, and stirring and reacting for 10-45 min to obtain a synergistic oxidized solution;
(3) Adjusting the pH value of the solution after the synergistic oxidation in the step (2) to 8-8.5, and adding a flocculating agent to perform flocculation reaction;
(4) Filtering the flocculation reaction liquid in the step (3), and separating to obtain heavy metal-removed liquid;
(5) Evaporating and concentrating the heavy metal removed liquid obtained in the step (4), and increasing the concentration of sodium sulfate in the system to 400-460 g/L to obtain sodium sulfate mother liquor;
(6) Cooling the sodium sulfate mother liquor obtained in the step (5), adding ammonium bicarbonate into the cooled sodium sulfate mother liquor for double decomposition reaction, carrying out solid-liquid separation after the reaction is finished to obtain sodium bicarbonate solid and sodium bicarbonate mother liquor respectively, washing the obtained sodium bicarbonate solid to obtain a sodium bicarbonate product, and returning washing liquor obtained after washing to the double decomposition reaction;
(7) Rectifying the sodium bicarbonate mother solution obtained by solid-liquid separation in the step (6), and returning an ammonium bicarbonate solution generated in rectification to the double decomposition reaction in the step (6) to obtain a rectified mother solution;
(8) Evaporating and concentrating the rectification mother liquor obtained in the step (7) at 80 ℃ to obtain primary ammonium sulfate crystals, condensed water and evaporation and concentration mother liquor, wherein the condensed water is used for cleaning the crystals, the redundant condensed water is used for cooling and crystallizing, and after the ammonium sulfate crystals are circularly cleaned, an ammonium sulfate product is obtained, and washing liquor returns to the rectification mother liquor in the step (7);
(9) And (3) cooling the evaporation and concentration mother liquor obtained in the step (8) to obtain cooling crystals and cooling mother liquor, circularly cleaning the cooling crystals, returning the cooling crystals to the double decomposition reaction in the step (6), and returning the cooling mother liquor to the rectification mother liquor in the step (7).
The method provided by the invention uses sodium sulfate wastewater containing heavy metals as raw materials to prepare sodium bicarbonate and ammonium sulfate, the wastewater is firstly subjected to high-phosphorus biological agent reaction to remove most heavy metal impurities, filtered and evaporated to reach the required concentration, ammonium bicarbonate is added into clear liquid to carry out double decomposition reaction, phosphate radical in the high-phosphorus biological agent is released into a system and can be combined with redundant sodium salt after double decomposition reaction, and in the process of evaporating and concentrating to obtain ammonium sulfate, the sodium salt is not mixed in the form of sodium sulfate to be separated out in the ammonium sulfate, but is kept in the form of disodium hydrogen phosphate to enter ion circulation.
Preferably, the wastewater in the step (2) is high-concentration sodium sulfate wastewater generated by a specific metal smelting process, wherein the concentration of sodium ions is 17-32 g/L, and the concentration of sulfate ions is 180-250 g/L.
Preferably, the mass ratio of the added volume of the high-phosphorus biological agent in the step (2) to the heavy metal in the wastewater is 3-15 ml/1 g.
Preferably, the synergistic oxidant in the step (2) is one or more of potassium ferrate, hydrogen peroxide and sodium hypochlorite, and the volume ratio of the addition amount of the oxidant to the addition amount of the high-phosphorus biological agent is 0.1-1.0:1.
Preferably, the mass concentration of sodium sulfate obtained after evaporation and concentration in the step (5) is 445-455 g/L.
Preferably, the temperature of the double decomposition reaction in the step (6) is 32-35 ℃, the addition amount of ammonium bicarbonate is 2.0-2.2 times of the molar amount of sodium sulfate in the system, and the reaction time is 1.5-5 h.
Preferably, in the step (7), the temperature of the rectifying tower kettle is 100-105 ℃, and the temperature of the tower top is 40-50 ℃.
Preferably, the substance recovered by rectification in the step (7) is saturated ammonium bicarbonate solution.
Preferably, in the step (8), the evaporating concentration temperature is 80-90 ℃, the evaporating condensation water amount is 60-70% of the total volume of the system, the evaporating amount is the optimal value for producing as much ammonium sulfate as possible on the premise of ensuring the purity of the ammonium sulfate, the condensed water is used for cleaning crystals, the crystal washing liquid is recycled, and the accumulated crystal washing liquid returns to evaporating concentration after being accumulated to a certain concentration.
Preferably, the cooling crystallization temperature in the step (9) is 30-40 ℃.
Compared with the prior art, the invention has the beneficial effects that:
(1) The technology of the invention takes the high-concentration sodium sulfate wastewater generated in the nonferrous smelting industry as a raw material, recycles sodium sulfate resources, and produces sodium bicarbonate with relatively high value and wide application field, thereby solving the problem of discharging sodium sulfate wastewater of enterprises on one hand and bringing economic benefits to enterprises on the other hand.
(2) The invention adopts the special high-phosphorus biological agent to reduce the heavy metal content in the wastewater, and the phytic acid in the system plays an auxiliary role in removing the heavy metal from the original biological agent, so that the ratio of various impurities in the product is effectively reduced, the quality of the sodium bicarbonate is improved, and simultaneously, the phytic acid metabolite is introduced into the system, thereby being beneficial to the subsequent evaporation concentration process.
(3) The high-phosphorus biological agent used in the invention provides phosphate ion pairing for redundant sodium ions in a system during evaporation concentration to form high-solubility disodium hydrogen phosphate, and the disodium hydrogen phosphate can not be separated out in the form of sodium sulfate in ammonium sulfate, so that the evaporation capacity of the system is increased as much as possible on the premise of ensuring the purity of the ammonium sulfate, the yield of the ammonium sulfate is improved, the circulating capacity of the system is reduced, and the running cost is greatly saved.
(4) The invention fully considers the ion recycling of each step, greatly improves the ion utilization rate, ensures the sodium ion utilization rate to be more than 97 percent and ensures the sulfate ion utilization rate to be more than 95 percent.
Drawings
FIG. 1 is a schematic diagram of the process flow of the present invention.
The technical scheme of the invention is further described below by the specific embodiments with reference to the accompanying drawings.
Detailed Description
Example 1
The method for preparing sodium bicarbonate and ammonium sulfate after treating the sodium sulfate wastewater containing heavy metals comprises the following steps:
(1) According to (NH) 4 ) 2 SO 4 1g/L、MgSO 4 ·7H 2 O 0 .5g/L、FeSO 4 ·7H 2 O 20g/L、S 8g/L 、KCl 0.25g/L、Ca(NO 3 ) 0.01g/L of preparation culture medium, 20 g/L of Fe is added 2 SO 4 Adding 6g/L phytic acid, controlling the pH of the culture solution to be 3, adding the domesticated composite bacterial colony of the ferrous oxide thiobacillus and the thiobacillus thiooxidans into a culture medium, culturing for 3 hours in a culture environment at 38 ℃, filtering, and removing sediment in the culture medium solution to obtain the liquid-phase biological agent.
(2) Taking 1L of sodium sulfate wastewater containing lead and zinc heavy metals, wherein the sodium sulfate content is 298g/L, and the Ni and Zn ion concentration is 1.0 and 1.2g/L.
(3) Adding 10ml of high-phosphorus biological agent and 1ml of hydrogen peroxide into the wastewater, stirring and reacting for 30min, then adjusting the pH value to 9.0, adding flocculant PAM for reacting for 15min, filtering and separating, and detecting liquid after heavy metal removal, wherein the Pb content is 5.2mg/L, the Zn content is 8.0mg/L, the Pb removal rate is 99.5%, and the Zn removal rate is 99.3%.
(4) The treated wastewater was concentrated by high temperature evaporation to an evaporation capacity of 338ml, at which time the sodium sulfate concentration in the solution was 450g/L, and cooled to 38 ℃.
(5) Slowly adding ammonium bicarbonate solid, ammonium bicarbonate solution obtained by rectification and crystals obtained after cooling into the wastewater, stirring and reacting, wherein the total adding amount of ammonium bicarbonate is 2 times of the molar total amount of sodium sulfate, adding ammonia water in the process to keep the pH value of a system at 8.0-8.1, adjusting the pH value to 8.1 after the ammonium bicarbonate is completely added, centrifugally filtering and separating to obtain sodium bicarbonate solid and double decomposition mother liquor after reacting for 2 hours, cleaning the solid, and returning the washing liquid to the step (4).
(6) Rectifying the double decomposition mother liquor to recover ammonium bicarbonate, and returning the obtained ammonium bicarbonate solution to the double decomposition reaction in the step (5).
(7) Adding ammonium sulfate crystal washing liquid and cooling mother liquor into the solution after rectification, adjusting the pH value to 4.05, evaporating and concentrating at 80 ℃, wherein the evaporation and condensation water amount is 62% of the total volume of the solution, filtering while the solution is hot to obtain ammonium sulfate crystals, and using the evaporated and obtained condensed water for washing the crystals.
(8) And (3) cooling the mother solution after evaporation and concentration to 30 ℃, returning the cooled crystal to the double decomposition reaction in the step (5), and returning the cooled mother solution to the solution after rectification in the step (5).
In the product prepared by the embodiment, the ammonia nitrogen content in the ammonium sulfate is 21.0%, the free acid is less than 0.1%, the requirements of GB535-1995 are met, the ammonia nitrogen precipitation rate is 55%, the sodium bicarbonate purity is 97%, and the utilization rate of sodium sulfate is 95%.
Comparative example 1
The comparative example of example 1 was different from example 1 in that phytic acid was not added at the time of culturing the bacterial flora, and the bacterial flora was cultured using only 9K medium, and the other process steps were exactly the same as in example 1.
The Pb content in the treated wastewater is 43mg/L, the Zn content is 61mg/L, the Pb removal rate is 94.6%, and the Zn removal rate is 94.9%.
In the obtained product, the ammonia nitrogen content in the ammonium sulfate is 13.0%, the free acid is less than 0.1%, the requirement of GB535-1995 is not met, the ammonia nitrogen precipitation rate is 43%, the purity of sodium bicarbonate is 95%, and the utilization rate of sodium sulfate is 93%.
Example 2
The method for preparing sodium bicarbonate and ammonium sulfate after treating the sodium sulfate wastewater containing heavy metals comprises the following steps:
(1) 1L of sodium sulfate wastewater containing cobalt-nickel heavy metals is taken, wherein the sodium sulfate content is 160g/L, and the Co and Ni ion concentration is 0.8 g/L and 0.6g/L.
(2) Adding 3ml of the high-phosphorus biological agent in the example 1 and 0.3ml of hydrogen peroxide into the wastewater, stirring and reacting for 30min, then adjusting the pH value to 8.5, adding a flocculating agent PAM for reacting for 15min, filtering and separating, detecting liquid after heavy metal removal, wherein the Co content is 1.8mg/L, the Ni content is 0.7mg/L, the Co removal rate is 99.8%, and the Ni removal rate is 99.9%.
(4) The treated wastewater was concentrated by high temperature evaporation to 644ml of sodium sulfate at a concentration of 450g/L in solution and cooled to 35 ℃.
(5) Slowly adding ammonium bicarbonate solid, ammonium bicarbonate solution obtained by rectification and crystals obtained after cooling into the wastewater, stirring and reacting, wherein the total adding amount of ammonium bicarbonate is 2 times of the molar total amount of sodium sulfate, adding ammonia water in the process to keep the pH value of a system at 8.0-8.1, adjusting the pH value to 8.2 after the ammonium bicarbonate is completely added, reacting for 3.5 hours, centrifugally filtering and separating to obtain sodium bicarbonate solid and double decomposition mother liquor, washing the solid, and returning washing liquid to the step (4).
(6) Rectifying the double decomposition mother liquor to recover ammonium bicarbonate, and returning the obtained ammonium bicarbonate solution to the double decomposition reaction in the step (5).
(7) Adding ammonium sulfate crystal washing liquid and cooling mother liquor into the solution after rectification, adding sulfuric acid to adjust the pH value to 4.10, evaporating and concentrating at 83 ℃, wherein the evaporation and condensation water amount is 68% of the total volume of the solution, filtering while the solution is hot to obtain ammonium sulfate crystals, and using the evaporated and obtained condensed water for washing the crystals.
(8) And (3) cooling the mother solution after evaporation and concentration to 35 ℃, returning the cooled crystal to the double decomposition reaction in the step (5), and returning the cooled mother solution to the solution after rectification in the step (5).
In the product prepared by the embodiment, the ammonia nitrogen content in the ammonium sulfate is 21.0%, the free acid is less than 0.1%, the requirements of GB535-1995 are met, the ammonia nitrogen precipitation rate is 59%, the sodium bicarbonate purity is 96%, and the utilization rate of sodium sulfate is 95%.
Comparative example 2
The comparative example of example 2 was different from example 2 in that phytic acid was not added at the time of culturing the bacterial flora, and the bacterial flora was cultured using only 9K medium, and the other process steps were exactly the same as in example 2.
The Co content in the treated wastewater is 37mg/L, the Ni content is 22mg/L, the Co removal rate is 95.4%, and the Ni removal rate is 96.3%.
In the obtained product, the ammonia nitrogen content in the ammonium sulfate is 9.4%, the free acid is less than 0.1%, the requirements of GB535-1995 are not met, the ammonia nitrogen precipitation rate is 47%, the sodium bicarbonate purity is 94%, and the utilization rate of sodium sulfate is 92%.
Example 3
The method for preparing sodium bicarbonate and ammonium sulfate after treating the sodium sulfate wastewater containing heavy metals comprises the following steps:
(1) 1L of sodium sulfate wastewater containing cadmium heavy metal is taken, wherein the content of sodium sulfate is 287g/L, and the concentration of Cd ions is 1.1g/L.
(2) 10ml of the high-phosphorus biological agent in the example 1 and 1ml of hydrogen peroxide are added into the wastewater, the mixture is stirred and reacted for 30min, then the pH value of the mixture is regulated to 8, a flocculating agent PAM is added for reaction for 15min, and after filtration and separation, the liquid-liquid detection after heavy metal removal is carried out, the Cd content is 2.9mg/L, and the Cd removal rate is 99.7%.
(4) The treated wastewater was concentrated by high temperature evaporation to an evaporation capacity of 362ml, at which time the sodium sulfate concentration in the solution was 450g/L, and cooled to 37 ℃.
(5) Slowly adding ammonium bicarbonate solid, rectifying to obtain ammonium bicarbonate solution and cooling crystallization to perform stirring reaction, wherein the total adding amount of ammonium bicarbonate is 2 times of the molar total amount of sodium sulfate, adding ammonia water in the process to keep the pH value of a system at 8.0-8.1, adjusting the pH value to 8.0 after the ammonium bicarbonate is completely added, performing centrifugal filtration and separation after reacting for 1.5 hours to obtain sodium bicarbonate solid and double decomposition mother liquor, cleaning the solid, and returning a washing liquid to the step (4).
(6) Rectifying the double decomposition mother liquor to recover ammonium bicarbonate, and returning the obtained ammonium bicarbonate solution to the double decomposition reaction in the step (5).
(7) Adding ammonium sulfate crystal washing liquid and cooling mother liquor into the solution after rectification, adding sulfuric acid to adjust the pH value to 4.30, evaporating and concentrating at 85 ℃, wherein the evaporation and condensation water amount is 65% of the total volume of the solution, filtering while the solution is hot to obtain ammonium sulfate crystals, and using the evaporated and obtained condensed water for washing the crystals.
(8) And (3) cooling the mother solution after evaporation and concentration to 30 ℃, returning the cooled crystal to the double decomposition reaction in the step (5), and returning the cooled mother solution to the solution after rectification in the step (5).
In the product prepared by the embodiment, the ammonia nitrogen content in the ammonium sulfate is 21.0%, the free acid is less than 0.1%, the requirements of GB535-1995 are met, the ammonia nitrogen precipitation rate is 52%, the sodium bicarbonate purity is 95%, and the utilization rate of sodium sulfate is 96%.
Comparative example 3
The comparative example of example 3 was different from example 3 in that phytic acid was not added at the time of culturing the bacterial flora, and the bacterial flora was cultured using only 9K medium, and the other process steps were exactly the same as in example 2.
The Cd content in the treated wastewater is 91mg/L, and the Cd removal rate is 91.7%.
In the obtained product, the ammonia nitrogen content in the ammonium sulfate is 12.5%, the free acid is less than 0.1%, the requirements of GB535-1995 are not met, the ammonia nitrogen precipitation rate is 47%, the sodium bicarbonate purity is 94%, and the utilization rate of sodium sulfate is 92%.
The crystal composition pairs of ammonium sulfate obtained in the examples and comparative examples are shown in Table 2.
Table 2 comparison of the ammonium sulfate Crystal Components produced in examples and comparative examples
As can be seen from Table 2, in the example product (NH 4 ) 2 SO 4 Is significantly higher than the comparative example, while Na 2 SO 4 The content of (C) is much lower than that of the comparative example.
Claims (10)
1. A method for recycling sodium sulfate wastewater containing heavy metals is characterized in that a high-phosphorus biological agent is used for removing heavy metal impurities in the high-concentration sodium sulfate wastewater, ammonium bicarbonate is added into the treated wastewater to carry out double decomposition reaction to prepare sodium bicarbonate, and then the ammonium sulfate is prepared through evaporation and concentration; the high-phosphorus biological agent is doped with phytic acid in the microbial cultivation process to promote the growth of microorganisms, and a large amount of metabolites are produced after the phytic acid is decomposed and utilized by the microorganisms; the metabolite is combined with sodium ions in a circulating system, so that precipitation of sodium sulfate in the process of producing ammonium sulfate by evaporation and concentration is reduced, and the yield and purity of the ammonium sulfate are improved;
the method comprises the following specific steps:
(1) Culturing composite bacterial colony of thiobacillus ferrooxidans and thiobacillus thiooxidans in any proportion in culture medium, adding FeSO into every liter 4 ·7H 2 10-150 g of O, then adding 5-20 g of phytic acid, culturing at 30-38 ℃ and pH of 3.5-5 for 3-5 hours, and performing solid-liquid separation after culturing, so as to remove solid impurities in the solid-liquid separation to obtain the high-phosphorus biological preparation;
(2) Adding a high-phosphorus biological agent according to the mass of heavy metal ions in sodium sulfate wastewater, wherein the volume-mass ratio is 1-30 ml to 1g, adding a synergistic oxidant according to the volume of 0.1-1.0 times of the high-phosphorus biological agent, and stirring for reacting for 10-45 min to obtain a synergistic oxidized solution;
(3) Adjusting the pH value of the solution after the synergistic oxidation in the step (2) to 8-8.5, and adding a flocculating agent to perform flocculation reaction to obtain a solution after the flocculation reaction;
(4) Filtering the liquid obtained in the step (3), and separating to obtain a heavy metal-removed liquid;
(5) Evaporating and concentrating the heavy metal removed liquid obtained in the step (4), and increasing the concentration of sodium sulfate in the system to 400-460 g/L to obtain sodium sulfate mother liquor;
(6) Cooling the sodium sulfate mother liquor obtained in the step (5), adding ammonium bicarbonate for double decomposition reaction, carrying out solid-liquid separation after the reaction is finished to obtain sodium bicarbonate solid and sodium bicarbonate mother liquor respectively, washing the obtained sodium bicarbonate solid to obtain a sodium bicarbonate product, and returning washing liquor obtained after washing to the double decomposition reaction;
(7) Rectifying the sodium bicarbonate mother solution obtained by solid-liquid separation in the step (6), and returning an ammonium bicarbonate solution generated in rectification to the double decomposition reaction in the step (6) to obtain a rectified mother solution;
(8) Evaporating and concentrating the rectification mother liquor obtained in the step (7) at 80 ℃ to obtain primary ammonium sulfate crystals, condensed water and evaporation and concentration mother liquor, wherein the condensed water is used for cleaning the crystals, the redundant condensed water is used for cooling and crystallizing, and after the ammonium sulfate crystals are circularly cleaned, an ammonium sulfate product is obtained, and a washing solution is merged into the rectification mother liquor in the step (7);
(9) And (3) cooling the evaporation and concentration mother liquor obtained in the step (8) to obtain cooling crystals and cooling mother liquor, returning the cooling crystals to the double decomposition reaction in the step (6), and merging the cooling mother liquor into the rectification mother liquor in the step (7).
2. The method for recycling sodium sulfate wastewater containing heavy metals according to claim 1, wherein the wastewater in the step (2) is high-concentration sodium sulfate wastewater generated by a metal smelting process, wherein the concentration of sodium ions is 17-32 g/L and the concentration of sulfate ions is 180-250 g/L.
3. The method for recycling sodium sulfate wastewater containing heavy metals according to claim 1, wherein the mass ratio of the added volume of the high-phosphorus biological agent to the heavy metals in the wastewater in the step (2) is 1-15 ml/1 g.
4. The method for recycling sodium sulfate wastewater containing heavy metals according to claim 1, wherein the synergistic oxidant in the step (2) is one or more of potassium ferrate, hydrogen peroxide and sodium hypochlorite.
5. The method for recycling sodium sulfate wastewater containing heavy metals according to claim 1, wherein the mass concentration of sodium sulfate after evaporation and concentration in the step (5) is 445-4575 g/L.
6. The method for recycling sodium sulfate wastewater containing heavy metals according to claim 1, wherein the temperature of the double decomposition reaction in the step (6) is 32-35 ℃, the addition amount of ammonium bicarbonate is 2.0-2.2 times of the molar amount of sodium sulfate in the system, and the reaction time is 1.5-5 hours.
7. The method for recycling sodium sulfate wastewater containing heavy metals according to claim 1, wherein the temperature of a rectifying tower kettle in the step (7) is 100-105 ℃, and the temperature of a tower top is 40-50 ℃.
8. The method for recycling sodium sulfate wastewater containing heavy metals according to claim 1, wherein the substance obtained by rectification and recovery in the step (7) is saturated ammonium bicarbonate solution.
9. The method for recycling sodium sulfate wastewater containing heavy metals according to claim 1, wherein the evaporating concentration temperature in the step (8) is 80-90 ℃, and the evaporating condensation water amount is 60-70% of the total volume of the system.
10. The method for recycling sodium sulfate wastewater containing heavy metals according to claim 1, wherein the cooling crystallization temperature in the step (9) is 30-40 ℃.
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