CN113213549A - Method for producing polymeric ferric sulfate by recycling waste acid - Google Patents
Method for producing polymeric ferric sulfate by recycling waste acid Download PDFInfo
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- CN113213549A CN113213549A CN202110475901.6A CN202110475901A CN113213549A CN 113213549 A CN113213549 A CN 113213549A CN 202110475901 A CN202110475901 A CN 202110475901A CN 113213549 A CN113213549 A CN 113213549A
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- China
- Prior art keywords
- ferric sulfate
- polymeric ferric
- acid
- waste
- nitric acid
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- 239000002699 waste material Substances 0.000 title claims abstract description 68
- 239000002253 acid Substances 0.000 title claims abstract description 62
- RUTXIHLAWFEWGM-UHFFFAOYSA-H iron(3+) sulfate Chemical compound [Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RUTXIHLAWFEWGM-UHFFFAOYSA-H 0.000 title claims abstract description 43
- 229910000360 iron(III) sulfate Inorganic materials 0.000 title claims abstract description 43
- 238000004064 recycling Methods 0.000 title claims abstract description 28
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 22
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims abstract description 55
- 229910017604 nitric acid Inorganic materials 0.000 claims abstract description 55
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 53
- 238000000034 method Methods 0.000 claims abstract description 52
- 238000003756 stirring Methods 0.000 claims abstract description 35
- 229910002651 NO3 Inorganic materials 0.000 claims abstract description 27
- 239000007788 liquid Substances 0.000 claims abstract description 27
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 25
- 238000001704 evaporation Methods 0.000 claims abstract description 23
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims abstract description 22
- 230000008020 evaporation Effects 0.000 claims abstract description 22
- 239000000243 solution Substances 0.000 claims abstract description 19
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 18
- 229910052742 iron Inorganic materials 0.000 claims abstract description 18
- 239000011259 mixed solution Substances 0.000 claims abstract description 18
- 229910052979 sodium sulfide Inorganic materials 0.000 claims abstract description 16
- GRVFOGOEDUUMBP-UHFFFAOYSA-N sodium sulfide (anhydrous) Chemical compound [Na+].[Na+].[S-2] GRVFOGOEDUUMBP-UHFFFAOYSA-N 0.000 claims abstract description 16
- 238000007599 discharging Methods 0.000 claims abstract description 11
- 239000012716 precipitator Substances 0.000 claims abstract description 6
- 238000003825 pressing Methods 0.000 claims abstract description 6
- 238000005086 pumping Methods 0.000 claims abstract description 6
- 235000011121 sodium hydroxide Nutrition 0.000 claims abstract description 6
- MWUXSHHQAYIFBG-UHFFFAOYSA-N Nitric oxide Chemical compound O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 claims description 51
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 33
- 238000006243 chemical reaction Methods 0.000 claims description 23
- -1 nitrite iron sulfate Chemical compound 0.000 claims description 20
- 229910052759 nickel Inorganic materials 0.000 claims description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 16
- 238000010521 absorption reaction Methods 0.000 claims description 13
- 238000001556 precipitation Methods 0.000 claims description 12
- 239000000203 mixture Substances 0.000 claims description 10
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 claims description 9
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 9
- 229910001448 ferrous ion Inorganic materials 0.000 claims description 9
- 239000007789 gas Substances 0.000 claims description 9
- 229910052725 zinc Inorganic materials 0.000 claims description 9
- 239000011701 zinc Substances 0.000 claims description 9
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 8
- YPJKMVATUPSWOH-UHFFFAOYSA-N nitrooxidanyl Chemical compound [O][N+]([O-])=O YPJKMVATUPSWOH-UHFFFAOYSA-N 0.000 claims description 8
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 claims description 7
- 239000010802 sludge Substances 0.000 claims description 7
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 claims description 6
- 239000000920 calcium hydroxide Substances 0.000 claims description 6
- 229910001861 calcium hydroxide Inorganic materials 0.000 claims description 6
- 230000001590 oxidative effect Effects 0.000 claims description 6
- 238000007664 blowing Methods 0.000 claims description 5
- FPNCFEPWJLGURZ-UHFFFAOYSA-L iron(2+);sulfite Chemical compound [Fe+2].[O-]S([O-])=O FPNCFEPWJLGURZ-UHFFFAOYSA-L 0.000 claims description 5
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 claims description 4
- 239000000292 calcium oxide Substances 0.000 claims description 4
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 claims description 4
- 230000001376 precipitating effect Effects 0.000 claims description 4
- 239000000463 material Substances 0.000 claims 1
- 239000011790 ferrous sulphate Substances 0.000 abstract description 7
- 235000003891 ferrous sulphate Nutrition 0.000 abstract description 7
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 abstract description 7
- 229910000359 iron(II) sulfate Inorganic materials 0.000 abstract description 7
- 239000002920 hazardous waste Substances 0.000 abstract description 5
- 239000002351 wastewater Substances 0.000 abstract description 5
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 20
- 239000000047 product Substances 0.000 description 13
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 12
- 239000003546 flue gas Substances 0.000 description 12
- 238000005406 washing Methods 0.000 description 10
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 9
- 235000008733 Citrus aurantifolia Nutrition 0.000 description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 6
- 235000011941 Tilia x europaea Nutrition 0.000 description 6
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 description 6
- 239000004571 lime Substances 0.000 description 6
- 235000011116 calcium hydroxide Nutrition 0.000 description 5
- 238000001514 detection method Methods 0.000 description 5
- 238000004821 distillation Methods 0.000 description 5
- 239000007787 solid Substances 0.000 description 5
- 159000000007 calcium salts Chemical class 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- 238000005530 etching Methods 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 238000005554 pickling Methods 0.000 description 4
- 238000004094 preconcentration Methods 0.000 description 4
- 150000003839 salts Chemical class 0.000 description 4
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 description 4
- WUKWITHWXAAZEY-UHFFFAOYSA-L calcium difluoride Chemical compound [F-].[F-].[Ca+2] WUKWITHWXAAZEY-UHFFFAOYSA-L 0.000 description 3
- 229910001634 calcium fluoride Inorganic materials 0.000 description 3
- 238000000354 decomposition reaction Methods 0.000 description 3
- 238000006073 displacement reaction Methods 0.000 description 3
- 239000011737 fluorine Substances 0.000 description 3
- 229910052731 fluorine Inorganic materials 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- 150000002505 iron Chemical class 0.000 description 3
- 230000033116 oxidation-reduction process Effects 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 229910001220 stainless steel Inorganic materials 0.000 description 3
- 239000010935 stainless steel Substances 0.000 description 3
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- JUNWLZAGQLJVLR-UHFFFAOYSA-J calcium diphosphate Chemical compound [Ca+2].[Ca+2].[O-]P([O-])(=O)OP([O-])([O-])=O JUNWLZAGQLJVLR-UHFFFAOYSA-J 0.000 description 2
- ZCCIPPOKBCJFDN-UHFFFAOYSA-N calcium nitrate Chemical compound [Ca+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ZCCIPPOKBCJFDN-UHFFFAOYSA-N 0.000 description 2
- 239000001506 calcium phosphate Substances 0.000 description 2
- 229910000389 calcium phosphate Inorganic materials 0.000 description 2
- 235000011010 calcium phosphates Nutrition 0.000 description 2
- 229940043256 calcium pyrophosphate Drugs 0.000 description 2
- 229910052804 chromium Inorganic materials 0.000 description 2
- 239000011651 chromium Substances 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 235000019821 dicalcium diphosphate Nutrition 0.000 description 2
- XPPKVPWEQAFLFU-UHFFFAOYSA-N diphosphoric acid Chemical compound OP(O)(=O)OP(O)(O)=O XPPKVPWEQAFLFU-UHFFFAOYSA-N 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 229910001385 heavy metal Inorganic materials 0.000 description 2
- 238000006386 neutralization reaction Methods 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 238000011085 pressure filtration Methods 0.000 description 2
- 229940005657 pyrophosphoric acid Drugs 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 235000010344 sodium nitrate Nutrition 0.000 description 2
- 239000004317 sodium nitrate Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000006228 supernatant Substances 0.000 description 2
- 239000008399 tap water Substances 0.000 description 2
- 235000020679 tap water Nutrition 0.000 description 2
- QORWJWZARLRLPR-UHFFFAOYSA-H tricalcium bis(phosphate) Chemical compound [Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O QORWJWZARLRLPR-UHFFFAOYSA-H 0.000 description 2
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical compound [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- 238000003723 Smelting Methods 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000011449 brick Substances 0.000 description 1
- 239000004566 building material Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000004568 cement Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000000498 cooling water Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 229910001447 ferric ion Inorganic materials 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- VPBPOXIFRZBJEU-UHFFFAOYSA-L iron(2+);dinitrite Chemical compound [Fe+2].[O-]N=O.[O-]N=O VPBPOXIFRZBJEU-UHFFFAOYSA-L 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910000000 metal hydroxide Inorganic materials 0.000 description 1
- 150000004692 metal hydroxides Chemical class 0.000 description 1
- 229910001960 metal nitrate Inorganic materials 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 239000003595 mist Substances 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G49/00—Compounds of iron
- C01G49/14—Sulfates
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B21/00—Nitrogen; Compounds thereof
- C01B21/20—Nitrogen oxides; Oxyacids of nitrogen; Salts thereof
- C01B21/38—Nitric acid
- C01B21/46—Purification; Separation ; Stabilisation
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F9/00—Multistage treatment of water, waste water or sewage
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/001—Processes for the treatment of water whereby the filtration technique is of importance
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/02—Treatment of water, waste water, or sewage by heating
- C02F1/04—Treatment of water, waste water, or sewage by heating by distillation or evaporation
- C02F1/048—Purification of waste water by evaporation
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/20—Treatment of water, waste water, or sewage by degassing, i.e. liberation of dissolved gases
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/52—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
- C02F1/5236—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using inorganic agents
-
- 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
- C02F1/58—Treatment of water, waste water, or sewage by removing specified dissolved compounds
- C02F1/583—Treatment of water, waste water, or sewage by removing specified dissolved compounds by removing fluoride or fluorine 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
- C02F1/58—Treatment of water, waste water, or sewage by removing specified dissolved compounds
- C02F1/62—Heavy metal 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
- C02F1/70—Treatment of water, waste water, or sewage by reduction
- C02F1/705—Reduction by metals
-
- 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
- C02F2101/12—Halogens or halogen-containing compounds
- C02F2101/14—Fluorine or fluorine-containing 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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Manufacture And Refinement Of Metals (AREA)
- Treatment Of Water By Oxidation Or Reduction (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
Abstract
The invention belongs to the technical field of environment-friendly wastewater and hazardous waste treatment, and provides a method for producing polymeric ferric sulfate by recycling waste acid, which comprises the following steps: adding iron powder into the waste nitric acid, stirring for 0.5-2 hours, and controlling the pH value of the solution in the stirring process; adding a precipitator, adding liquid caustic soda to adjust the pH value to 4.5-4.8, and fully stirring for 0.5-2 hours; adding sodium sulfide, and fully stirring for 1-4 hours; carrying out filter pressing on the mixed solution to obtain nitrate-containing ferrous sulfate iron; adding sufficient concentrated sulfuric acid, pumping into a negative pressure evaporator for evaporation concentration, detecting nitrate radicals during the evaporation concentration, discharging to a transfer tank for air stripping after the iron content of the nitrate radicals is 8-15%, obtaining a polymeric ferric sulfate product with the basicity of 5-20%, and storing in a warehouse. The invention provides a process for recycling waste nitric acid and mixed acid, which has the advantages of low cost, safety, no pollution and waste recycling, can recycle national standard polymeric ferric sulfate and about 30 percent of dilute nitric acid, and has very good application prospect from the perspective of recycling dangerous waste.
Description
Technical Field
The invention relates to a method for recycling and comprehensively utilizing waste nitric acid and mixed acid, belongs to the technical field of treatment of environment-friendly wastewater and hazardous waste, and particularly relates to a method for recycling waste acid to produce polymeric ferric sulfate.
Background
In the stainless steel pickling and etching industry and the printed circuit board industry, mixed acid formed by preparing nitric acid, hydrofluoric acid, sulfuric acid, hydrochloric acid and the like is widely applied, the required proportion is different for different industries, but the waste acid liquid which is finally scrapped generally contains a large amount of nitrate, fluorine ions, sulfate radicals, ferric ions and heavy metal ions. At present, each hazardous waste disposal factory with great capability of recovering and treating the waste acid mainly depends on two modes for treatment: lime neutralization; high-temperature evaporation and recycling; or (II) combining.
In the prior art, a lime neutralization method mainly comprises the following steps:
1) lime is used as neutralizing agent to treat waste acid liquid and washing waste water by fractional precipitation. Calcium sulfate or calcium fluoride or a mixture thereof is obtained by precipitation under an acidic condition (pH = 3.0 +/-0.5), and the calcium salt for removing heavy metal pollution can be used as a cement filler or a brick making or building material. The metal hydroxide is obtained by precipitation under the alkaline condition (the pH value is less than or equal to 9.0), the quality of the product is superior to that of the laterite-nickel ore imported in China, and the product can be used as a stainless steel smelting raw material. The calcium nitrate-containing wastewater after the waste acid liquid is treated does not need to be discharged or treated, can be recycled, and can be reused as production line washing water after the washing wastewater is treated (patent number: CN 201410577338);
2) the etching waste liquid mixed acid comprises: reacting etching waste liquid mixed acid with lime to enable the fluoride ions, the sulfate ions and the fluosilicic acid ions to prepare calcium salts, and reacting the nitrate ions with sodium salts to prepare sodium nitrate and removing the sodium nitrate through crystallization; or reacting the etching waste liquid mixed acid with lime to make fluoride ions, sulfate ions, fluosilicate ions and nitrate ions all prepare calcium salts. Valuable hydrofluoric acid, nitric acid, sulfuric acid and fluosilicic acid in the waste liquid can be recovered according to the situation of metal salt (patent number: CN 201910507925);
3) mixing the mixed acid with calcium salt, and carrying out solid-liquid separation after reaction to obtain calcium fluoride precipitate and supernatant; sequentially carrying out primary distillation and secondary distillation on the supernatant, wherein nitric acid is separated during the primary distillation, and sulfuric acid and pyrophosphoric acid are obtained during the secondary distillation; mixing the calcium fluoride precipitate with sulfuric acid, and reacting to obtain hydrofluoric acid and calcium sulfate; mixing pyrophosphoric acid with an additive, reacting to obtain calcium pyrophosphate, and converting the calcium pyrophosphate into calcium phosphate; mixing the calcium phosphate with sulfuric acid, and reacting to obtain phosphoric acid and calcium sulfate. The invention separates different kinds of acids in the mixed acid by sequentially carrying out the operations of reaction precipitation and two-stage distillation on the mixed acid, and the mixed acid is thoroughly separated (patent number: CN 202010479400).
The high-temperature evaporation decomposition recycling method mainly comprises the following steps:
1) concentrating the pickling waste liquid in a preconcentrator by high-temperature flue gas, then feeding the concentrated pickling waste liquid into a hydrolysis roasting furnace for high-temperature decomposition, feeding the flue gas containing HF, NOx and HNO3 into the preconcentrator for dedusting and cooling, then feeding the flue gas into an acid absorption tower for acid absorption, washing the flue gas by a washing tower, condensing the flue gas in a condenser by circulating cooling water, using a condensate liquid as a washing liquid to participate in washing in the washing tower, and using the washed washing liquid as an absorption liquid of the acid absorption tower; and (4) enabling the condensed gas to enter a catalytic denitrator for denitration reaction, and discharging the gas after removing NOx. The invention cools the flue gas before acid absorption, thereby effectively improving the absorption rate of nitric acid, and simultaneously, the oxidant is sprayed into the flue gas, NO can be oxidized into high-valence substances such as N2O5 and the like, and the yield of the nitric acid is further improved (patent number: CN 201710984116);
2) the mixed acid waste liquid enters a pre-concentration displacement device for pre-concentration treatment and displacement reaction; HF gas is absorbed by water to form hydrofluoric acid, and the hydrofluoric acid and metal nitrate in the mixed acid waste liquid are subjected to displacement reaction to generate nitric acid and fluoride; directly contacting the mixed acid waste liquid with high-temperature flue gas generated by high-temperature decomposition in a reaction furnace for heat exchange, evaporating nitric acid in the mixed acid waste liquid into the high-temperature flue gas to obtain a concentrated solution of the mixed acid waste liquid, and washing and separating solid particles in the high-temperature flue gas; the concentrated solution of the mixed acid waste liquid enters a reaction furnace for pyrolysis; and (3) the high-temperature flue gas after dust separation enters an absorption tower, and HF and HNO3 in the high-temperature flue gas are absorbed by water to form regenerated acid after water spray rinsing. The stainless steel mixed acid waste liquid regenerated acid process provided by the invention carries out pre-concentration treatment and replacement reaction in a pre-concentration replacement device, so that the recovery rate of nitric acid is improved (patent number: CN 201811459327);
3) the method is characterized in that a triple-effect evaporation process is adopted to implement early-stage concentration treatment of waste acid, saturated iron salt is evaporated from substances containing hydrofluoric acid, nitric acid and iron salt, then sulfuric acid is used for replacing iron salt, the physical characteristic that the volatility of sulfuric acid is far lower than that of nitric acid and hydrofluoric acid is utilized, nitric acid and hydrofluoric acid are volatilized and separated from mixed acid by adopting a heating and temperature-rising and pressure-reducing method, and then volatilized acid mist and water vapor are condensed, so that a large amount of nitric acid and hydrofluoric acid are obtained for acid pickling (patent number: CN 201510163846).
In the above two methods, the solute and the solvent in the solution can be completely separated, but this also determines that the two processes have the problems of high cost, high risk and extremely high equipment requirement. Therefore, how to overcome the defects of the prior art and combine the advantages of the prior art, the process for recycling the waste nitric acid and the mixed acid, which has the advantages of low cost, safety, no pollution and waste recycling, can produce the dilute nitric acid for recycling, and has a very good development and application prospect from the perspective of recycling the hazardous waste.
Disclosure of Invention
In view of the above, the invention provides a method for producing polymeric ferric sulfate by recycling waste acid. The invention aims to overcome the defects of the prior art, provides a process for recycling waste nitric acid and mixed acid, which has the advantages of low cost, safety, no pollution and waste recycling, can recycle national standard polymeric ferric sulfate and about 30 percent of dilute nitric acid, and has good application prospect in the aspect of recycling hazardous waste.
The technical scheme of the invention is as follows:
the method for producing the polymeric ferric sulfate by recycling the waste acid is characterized by comprising the following steps of:
s1, adding iron powder into the waste nitric acid, stirring for 0.5-2 hours, and controlling the pH value of the solution in the stirring process;
s2, after the reaction in the step S1 is finished, adding a precipitator, adding liquid caustic soda to adjust the pH value to 4.5-4.8, and fully stirring for 0.5-2 hours;
s3, after the reaction in the step S2 is finished, adding sodium sulfide, and fully stirring for 1-4 hours;
s4, after the reaction in the step S3 is finished, filter-pressing the mixed solution to obtain nitrate-containing molten iron sulfite, storing in a warehouse, and treating the generated sludge;
and S5, adding sufficient concentrated sulfuric acid into the nitrite iron sulfate containing the nitrate radical obtained in the step S4, pumping the nitrite iron sulfate into a negative pressure evaporator for evaporation concentration, detecting the nitrate radical during the evaporation concentration, discharging the nitrate radical into a transfer tank, oxidizing the residual unreacted ferrous ions by using air and blowing off the complexed nitrogen oxide after the iron content is 8-15%, thus obtaining a polymeric ferric sulfate product with the basicity of 5-20%, and storing the polymeric ferric sulfate product in a warehouse.
The invention provides a process for continuously treating waste nitric acid and mixed acid and realizing recycling of the waste nitric acid, the mixed acid and ferric salt by combining various redox technologies, which combines and improves the process of 'oxidation reduction + evaporative concentration + air stripping', solves the problems of difficult treatment, high cost, high requirement on equipment and the like of the waste nitric acid and the mixed acid, and greatly reduces the water volume and improves the concentration by matching with methods such as negative pressure evaporative concentration and the like, so that the cost is greatly reduced; the concentrated sulfuric acid is mixed according to a certain proportion, the required acidity is provided for reducing nitrate radicals in ferrous sulfate water produced by waste nitric acid and mixed acid, and the required condition is provided for a large amount of nitrogen oxides in the subsequent evaporation process; the addition of the lime can reduce fluorine in the waste nitric acid and the mixed acid to a certain degree, so that the equipment cannot be corroded, and particularly, the titanium plate heat exchanger cannot be corroded by fluorine ions. The nitrogen oxides generated in the evaporation concentration and reaction processes are absorbed by a 6-stage clean water tail gas absorption tower to form pure 30 wt% dilute nitric acid which is returned to a factory for use, so that the resource can be realized, the equipment requirement is reduced, and the risk of environmental pollution is reduced. The process realizes continuous, low-cost and large-scale clean production of the waste nitric acid and the mixed acid.
Further, in the step S1, a sufficient amount of iron powder is added to fully react with the waste nitric acid.
Further, in the step S1, during the stirring, the pH of the solution is controlled to be 3.2 to 3.9.
Further, in step S2, the precipitating agent includes any one of calcium oxide and calcium hydroxide or a mixture of the two.
Further, in the step S2, the concentration of the fluoride ion in the mixed solution is first measured, and the amount of the precipitant added is 1.1 to 1.2 times of the theoretical amount of the fluoride ion added for complete precipitation.
Further, in step S3, the concentrations of nickel and zinc in the mixed solution are measured, and the amount of sodium sulfide added is 1 to 5 times the theoretical amount of sodium sulfide added for complete precipitation of nickel and zinc ions.
In step S3, the concentrations of nickel and zinc in the mixed solution are measured, and the amount of sodium sulfide added is 2 to 3 times the theoretical amount of nickel and zinc ions to be completely precipitated.
Further, in the step S5, in the evaporation and concentration process, after the iron content is 10 to 11%, discharging to a transfer tank.
Further, the method further includes step S6, where the step S6 specifically includes: in the whole process, the main places for releasing the nitrogen oxides are that iron powder is added in the step S1 and polyferric sulfate is produced in the step S5, and the nitrogen oxides generated in the process are absorbed by a 6-grade clean water tail gas absorption tower.
Further, in step S6, pure dilute nitric acid is finally generated for sale or return to the factory for use.
The invention realizes the reutilization of waste nitric acid and mixed acid (at least containing two inorganic acids of hydrofluoric acid, sulfuric acid and nitric acid) through the reasonable process steps and the practical reaction, avoids the waste of ferric salt resources, solves the problems of difficult treatment and high cost discharge of the waste nitric acid and the mixed acid, realizes the comprehensive treatment and utilization of the waste nitric acid and the mixed acid, and has simple process, lower cost and environmental protection.
The invention has the beneficial effects that:
the invention realizes the process of recycling the waste nitric acid, the mixed acid and the ferric salt by continuously treating the waste nitric acid and the mixed acid and combining various oxidation reduction technologies, is a process combining and improving the methods of oxidation reduction, evaporative concentration and air stripping, solves the problems of difficult treatment, high cost, high requirement on equipment and the like of the waste nitric acid and the mixed acid, and greatly reduces the water quantity and improves the concentration by matching with the methods of negative pressure evaporative concentration and the like so as to greatly reduce the cost.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is further described in detail with reference to the following embodiments. It should be understood that the detailed description and specific examples, while indicating the scope of the invention, are intended for purposes of illustration only and are not intended to limit the scope of the invention.
Example 1
A method for producing polymeric ferric sulfate by recycling waste acid comprises the following steps:
adding 4t of waste nitric acid into a stirring tank, wherein the waste nitric acid raw material contains 5% of nitrate, 7.98% of total iron, 1.3% of acidity (calculated by hydrochloric acid) and 0.5% of fluoride ions; after fully stirring, slowly adding 0.275t of reducing iron powder, and fully reacting for 1 hour. At this time, the pH value reached 3.82, and 0.5t of tap water was added to control the ferrous ion concentration of the solution in the stirred tank to be about 8.02%, thereby preventing the ferrous sulfate solid from being precipitated. Then 50kg of slaked lime powder (the content is about 80 percent) is added into the stirring tank, the pH value is adjusted to 4.61, 25kg of sodium sulfide solid is added, and the mixture is fully stirred for 2 hours and then is subjected to pressure filtration. 4t of nitrite iron containing nitrate and sulfate (containing 7.49 percent of ferrous ions, 2.3 percent of nitrate, 8.9ppm of nickel, 3.1ppm of zinc and 7.8ppm of chromium) and 0.5t of sludge are obtained. 0.34t of 98 percent concentrated sulfuric acid is added into the nitrate radical-containing ferrous sulfate water, the mixture is pumped into a negative pressure evaporator to be evaporated until the total iron content in the solution is 10.23 percent, and the mixture is pumped into a transfer tank to be blown off by air oxidation, so that 2.76t of polymeric ferric sulfate (the total iron content is 10.97 percent, and the basicity is 11.68 percent) is obtained, and the polymeric ferric sulfate meets the requirements of various indexes of the national standard polymeric ferric sulfate through detection.
Example 2
A method for producing polymeric ferric sulfate by recycling waste acid comprises the following steps:
adding 20t of waste nitric acid into a stirring tank, wherein the waste nitric acid raw material contains 5% of nitrate, 7.98% of total iron, 1.3% of acidity (calculated by hydrochloric acid) and 0.5% of fluoride ions; after fully stirring, slowly adding 1.375t of reducing iron powder, and then fully reacting for 1 hour. At this time, the pH value reached 3.66, and 8t of tap water was added to control the ferrous ion concentration of the solution in the stirred tank to be about 7.92%, thereby preventing the precipitation of ferrous sulfate solids. Then 250kg of slaked lime powder (the content is about 80 percent) is added into the stirring tank, the pH value is adjusted to 4.73, 125kg of sodium sulfide solid is added, and the mixture is fully stirred for 2 hours and then is subjected to pressure filtration. 27t of molten ferrous sulfate containing nitrate (containing 7.35 percent of ferrous ions, 2.15 percent of nitrate, 11.3ppm of nickel, 3.6ppm of zinc and 9.4ppm of chromium) and 2.67t of sludge are obtained. 2.25t of 98 percent concentrated sulfuric acid is added into the nitrate radical-containing ferrous sulfate water, the mixture is pumped into a negative pressure evaporator to be evaporated until the total iron content in the solution is 10.51 percent, and the mixture is pumped into a transfer tank to be blown off by air oxidation, so that 18.6t of polymeric ferric sulfate (the total iron content is 11.03 percent, and the basicity is 9.03 percent) is obtained, and the polymeric ferric sulfate meets the requirements of various indexes of the national standard polymeric ferric sulfate through detection.
Example 3
The method for producing the polymeric ferric sulfate by recycling the waste acid is characterized by comprising the following steps of:
s1, adding iron powder into the waste nitric acid, stirring for 0.8 hour, and controlling the pH value of the solution in the stirring process;
s2, after the reaction in the step S1 is finished, adding a precipitator, adding liquid caustic soda to adjust the pH value to 4.5, and fully stirring for 0.8 hour;
s3, after the reaction in the step S2 is finished, adding sodium sulfide, and fully stirring for 1.5 hours;
s4, after the reaction in the step S3 is finished, filter-pressing the mixed solution to obtain nitrate-containing molten iron sulfite, storing in a warehouse, and treating the generated sludge;
and S5, adding sufficient concentrated sulfuric acid into the nitrite iron sulfate containing the nitrate obtained in the step S4, pumping the nitrite iron sulfate into a negative pressure evaporator for evaporation concentration, detecting the nitrate during the evaporation concentration, discharging the nitrate into a transfer tank, oxidizing the residual unreacted ferrous ions by using air and blowing off the complexed nitrogen oxide after the iron content is 8-15%, thus obtaining a polymeric ferric sulfate product with the basicity of 8%, and storing the polymeric ferric sulfate product in a warehouse.
Further, in the step S1, a sufficient amount of iron powder is added to fully react with the waste nitric acid.
Further, in the step S1, during the stirring, the pH of the solution is controlled to be 3.3.
Further, in step S2, the precipitating agent is calcium oxide.
Further, in step S2, the concentration of the fluoride ion in the mixed solution is first measured, and the amount of the precipitant added is 1.1 times of the theoretical amount of the fluoride ion added for complete precipitation.
Further, in step S3, the concentrations of nickel and zinc in the mixed solution are measured, and the amount of sodium sulfide added is 2 times the theoretical amount of nickel and zinc ions to be completely precipitated.
Further, in the step S5, in the evaporation and concentration process, after the content of iron is 10%, discharging to a transfer tank.
Further, the method further includes step S6, where the step S6 specifically includes: in the whole process, the main places for releasing the nitrogen oxides are that iron powder is added in the step S1 and polyferric sulfate is produced in the step S5, and the nitrogen oxides generated in the process are absorbed by a 6-grade clean water tail gas absorption tower.
Further, in step S6, pure dilute nitric acid is finally generated for sale or return to the factory for use.
Through detection, the polymeric ferric sulfate product prepared by the method of the embodiment meets the requirements of various indexes of the national standard.
Example 4
The method for producing the polymeric ferric sulfate by recycling the waste acid is characterized by comprising the following steps of:
s1, adding iron powder into the waste nitric acid, stirring for 1.5 hours, and controlling the pH value of the solution in the stirring process;
s2, after the reaction in the step S1 is finished, adding a precipitator, adding liquid caustic soda to adjust the pH value to 4.6, and fully stirring for 1.5 hours;
s3, after the reaction in the step S2 is finished, adding sodium sulfide, and fully stirring for 2.5 hours;
s4, after the reaction in the step S3 is finished, filter-pressing the mixed solution to obtain nitrate-containing molten iron sulfite, storing in a warehouse, and treating the generated sludge;
and S5, adding sufficient concentrated sulfuric acid into the nitrite iron sulfate containing the nitrate obtained in the step S4, pumping the nitrite iron sulfate into a negative pressure evaporator for evaporation concentration, detecting the nitrate during the evaporation concentration, discharging the nitrate into a transfer tank, oxidizing the residual unreacted ferrous ions by using air and blowing off the complexed nitrogen oxide after the iron content is 12%, thus obtaining a polymeric ferric sulfate product with the basicity of 15%, and storing the polymeric ferric sulfate product in a warehouse.
Further, in the step S1, a sufficient amount of iron powder is added to fully react with the waste nitric acid.
Further, in the step S1, during the stirring, the pH of the solution is controlled to be 3.5.
Further, in the step S2, the precipitant is a mixture of calcium oxide and calcium hydroxide, and the mass ratio is 1: 1.
Further, in step S2, the concentration of the fluoride ion in the mixed solution is first measured, and the amount of the precipitant added is 1.15 times of the theoretical amount of the fluoride ion added for complete precipitation.
Further, in step S3, the concentrations of nickel and zinc in the mixed solution are measured, and the amount of sodium sulfide added is 3 times the theoretical amount of nickel and zinc ions to be completely precipitated.
Further, in the step S5, in the evaporation and concentration process, after the iron content is 11%, discharging to a transfer tank.
Further, the method further includes step S6, where the step S6 specifically includes: in the whole process, the main places for releasing the nitrogen oxides are that iron powder is added in the step S1 and polyferric sulfate is produced in the step S5, and the nitrogen oxides generated in the process are absorbed by a 6-grade clean water tail gas absorption tower.
Further, in step S6, pure dilute nitric acid is finally generated for sale or return to the factory for use.
Through detection, the polymeric ferric sulfate product prepared by the method of the embodiment meets the requirements of various indexes of the national standard.
Example 5
The method for producing the polymeric ferric sulfate by recycling the waste acid is characterized by comprising the following steps of:
s1, adding iron powder into the waste nitric acid, stirring for 2 hours, and controlling the pH value of the solution in the stirring process;
s2, after the reaction in the step S1 is finished, adding a precipitator, adding liquid caustic soda to adjust the pH value to 4.8, and fully stirring for 2 hours;
s3, after the reaction in the step S2 is finished, adding sodium sulfide, and fully stirring for 4 hours;
s4, after the reaction in the step S3 is finished, filter-pressing the mixed solution to obtain nitrate-containing molten iron sulfite, storing in a warehouse, and treating the generated sludge;
and S5, adding sufficient concentrated sulfuric acid into the nitrite iron sulfate containing the nitrate obtained in the step S4, pumping the nitrite iron sulfate into a negative pressure evaporator for evaporation concentration, detecting the nitrate during the evaporation concentration, discharging the nitrate into a transfer tank, oxidizing the residual unreacted ferrous ions by using air and blowing off the complexed nitrogen oxide after the iron content is 15%, thus obtaining a polymeric ferric sulfate product with the basicity of 20%, and storing the polymeric ferric sulfate product in a warehouse.
Further, in the step S1, a sufficient amount of iron powder is added to fully react with the waste nitric acid.
Further, in the step S1, during the stirring, the pH of the solution is controlled to be 3.9.
Further, in step S2, the precipitating agent is calcium hydroxide.
Further, in step S2, the concentration of the fluoride ion in the mixed solution is first measured, and the amount of the precipitant added is 1.2 times of the theoretical amount of the fluoride ion added for complete precipitation.
In step S3, the concentrations of nickel and zinc in the mixed solution are measured, and the amount of sodium sulfide added is 5 times the theoretical amount of nickel and zinc ions to be completely precipitated.
Further, in the step S5, in the evaporation and concentration process, after the iron content is 11%, discharging to a transfer tank.
Further, the method further includes step S6, where the step S6 specifically includes: in the whole process, the main places for releasing the nitrogen oxides are that iron powder is added in the step S1 and polyferric sulfate is produced in the step S5, and the nitrogen oxides generated in the process are absorbed by a 6-grade clean water tail gas absorption tower.
Further, in step S6, pure dilute nitric acid is finally generated for sale or return to the factory for use.
Through detection, the polymeric ferric sulfate product prepared by the method of the embodiment meets the requirements of various indexes of the national standard.
It will be evident to those skilled in the art that the invention is not limited to the details of the foregoing illustrative embodiments, and that the present invention may be embodied in other specific forms without departing from the spirit or essential attributes thereof. The present embodiments are therefore to be considered in all respects as illustrative and not restrictive, the scope of the invention being indicated by the appended claims rather than by the foregoing description, and all changes which come within the meaning and range of equivalency of the claims are therefore intended to be embraced therein.
Furthermore, it should be understood that although the present description refers to embodiments, not every embodiment may contain only a single embodiment, and such description is for clarity only, and those skilled in the art should integrate the description, and the embodiments may be combined as appropriate to form other embodiments understood by those skilled in the art. It should be noted that the technical features not described in detail in the present invention can be implemented by any prior art in the field.
Claims (10)
1. The method for producing the polymeric ferric sulfate by recycling the waste acid is characterized by comprising the following steps of:
s1, adding iron powder into the waste nitric acid, stirring for 0.5-2 hours, and controlling the pH value of the solution in the stirring process;
s2, after the reaction in the step S1 is finished, adding a precipitator, adding liquid caustic soda to adjust the pH value to 4.5-4.8, and fully stirring for 0.5-2 hours;
s3, after the reaction in the step S2 is finished, adding sodium sulfide, and fully stirring for 1-4 hours;
s4, after the reaction in the step S3 is finished, filter-pressing the mixed solution to obtain nitrate-containing molten iron sulfite, storing in a warehouse, and treating the generated sludge;
and S5, adding sufficient concentrated sulfuric acid into the nitrite iron sulfate containing the nitrate radical obtained in the step S4, pumping the nitrite iron sulfate into a negative pressure evaporator for evaporation concentration, detecting the nitrate radical during the evaporation concentration, discharging the nitrate radical into a transfer tank, oxidizing the residual unreacted ferrous ions by using air and blowing off the complexed nitrogen oxide after the iron content is 8-15%, thus obtaining a polymeric ferric sulfate product with the basicity of 5-20%, and storing the polymeric ferric sulfate product in a warehouse.
2. The method for producing polymeric ferric sulfate as claimed in claim 1, wherein in the step S1, sufficient iron powder is added to fully react with the waste nitric acid.
3. The method for producing polymeric ferric sulfate as claimed in claim 2, wherein in the step S1, the pH of the solution is controlled to 3.2-3.9 during stirring.
4. The method for producing the polymeric ferric sulfate as claimed in claim 1, wherein in the step S2, the precipitant comprises one or a mixture of calcium oxide and calcium hydroxide.
5. The method for producing polymeric ferric sulfate as claimed in claim 3, wherein in step S2, the concentration of the fluoride ions in the mixed solution is determined, and the addition amount of the precipitant is 1.1-1.2 times of the theoretical addition amount of the fluoride ions in complete precipitation.
6. The method for producing polymeric ferric sulfate by recycling waste acid as claimed in claim 1, wherein in step S3, the concentrations of nickel and zinc in the mixed solution are measured, and the addition amount of the sodium sulfide is 1-5 times of the theoretical addition amount for completely precipitating nickel and zinc ions.
7. The method for producing polymeric ferric sulfate as claimed in claim 6, wherein in step S3, the concentrations of nickel and zinc in the mixed solution are measured, and the adding amount of the sodium sulfide is 2-3 times of the theoretical adding amount of nickel and zinc ions for complete precipitation.
8. The method for producing polymeric ferric sulfate as claimed in claim 1, wherein in the step S5, after the iron content is 10-11% during the evaporation concentration process, the material is discharged to a transfer tank.
9. The method for producing polymeric ferric sulfate by using waste acid as resource as claimed in claim 1, further comprising step S6, wherein the step S6 specifically comprises: in the whole process, the main places for releasing the nitrogen oxides are that iron powder is added in the step S1 and polyferric sulfate is produced in the step S5, and the nitrogen oxides generated in the process are absorbed by a 6-grade clean water tail gas absorption tower.
10. The method for producing polymeric ferric sulfate as claimed in claim 9, wherein in step S6, pure dilute nitric acid is finally generated for sale or return to the factory.
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