CN115557635B - Treatment method of nitric acid type tin stripping wastewater - Google Patents
Treatment method of nitric acid type tin stripping wastewater Download PDFInfo
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- CN115557635B CN115557635B CN202211214938.4A CN202211214938A CN115557635B CN 115557635 B CN115557635 B CN 115557635B CN 202211214938 A CN202211214938 A CN 202211214938A CN 115557635 B CN115557635 B CN 115557635B
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- tin
- nitric acid
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- hydrogen peroxide
- stripping wastewater
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- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 title claims abstract description 205
- 239000002351 wastewater Substances 0.000 title claims abstract description 68
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 title claims abstract description 63
- 229910017604 nitric acid Inorganic materials 0.000 title claims abstract description 63
- 238000000034 method Methods 0.000 title claims abstract description 46
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims abstract description 76
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims abstract description 45
- 235000011114 ammonium hydroxide Nutrition 0.000 claims abstract description 45
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 claims abstract description 19
- 229910052921 ammonium sulfate Inorganic materials 0.000 claims abstract description 19
- 235000011130 ammonium sulphate Nutrition 0.000 claims abstract description 19
- 238000004821 distillation Methods 0.000 claims abstract description 13
- 239000013078 crystal Substances 0.000 claims abstract description 10
- 238000001704 evaporation Methods 0.000 claims abstract description 6
- 239000010949 copper Substances 0.000 claims description 50
- 239000000243 solution Substances 0.000 claims description 48
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 44
- 229910052802 copper Inorganic materials 0.000 claims description 43
- 239000000706 filtrate Substances 0.000 claims description 31
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 26
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 24
- 239000008367 deionised water Substances 0.000 claims description 23
- 229910021641 deionized water Inorganic materials 0.000 claims description 23
- 239000010802 sludge Substances 0.000 claims description 17
- 239000012535 impurity Substances 0.000 claims description 15
- PAWQVTBBRAZDMG-UHFFFAOYSA-N 2-(3-bromo-2-fluorophenyl)acetic acid Chemical compound OC(=O)CC1=CC=CC(Br)=C1F PAWQVTBBRAZDMG-UHFFFAOYSA-N 0.000 claims description 12
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 11
- 229910052742 iron Inorganic materials 0.000 claims description 11
- 229910002651 NO3 Inorganic materials 0.000 claims description 10
- BIGPRXCJEDHCLP-UHFFFAOYSA-N ammonium bisulfate Chemical compound [NH4+].OS([O-])(=O)=O BIGPRXCJEDHCLP-UHFFFAOYSA-N 0.000 claims description 9
- YPJKMVATUPSWOH-UHFFFAOYSA-N nitrooxidanyl Chemical compound [O][N+]([O-])=O YPJKMVATUPSWOH-UHFFFAOYSA-N 0.000 claims description 9
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 8
- 229920002401 polyacrylamide Polymers 0.000 claims description 7
- 239000007864 aqueous solution Substances 0.000 claims description 5
- 230000003647 oxidation Effects 0.000 claims description 5
- 238000007254 oxidation reaction Methods 0.000 claims description 5
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 4
- 238000001816 cooling Methods 0.000 claims description 4
- 239000003456 ion exchange resin Substances 0.000 claims description 4
- 229920003303 ion-exchange polymer Polymers 0.000 claims description 4
- 230000001105 regulatory effect Effects 0.000 claims description 4
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- 230000008569 process Effects 0.000 claims description 3
- 230000007935 neutral effect Effects 0.000 claims description 2
- 239000011135 tin Substances 0.000 abstract description 201
- 238000011084 recovery Methods 0.000 abstract description 53
- 238000001556 precipitation Methods 0.000 abstract description 16
- 230000000694 effects Effects 0.000 abstract description 14
- KUNSUQLRTQLHQQ-UHFFFAOYSA-N copper tin Chemical compound [Cu].[Sn] KUNSUQLRTQLHQQ-UHFFFAOYSA-N 0.000 abstract description 13
- 238000000926 separation method Methods 0.000 abstract description 13
- 239000002253 acid Substances 0.000 abstract description 12
- 238000006243 chemical reaction Methods 0.000 abstract description 9
- 238000006386 neutralization reaction Methods 0.000 abstract description 9
- 238000004065 wastewater treatment Methods 0.000 abstract description 3
- 230000008020 evaporation Effects 0.000 abstract description 2
- 229910001428 transition metal ion Inorganic materials 0.000 abstract description 2
- 229910052718 tin Inorganic materials 0.000 description 187
- 230000000052 comparative effect Effects 0.000 description 16
- 239000000047 product Substances 0.000 description 15
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 12
- 238000005406 washing Methods 0.000 description 11
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 8
- 229910052751 metal Inorganic materials 0.000 description 7
- 239000002184 metal Substances 0.000 description 7
- 229910052757 nitrogen Inorganic materials 0.000 description 6
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 5
- 229910001431 copper ion Inorganic materials 0.000 description 5
- 239000007788 liquid Substances 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 239000002699 waste material Substances 0.000 description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- 229910021645 metal ion Inorganic materials 0.000 description 4
- 239000011347 resin Substances 0.000 description 4
- 229920005989 resin Polymers 0.000 description 4
- 238000001914 filtration Methods 0.000 description 3
- 238000004064 recycling Methods 0.000 description 3
- 229910021529 ammonia Inorganic materials 0.000 description 2
- CSGLCWIAEFNDIL-UHFFFAOYSA-O azanium;urea;nitrate Chemical compound [NH4+].NC(N)=O.[O-][N+]([O-])=O CSGLCWIAEFNDIL-UHFFFAOYSA-O 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 2
- QKSIFUGZHOUETI-UHFFFAOYSA-N copper;azane Chemical compound N.N.N.N.[Cu+2] QKSIFUGZHOUETI-UHFFFAOYSA-N 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 229910001432 tin ion Inorganic materials 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- 229910017518 Cu Zn Inorganic materials 0.000 description 1
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical group [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- MMDJDBSEMBIJBB-UHFFFAOYSA-N [O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[NH6+3] Chemical compound [O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[NH6+3] MMDJDBSEMBIJBB-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 239000013522 chelant Substances 0.000 description 1
- 230000000536 complexating effect Effects 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 229910001882 dioxygen Inorganic materials 0.000 description 1
- 238000011549 displacement method Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000003337 fertilizer Substances 0.000 description 1
- 238000005189 flocculation Methods 0.000 description 1
- 230000016615 flocculation Effects 0.000 description 1
- 150000002391 heterocyclic compounds Chemical class 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910000000 metal hydroxide Inorganic materials 0.000 description 1
- 150000004692 metal hydroxides Chemical class 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- -1 nitrate ions Chemical class 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen(.) Chemical compound [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000002957 persistent organic pollutant Substances 0.000 description 1
- 125000003367 polycyclic group Chemical group 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000012286 potassium permanganate Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 230000001698 pyrogenic effect Effects 0.000 description 1
- 230000001172 regenerating effect Effects 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910001415 sodium ion Inorganic materials 0.000 description 1
- 238000000638 solvent extraction Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- CVNKFOIOZXAFBO-UHFFFAOYSA-J tin(4+);tetrahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[Sn+4] CVNKFOIOZXAFBO-UHFFFAOYSA-J 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F9/00—Multistage treatment of water, waste water or sewage
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/66—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
- C02F1/722—Oxidation by peroxides
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/725—Treatment of water, waste water, or sewage by oxidation by catalytic oxidation
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/42—Treatment of water, waste water, or sewage by ion-exchange
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/16—Nitrogen compounds, e.g. ammonia
-
- 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
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/20—Heavy metals or heavy metal compounds
- C02F2101/203—Iron or iron compound
-
- 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
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
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- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Removal Of Specific Substances (AREA)
Abstract
The invention discloses a method for treating nitric acid type tin stripping wastewater, and belongs to the field of tin stripping wastewater treatment. The invention comprehensively treats the nitric acid type tin stripping wastewater by combining an ammonia water neutralization method and a Fenton-like method, and obtains nitric acid solution and ammonium sulfate crystals by reduced pressure distillation and evaporation concentration. The pH value of the precipitation reaction is controlled to be 0.8-1.5 by ammonia water, hydrogen peroxide is added to enable the hydrogen peroxide to form Fenton-like reaction with transition metal ions such as Fe 3+, cu 2+ and the like, organic matters are catalytically degraded, sn 2+ in the tin-removing wastewater is oxidized to Sn 4+, the generated n-stannic acid (Sn (H 2O)2(OH)4) is oxidized to alpha-stannic acid (Sn (OH) 4), the purity of tin products is improved, and finally, the better copper-tin separation effect is realized while the tin recovery rate is kept high.
Description
Technical Field
The invention relates to the field of tin stripping wastewater treatment, in particular to a method for treating nitric acid type tin stripping wastewater.
Background
The nitric acid type tin stripping wastewater is wastewater generated in the production process of Printed Circuit Boards (PCBs), generally contains various organic substances such as tin, copper, iron, nitric acid, heterocyclic compounds, polycyclic compounds, polymers and the like, and the direct discharge can seriously pollute the environment, so that the wastewater needs to be treated. In addition, due to the high potential value of the metallic tin, the improvement of the recovery purity of the tin is also very beneficial to the subsequent utilization of the metallic tin.
At present, the tin stripping wastewater is mainly treated by the following technical routes: acid-base neutralization, flocculation precipitation, electrolysis, solvent extraction, etc. The ammonia water neutralization method has the advantages of small investment of equipment, simple working procedures and mild reaction process, and is adopted by most tin stripping wastewater treatment enterprises. However, the ammonia water neutralization method in the prior art generally has the problems that the pH value is higher during tin precipitation, the obtained tin product often contains more copper metal, and the recovery purity of tin is low, and copper-tin alloy can be generated with copper during the recovery of tin by a pyrogenic process, so that the separation difficulty of copper and tin is high, the waste of metal tin is finally caused, and even the hidden danger of long-term environmental pollution can be brought. Therefore, it is very important to realize copper-tin separation and recovery in the treatment of tin stripping wastewater, but most ammonia neutralization processes do not solve the problem.
In order to improve the recovery purity of tin and realize the separation and recovery of copper and tin, the prior art discloses a treatment method of tin stripping waste liquid, which comprises the steps of oxidizing metals such as tin, iron, copper and the like by adding concentrated sulfuric acid to generate a metal sulfate solution, adding ammonia water and carrying out solid-liquid separation, and adjusting the pH value to be between 0.6 and 0.8 to facilitate the precipitation of tin hydroxide and minimize the precipitation of other metal hydroxides so as to separate and precipitate each metal.
The prior art also discloses a method for preparing urea ammonium nitrate solution by utilizing the circuit board tin stripping waste nitric acid, which is characterized in that tin mud, crude copper powder, iron mud and ammonium nitrate solution are obtained by processing the tin stripping waste nitric acid solution in a matching way through an acid-base neutralization method, a displacement method, a Fenton method and a precipitation method, urea is added into the ammonium nitrate solution to obtain urea ammonium nitrate solution with the total nitrogen content of 28-32%, however, in the technical scheme, the pH value of the acid-base neutralization precipitation reaction is 4-5, copper ions are easy to precipitate out at the moment, the copper-tin separation effect on waste liquid is poor, and the purity of tin in the obtained tin mud is low.
Disclosure of Invention
The invention provides a treatment method of nitric acid type tin stripping wastewater, which aims to solve the problems that the recovery purity of tin is low and the recovery rate of nitrate is low when an ammonia water neutralization method is used for treating nitric acid type tin stripping wastewater in the prior art, and improves the COD removal rate of the tin stripping wastewater while ensuring the high purity of tin in recovered tin mud, so that the nitrate and ammonium in high-nitrogen ammonia wastewater after tin precipitation are effectively recovered, and the effective recycling utilization of copper, tin and nitric acid is realized.
The technical problems to be solved by the invention are realized by the following technical scheme:
the method for treating the nitric acid type tin stripping wastewater specifically comprises the following steps:
s1, adding ammonia water into tin stripping wastewater of a nitric acid type circuit board, adjusting the pH to 0.8-1.5, adding hydrogen peroxide for oxidation, and separating to obtain primary tin mud and primary filtrate; the volume ratio of the tin stripping wastewater to the hydrogen peroxide is less than or equal to 10:1;
S2, adding deionized water or ammonia water into the primary tin mud obtained in the step S1 to remove copper impurities, separating to obtain secondary tin mud and secondary filtrate, and mixing the secondary filtrate with the primary filtrate obtained in the step S1 to obtain mixed filtrate;
S3, adding ammonia water into the mixed filtrate obtained in the step S2, adjusting the pH to 5.5-6, adding a polyacrylamide aqueous solution, and separating to obtain iron-containing copper sludge and a tertiary filtrate; treating the tertiary filtrate by ion exchange resin to obtain an ammonium nitrate solution;
S4, adding concentrated sulfuric acid into the ammonium nitrate solution in the step S3, wherein the molar ratio of nitrate radical to sulfate radical is less than or equal to 1:1, performing reduced pressure distillation to obtain a nitric acid solution and an ammonium bisulfate solution; and adding ammonia water into the ammonium bisulfate solution, regulating the pH value to be neutral, evaporating, concentrating, and cooling and crystallizing to obtain ammonium sulfate crystals.
The following are to be described:
According to the invention, ammonia water is added in the S1 to control the pH value of the tin stripping wastewater to be 0.8-1.5, then hydrogen peroxide is added, the hydrogen peroxide can oxidize Sn 2+ into Sn 4+, the optimal precipitation pH of tin ions in the wastewater is reduced to about 1, so that tin can be completely precipitated in the pH range of 0.8-1.5, the optimal precipitation pH of metal ions such as Fe 3+ and Cu 2+ in the wastewater is larger than 3, the tin ions are not easily precipitated when the pH is 0.8-1.5, the copper-tin separation effect of the treated tin stripping wastewater is good, and the recovery purity of tin in the obtained primary tin mud is high. Meanwhile, the generated n-stannic acid can be oxidized into alpha-stannic acid by the hydrogen peroxide, and compared with a n-stannic acid product, the adsorption of the alpha-stannic acid to copper and iron is less, so that the hydrogen peroxide is added to promote the generation of the alpha-stannic acid, the adsorption of tin precipitation to impurities such as copper, iron and the like can be further reduced, the tin purity is improved, and the recovery purity of tin in the finally obtained primary tin mud is high. In addition, hydrogen peroxide can form Fenton-like reaction with transition metal ions such as Fe 3+, cu 2+ and the like in the tin stripping wastewater, so that organic pollutants are catalytically degraded, and the COD concentration in the tin stripping wastewater is effectively reduced. Wherein, the volume fraction of the hydrogen peroxide is 27.5-35%, and the hydrogen peroxide with the volume fraction is more favorable for the oxidation of ions in the tin stripping wastewater and the occurrence of Fenton-like reaction, preferably 30%.
In addition, the pH value of the precipitation reaction is controlled to be 0.8-1.5, so that more hydroxyl free radicals can be generated by hydrogen peroxide, and the oxidability is stronger. When the pH is lower than 0.8, on one hand, tin is difficult to separate out, so that the tin recovery rate is not high; on the other hand, the hydrogen peroxide has low activity, and the oxidation of the n-stannic acid into alpha-stannic acid is difficult, so that the adsorbed copper impurities are increased, the purity of the recovered tin mud is low, and the copper-tin separation effect is poor; and when the pH is higher than 1.5, cu 2+ in the wastewater is also easier to precipitate out, and is also unfavorable for copper-tin separation.
When the volume ratio of the tin stripping wastewater to the hydrogen peroxide is less than or equal to 10:1, the hydrogen peroxide cannot completely oxidize Sn 2+ into Sn 4+, the precipitation pH of Sn 2+ is higher, at the moment, the tin is difficult to completely separate out, and at the moment, the tin recovery rate is lower; in addition, too little hydrogen peroxide is added, so that COD in the wastewater cannot be effectively removed.
In the invention S2, the deionized water is added to wash the primary tin slime, so that copper ions adsorbed on the tin slime can be further removed, the tin in the tin slime exists in the form of alpha-stannic acid, the alpha-stannic acid is insoluble in water, and the washing of the deionized water does not cause tin loss, thereby better realizing copper-tin separation; and ammonia water is added to react with copper ions adsorbed in the primary tin mud to generate a copper ammonia complex, so that copper ion impurities doped in the tin mud are removed, and the tin purity in the tin mud is further improved.
The ion exchange resin in the S3 is preferably sodium chelate resin, and the resin can be used for better taking away metal ions in the solution, and in addition, cu 2+ can be washed out after the regenerated resin is activated by hydrochloric acid to obtain a copper chloride solution, so that the utilization of Cu 2+ is further realized.
In the step S4, the concentrated sulfuric acid is added to promote the recovery of nitrate ions in the form of nitric acid solution, and when the molar ratio of nitrate to sulfate is less than or equal to 1:1, the high recovery rate of nitrate can be obtained, so that the recycling utilization of nitric acid in the nitric acid type tin stripping wastewater is realized. Among them, the reduced pressure distillation is preferable to be carried out under a pressure of 0.02 to 0.03MPa in order to ensure that nitric acid is not decomposed into nitrogen and oxygen gas and that the recovery rate of nitrate is low, and under this condition, the distillation temperature can be controlled more effectively to recover the nitric acid solution. In addition, after reduced pressure distillation in the step S4, the distillation component with extremely low nitric acid content in the front part is discarded, the distillation component in the front part is collected to obtain 23% -33% nitric acid solution and ammonium bisulfate concentrated solution, and the ammonium bisulfate concentrated solution is added with ammonia water for further evaporation and concentration to obtain an ammonium sulfate product with the total nitrogen content of more than 21%, wherein the prepared nitric acid solution accords with class III products in the standard regenerated tin stripping solution (2021-0025T-HG), and the ammonium sulfate crystal accords with class III products in the standard ammonium sulfate (GB 535-1995).
Preferably, in step S1, the pH is 0.8 to 1, more preferably 1.
Preferably, in step S1, the volume ratio of the tin stripping wastewater to the hydrogen peroxide is 10: (1-2).
When the hydrogen peroxide ratio is too high, the cost is increased, and the recovery rate of tin is not further improved.
More preferably, in step S1, the volume ratio of the tin stripping wastewater to the hydrogen peroxide is 10: (1 to 1.5), and more preferably 10:1.
Preferably, in step S2, the mass ratio of the primary tin mud to deionized water is 1: (5-11), more preferably (5-10), still more preferably 1:10.
When the proportion of deionized water is too low, the washing effect is poor, the copper ion removal rate is low, and when the proportion of deionized water is too high, the pH of tin sludge is raised due to the fact that the pH of the deionized water is 7, and at the moment, the impurity removal effect of Fe 3+ and Cu 2+ is poor.
Preferably, in step S2, after adding deionized water, the pH of the solution is adjusted to 0.9 to 1, more preferably 1, with dilute nitric acid.
After deionized water is added, the pH value of primary tin mud is increased, at the moment, fe 3+ and Cu 2+ are easy to form micro-precipitation and separate out to influence the purity of the tin mud, and dilute nitric acid is added to reduce the pH value, so that the removal of Fe 3+ and Cu 2+ is facilitated, and the pH value is insufficient to dissolve alpha-stannic acid and does not bring tin loss.
Preferably, in step S2, the mass ratio of the primary tin mud to the ammonia water is 10: (4 to 7), more preferably 10: (4-6), and more preferably 10:6.
The inventors found that when the mass ratio of the primary tin sludge to the ammonia water is within this range, the complexing reaction can take place better, and the Cu 2+ removal effect is better.
Preferably, in step S3, the mass concentration of the aqueous solution of polyacrylamide is 0.1%, and the volume ratio of the aqueous solution of polyacrylamide to the mixed filtrate is (1-2.5): 10.
Preferably, in step S4, the molar ratio of nitrate and sulfate is 1: (1 to 1.4), more preferably 1 (1 to 1.2), still more preferably 1:1.
When the molar ratio of nitrate radical to sulfate radical is in the range, the recovery of nitrate radical can be well promoted, and the problem of high cost caused by overlarge addition amount of subsequent ammonia water can be avoided.
Preferably, in step S4, the reduced pressure distillation treatment temperature is 80 to 100 ℃.
Compared with the prior art, the technical scheme of the invention has the following beneficial effects:
(1) According to the invention, pH is regulated, hydrogen peroxide is added, an ammonia water neutralization method and a Fenton-like method are combined to comprehensively treat nitric acid type tin stripping wastewater, deionized water or ammonia water is utilized to further wash primary tin mud, fe 3+ and Cu 2+ are removed, the total tin recovery rate is finally over 99%, the tin content in a tin product is over 55%, the copper content in the tin product is under 1.5%, the tin recovery rate is kept high, good copper-tin separation effect is realized, and the recovery purity of tin is high.
(2) According to the invention, the formation of nitric acid is promoted by adding concentrated sulfuric acid, reduced pressure distillation is carried out to obtain a nitric acid solution, ammonia water is added to treat ammonium bisulfate to obtain ammonium sulfate crystals, the recycling of nitrate radical in nitric acid type tin stripping wastewater is realized, sulfate radical and ammonium radical which are subsequently introduced are recycled, the obtained nitric acid solution accords with class III products in the standard regenerated tin stripping liquid (2021-0025T-HG), and the ammonium sulfate crystals accord with class III products in the standard ammonium sulfate (GB 535-1995).
Detailed Description
The invention will be further described with reference to the following specific embodiments, but the examples are not intended to limit the invention in any way. Raw materials reagents used in the examples of the present invention are conventionally purchased raw materials reagents unless otherwise specified. The tin stripping wastewater components in the following examples are shown in Table 1.
TABLE 1 main component of tin stripping wastewater
| Composition of the components | Sn | Fe | Cu | Zn | Mn | Ni | Bi |
| g/L | 87.31 | 15.75 | 9.88 | 0.07 | 0.07 | 0.01 | 0.01 |
| Composition of the components | H+ | COD | NO3-N | Cl- | SO4 2- | NO2-N | NH3-N |
| g/L | 3.37 | 5.45 | 54.4 | 5.51 | 7.5 | 54.4 | 0.00 |
Example 1
The treatment method of the tin stripping wastewater of the nitric acid type circuit board specifically comprises the following steps:
S1, placing a 2L beaker on an electric stirrer, adding 800mL of tin-stripping wastewater at the normal temperature and the rotating speed of 350r/min, and inserting a pH meter below the liquid level; adjusting the pH value to be 1 by using 13% ammonia water, and adding 80mL of 30% hydrogen peroxide (namely, the volume ratio of the tin stripping wastewater to the hydrogen peroxide is 10:1); after reacting for 1 hour, centrifugally filtering to obtain primary tin mud and primary filtrate; the tin and copper contents in the primary filtrate were detected, and the COD content in the primary filtrate was measured by the potassium permanganate method, and the recovery rate of tin and copper and the COD removal rate were calculated by the following formulas, and the results are recorded in table 2:
s2, adding deionized water into the primary tin mud, wherein the mass ratio of the primary tin mud to the deionized water is 1:10, at this time, the pH value of the system was 1.8, then the ph=1 was adjusted with dilute nitric acid to wash out a small amount of metal impurities adsorbed in the primary tin slime, and after stirring for 15 minutes, centrifugal filtration was performed to obtain secondary tin slime and secondary filtrate, and the secondary filtrate was mixed with the primary filtrate to obtain a mixed filtrate. The tin and copper contents in the secondary tin sludge and the tin content in the mixed filtrate were measured, and the final tin recovery was calculated according to the following formula, and the results are recorded in table 3:
S3, adding 13% ammonia water into the mixed filtrate obtained in the step S2, adjusting the pH to 5.5, reacting for 5 minutes, and then mixing the mixed filtrate with a polyacrylamide aqueous solution (0.1 wt%) according to the volume ratio of 10:2.5 adding the iron-containing copper sludge and tertiary filtrate into the system, and centrifugally filtering after the reaction; treating the three filtrates with sodium ion exchange resin to obtain ammonium nitrate solution, wherein the main components of the ammonium nitrate solution are recorded in table 4; then hydrochloric acid is used for regenerating resin and washing copper out to obtain a copper chloride solution byproduct;
S4, adding 98% concentrated sulfuric acid into the ammonium nitrate solution in the step S3, wherein the molar ratio of nitrate radical to sulfate radical is 1:1, carrying out reduced pressure distillation at the temperature of 80 ℃ under the pressure of 0.02MPa, discarding the fraction with extremely low nitric acid content in the front part, collecting the distillation components in the rear part, obtaining 23.16% nitric acid solution and ammonium bisulfate concentrated solution, wherein the main components of the nitric acid solution are recorded in table 5; and adding 13% ammonia water into the ammonium bisulfate concentrated solution, adjusting the pH value to 7, evaporating and concentrating, cooling to room temperature and crystallizing to obtain ammonium sulfate crystals, wherein the main components of the ammonium sulfate crystals are recorded in Table 6.
Example 2
The treatment method of the nitric acid type circuit board tin stripping wastewater is basically the same as that of the embodiment 1, and the difference is that the volume ratio of the tin stripping wastewater to the hydrogen peroxide in the step S1 is 10:1.5.
Example 3
The treatment method of the nitric acid type circuit board tin stripping wastewater is basically the same as that of the embodiment 1, and the difference is that the volume ratio of the tin stripping wastewater to the hydrogen peroxide in the step S1 is 10:2.
Example 4
The treatment method of the nitric acid type circuit board tin stripping wastewater is basically the same as that of the embodiment 1, except that the ph=0.8 is adjusted by ammonia water in the step S1.
Example 5
The treatment method of the nitric acid type circuit board tin stripping wastewater is basically the same as that of the embodiment 1, except that the ph=1.5 is adjusted by ammonia water in the step S1.
Example 6
The treatment method of the nitric acid type circuit board tin stripping wastewater is basically the same as that of the embodiment 1, and the difference is that the mass ratio of primary tin mud to deionized water in the step S2 is 1:5.
Example 7
The treatment method of the tin stripping wastewater of the nitric acid type circuit board is basically the same as that of the embodiment 1, except that the pH is not adjusted by dilute nitric acid in the step S2.
Example 8
The treatment method of the nitric acid type circuit board tin stripping wastewater is basically the same as that of the embodiment 1, and the difference is that in the step S2, deionized water is replaced by 13% ammonia water, and the copper content in primary tin mud is measured before the ammonia water is added, wherein the mass ratio of the primary tin mud to the ammonia water is 10: and 4, adding ammonia water.
Example 9
The treatment method of the nitric acid type circuit board tin stripping wastewater is basically the same as that of the embodiment 1, and the difference is that in the step S2, deionized water is replaced by 13% ammonia water, and the copper content in primary tin mud is measured before the ammonia water is added, wherein the mass ratio of the primary tin mud to the ammonia water is 10: and 6, adding ammonia water.
Example 10
The treatment method of the tin stripping wastewater of the nitric acid type circuit board is basically the same as that of the embodiment 1, and the difference is that the molar ratio of nitrate radical to sulfate radical in the step S4 is 1:1.2.
Example 11
The treatment method of the tin stripping wastewater of the nitric acid type circuit board is basically the same as that of the embodiment 1, and the difference is that the molar ratio of nitrate radical to sulfate radical in the step S4 is 1:1.4.
Comparative example 1
The treatment method of the nitric acid type circuit board tin stripping wastewater is basically the same as that of the embodiment 1, and the difference is that the volume ratio of the tin stripping wastewater to the hydrogen peroxide in the step S1 is 10:0.5.
Comparative example 2
The treatment method of the nitric acid type circuit board tin stripping wastewater is basically the same as that of the embodiment 1, except that hydrogen peroxide is not added in the step S1.
Comparative example 3
The treatment method of the nitric acid type circuit board tin stripping wastewater is basically the same as that of the embodiment 1, except that hydrogen peroxide is not added in the step S1, and ammonia water is used for adjusting the pH value to 2.5.
Comparative example 4
The treatment method of the nitric acid type circuit board tin stripping wastewater is basically the same as that of the embodiment 1, except that the ph=0.5 is adjusted by ammonia water in the step S1.
Comparative example 5
The treatment method of the nitric acid type circuit board tin stripping wastewater is basically the same as that of the embodiment 1, except that the ph=3 is adjusted by ammonia water in the step S1.
Comparative example 6
The treatment method of the tin stripping wastewater of the nitric acid type circuit board is basically the same as that of the embodiment 1, and the difference is that the molar ratio of nitrate radical to sulfate radical in the step S4 is 1:0.8.
Results and analysis
TABLE 2S 1COD removal rates and tin-copper recovery rates in Primary tin sludge for examples 1 to 5 and comparative examples 1 to 5
The S1 tin and copper recovery rates and COD removal rates of examples 1 to 5 and comparative examples 1 to 5 are shown in Table 2. It is known from examples 1 to 3 and comparative examples 1 to 2 that when the volume ratio of the tin stripping wastewater to the hydrogen peroxide is lower than 10:1, the tin recovery rate is 99% or more, and the copper recovery rate is lower than 30%, that is, the doping of copper can be reduced when the tin is recovered by precipitation, so that the higher recovery purity of the tin is realized, meanwhile, COD in the wastewater is effectively removed, the COD removal rate is 90% or more, and the tin recovery rate is further improved along with the increase of the hydrogen peroxide addition amount, when the volume ratio of the tin stripping wastewater to the hydrogen peroxide is 10:2, the tin recovery rate reaches 100%, and when the hydrogen peroxide addition amount is too low, the oxidation effect on Sn 2+ is not obvious, the pH of the tin completely precipitated is still higher, the tin cannot be completely precipitated and separated out when the pH=1, at this time, the tin recovery rate is lower, only 93.76%, and the COD removal rate is also lower. If hydrogen peroxide is not added, tin is not completely precipitated at ph=1, and the tin recovery rate is low. As can be seen from comparative examples 2 to 3, at ph=2.5, the tin recovery rate can be 99% or more even without adding hydrogen peroxide, but at this time the copper recovery rate is also high, i.e., the primary tin sludge also contains a large amount of copper impurities, and the tin recovery purity is low.
From examples 4 to 5 and comparative examples 4 to 5, it is understood that the adjustment of the pH of the solution to 0.8 to 1.5 effectively improves the recovery rate of tin, reduces the doping of copper, and removes COD in the wastewater. When the pH value is 1.5, the tin recovery rate reaches 100%, the copper recovery rate is lower than 30%, the tin recovery purity is high, and when the pH value is higher than 1.5, the tin recovery rate also reaches 100%, the COD removal rate also reaches 100%, but other impurities such as copper, iron and the like are separated out due to the rising of the pH value, so that a great amount of copper is doped in the tin sludge, the copper recovery rate reaches 43.19%, and the tin recovery purity is low; when the pH value is lower than 0.8, tin cannot be completely precipitated, the recovery rate of tin is only 95.68%, and the COD removal rate is also lower than 90%.
TABLE 3 tin copper content and tin recovery in the secondary tin sludge of examples 1, 6-9
The primary tin sludge obtained in examples 1 and 6 to 9 had a tin content of 44.30%, a copper content of 1.30% and a tin recovery of 99.97%, and the primary tin sludge was treated in step S2 to obtain the results shown in Table 3.
From examples 1, 6 to 9, it is known that the primary tin sludge is washed with deionized water to obtain secondary tin sludge with higher tin content and lower copper content, and when the mass ratio of the primary tin sludge to the deionized water is 1: (5-10), and when washing is carried out by using dilute nitric acid to adjust the pH value to be 1, copper impurities in primary tin mud can be effectively removed, meanwhile, tin treated by the steps is not easy to dissolve in a solution with the pH value of=1, precipitation of tin can be effectively inhibited, loss of tin during washing is reduced, and tin mud with higher tin recovery rate and higher purity is obtained; if dilute nitric acid is not used for regulating the pH value, deionized water is directly used for washing, copper impurities can be removed, but the pH value is 1.8, and more copper and iron can be enriched in the secondary tin slime, so that the tin content is relatively low. The deionized water is used for washing, so that the total recovery rate of tin is more than 99.47%, the tin content in a tin product is more than 55.40%, the copper content in the tin product is less than 0.66%, and a better copper-tin separation effect is realized while the recovery rate of tin is kept higher.
From examples 8 to 9, the mass ratio of the primary tin sludge to the aqueous ammonia was 10: in the cases (4) to (6), the copper impurities in the primary tin sludge can be removed by washing with aqueous ammonia, mainly by forming a copper ammonia complex with copper, and the dissolution of tin can be suppressed by washing with aqueous ammonia, so that the effect on the final recovery rate of tin is small, but the effect of removing copper impurities is not as good as that by washing with deionized water. The ammonia water is used for washing, so that the total recovery rate of tin is up to 99.96%, the tin content in a tin product is over 55.76%, the copper content in the tin product is below 1.18%, and a better copper-tin separation effect is realized while the recovery rate of tin is kept high.
TABLE 4 essential components of ammonium nitrate solution in example 1
| Composition of the components | Sn | Fe | Cu |
| g/L | 0.002 | 0 | 0.002 |
| Composition of the components | NO3-N | NH3-N | SO4 2- |
| mol/L | 2.79 | 3 | 0.001 |
As can be seen from Table 4, the ammonium nitrate solution obtained in example 1 has extremely low metal ion content, which further demonstrates that the metal impurities such as tin, iron, copper and the like in the tin stripping wastewater are effectively removed by the treatment in steps S1 to S3, and the metal ion content in the filtrate is low, so that the obtained ammonium nitrate solution has high purity.
TABLE 5 essential components of nitric acid solutions of example 1, example 10, example 11 and comparative example 6
As is clear from Table 5, the 23.16% -23.98% nitric acid solution obtained by adding concentrated sulfuric acid and distilling under reduced pressure has little residual impurities, high purity and meets the industry standard of regenerated tin stripping solution
Class III in (2021-0025T-HG). In comparative example 6, when the amount of concentrated sulfuric acid added was small, a 22.7% nitric acid solution was obtained, which did not correspond to the class III product in (2021-0025T-HG).
TABLE 6 nitrate recovery and corresponding ammonium sulfate composition for example 1, example 10, example 11 and comparative example 6
As can be seen from Table 6, the recovery rate of nitrate in the nitric acid type tin stripping wastewater is high and is not lower than 84%, and the finally obtained ammonium sulfate has less nitrate residues and high purity.
TABLE 7 essential components of the ammonium sulfate products of example 1, example 10, example 11, comparative example 6
As is clear from Table 7, the ammonium sulfate crystals, which were obtained by adding aqueous ammonia, evaporating, concentrating, cooling and crystallizing, were first-grade ammonium sulfate crystals satisfying the standard of ammonium sulfate (GB 535-1995), and were used as fertilizers, wherein the nitrogen content was greater than 21.67%. Although the nitrogen content in the ammonium sulfate obtained in comparative example 6 was also greater than 21%, it is found from table 5 that the nitrogen content was also high because nitrate residues were large, that is, nitrate nitrogen was contained in the ammonium sulfate.
It should be understood that the above examples of the present invention are provided for clarity of illustration only and are not intended to limit the embodiments of the present invention. Other variations or modifications of the above teachings will be apparent to those of ordinary skill in the art. It is not necessary here nor is it exhaustive of all embodiments. Any modification, equivalent replacement, improvement, etc. which come within the spirit and principles of the invention are desired to be protected by the following claims.
Claims (7)
1. The method for treating the nitric acid type tin stripping wastewater is characterized by comprising the following steps of:
S1, adding ammonia water into tin stripping wastewater of a nitric acid type circuit board, adjusting the pH to 0.8-1.5, adding hydrogen peroxide for oxidation, and separating to obtain primary tin mud and primary filtrate; the volume ratio of the tin stripping wastewater to the hydrogen peroxide is less than or equal to 10:1, and the volume fraction of the hydrogen peroxide is 27.5-35%;
S2, adding deionized water or ammonia water into the primary tin mud obtained in the step S1 to remove copper impurities, separating to obtain secondary tin mud and secondary filtrate, mixing the secondary filtrate with the primary filtrate obtained in the step S1 to obtain mixed filtrate,
Wherein the mass ratio of the primary tin mud to the deionized water is 1: (5-11), adding deionized water, and then adjusting the pH value of the solution to 0.9-1 by dilute nitric acid;
The mass ratio of the primary tin mud to the ammonia water is 10: (4-7);
S3, adding ammonia water into the mixed filtrate obtained in the step S2, adjusting the pH to 5.5-6, adding a polyacrylamide aqueous solution, and separating to obtain iron-containing copper sludge and a tertiary filtrate; treating the tertiary filtrate by ion exchange resin to obtain an ammonium nitrate solution;
S4, adding concentrated sulfuric acid into the ammonium nitrate solution in the step S3, wherein the molar ratio of nitrate radical to sulfate radical is less than or equal to 1:1, performing reduced pressure distillation to obtain a nitric acid solution and an ammonium bisulfate solution; and adding ammonia water into the ammonium bisulfate solution, regulating the pH value to be neutral, evaporating, concentrating, and cooling and crystallizing to obtain ammonium sulfate crystals.
2. The method according to claim 1, wherein the pH is 0.8 to 1 in step S1.
3. The treatment method according to claim 1, wherein in step S1, the volume ratio of the tin stripping wastewater to the hydrogen peroxide is 10: (1-2).
4. The method according to claim 3, wherein in step S1, the volume ratio of the tin stripping wastewater to the hydrogen peroxide is 10: (1-1.5).
5. The method according to claim 1, wherein in step S3, the mass concentration of the aqueous polyacrylamide solution is 0.1%, and the volume ratio of the aqueous polyacrylamide solution to the mixed filtrate is (1 to 2.5): 10.
6. The process according to claim 1, characterized in that in step S4, the molar ratio of nitrate and sulfate is 1: (1-1.4).
7. The method according to claim 1, wherein in step S4, the reduced pressure distillation treatment temperature is 80 to 100 ℃.
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