CN113816529A - Method for recovering and separating vanadium and chromium in vanadium and chromium wastewater - Google Patents
Method for recovering and separating vanadium and chromium in vanadium and chromium wastewater Download PDFInfo
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- CN113816529A CN113816529A CN202111186107.6A CN202111186107A CN113816529A CN 113816529 A CN113816529 A CN 113816529A CN 202111186107 A CN202111186107 A CN 202111186107A CN 113816529 A CN113816529 A CN 113816529A
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- chromium
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- sodium
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- 239000002351 wastewater Substances 0.000 title claims abstract description 83
- 229910052720 vanadium Inorganic materials 0.000 title claims abstract description 82
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 title claims abstract description 82
- 239000011651 chromium Substances 0.000 title claims abstract description 79
- 238000000034 method Methods 0.000 title claims abstract description 74
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 title claims abstract description 57
- 229910052804 chromium Inorganic materials 0.000 title claims abstract description 57
- JPIHMDPPRPVWNJ-UHFFFAOYSA-F S(=O)(=O)([O-])[O-].[V+5].[Cr+3].S(=O)(=O)([O-])[O-].S(=O)(=O)([O-])[O-].S(=O)(=O)([O-])[O-] Chemical compound S(=O)(=O)([O-])[O-].[V+5].[Cr+3].S(=O)(=O)([O-])[O-].S(=O)(=O)([O-])[O-].S(=O)(=O)([O-])[O-] JPIHMDPPRPVWNJ-UHFFFAOYSA-F 0.000 claims abstract description 39
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 37
- 239000010703 silicon Substances 0.000 claims abstract description 37
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 36
- WFISYBKOIKMYLZ-UHFFFAOYSA-N [V].[Cr] Chemical compound [V].[Cr] WFISYBKOIKMYLZ-UHFFFAOYSA-N 0.000 claims abstract description 31
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 claims abstract description 30
- 229910000423 chromium oxide Inorganic materials 0.000 claims abstract description 30
- 229920002401 polyacrylamide Polymers 0.000 claims abstract description 29
- 238000001354 calcination Methods 0.000 claims abstract description 20
- 238000000926 separation method Methods 0.000 claims abstract description 19
- 239000007788 liquid Substances 0.000 claims abstract description 16
- 239000002244 precipitate Substances 0.000 claims abstract description 16
- 238000005406 washing Methods 0.000 claims abstract description 14
- GNTDGMZSJNCJKK-UHFFFAOYSA-N Vanadium(V) oxide Inorganic materials O=[V](=O)O[V](=O)=O GNTDGMZSJNCJKK-UHFFFAOYSA-N 0.000 claims abstract description 12
- 238000001556 precipitation Methods 0.000 claims abstract description 12
- 239000000126 substance Substances 0.000 claims abstract description 8
- -1 vanadium pentoxide anhydride Chemical class 0.000 claims abstract description 5
- 238000006386 neutralization reaction Methods 0.000 claims abstract description 4
- 238000006722 reduction reaction Methods 0.000 claims abstract description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 18
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 15
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 claims description 12
- 239000011734 sodium Substances 0.000 claims description 9
- QAOWNCQODCNURD-UHFFFAOYSA-L sulfate group Chemical group S(=O)(=O)([O-])[O-] QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 9
- 239000002893 slag Substances 0.000 claims description 8
- 239000003638 chemical reducing agent Substances 0.000 claims description 7
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 6
- 229910052708 sodium Inorganic materials 0.000 claims description 6
- 235000010265 sodium sulphite Nutrition 0.000 claims description 6
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 5
- DWAQJAXMDSEUJJ-UHFFFAOYSA-M Sodium bisulfite Chemical compound [Na+].OS([O-])=O DWAQJAXMDSEUJJ-UHFFFAOYSA-M 0.000 claims description 5
- HRZFUMHJMZEROT-UHFFFAOYSA-L sodium disulfite Chemical compound [Na+].[Na+].[O-]S(=O)S([O-])(=O)=O HRZFUMHJMZEROT-UHFFFAOYSA-L 0.000 claims description 5
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 claims description 5
- 235000010262 sodium metabisulphite Nutrition 0.000 claims description 5
- 229910000013 Ammonium bicarbonate Inorganic materials 0.000 claims description 4
- 235000012538 ammonium bicarbonate Nutrition 0.000 claims description 4
- 239000001099 ammonium carbonate Substances 0.000 claims description 4
- 159000000000 sodium salts Chemical class 0.000 claims description 3
- VQBIMXHWYSRDLF-UHFFFAOYSA-M sodium;azane;hydrogen carbonate Chemical compound [NH4+].[Na+].[O-]C([O-])=O VQBIMXHWYSRDLF-UHFFFAOYSA-M 0.000 claims description 3
- DKAGJZJALZXOOV-UHFFFAOYSA-N hydrate;hydrochloride Chemical compound O.Cl DKAGJZJALZXOOV-UHFFFAOYSA-N 0.000 claims description 2
- VWBLQUSTSLXQON-UHFFFAOYSA-N N.[V+5] Chemical compound N.[V+5] VWBLQUSTSLXQON-UHFFFAOYSA-N 0.000 claims 1
- 238000002386 leaching Methods 0.000 claims 1
- 239000012716 precipitator Substances 0.000 claims 1
- CMZUMMUJMWNLFH-UHFFFAOYSA-N sodium metavanadate Chemical compound [Na+].[O-][V](=O)=O CMZUMMUJMWNLFH-UHFFFAOYSA-N 0.000 abstract description 8
- 229910000166 zirconium phosphate Inorganic materials 0.000 abstract description 8
- 230000000694 effects Effects 0.000 abstract description 7
- PXLIDIMHPNPGMH-UHFFFAOYSA-N sodium chromate Chemical compound [Na+].[Na+].[O-][Cr]([O-])(=O)=O PXLIDIMHPNPGMH-UHFFFAOYSA-N 0.000 abstract description 5
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 abstract 1
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 abstract 1
- 229910052921 ammonium sulfate Inorganic materials 0.000 abstract 1
- 235000011130 ammonium sulphate Nutrition 0.000 abstract 1
- HBXWYZMULLEJSG-UHFFFAOYSA-N chromium vanadium Chemical compound [V][Cr][V][Cr] HBXWYZMULLEJSG-UHFFFAOYSA-N 0.000 abstract 1
- 229910052938 sodium sulfate Inorganic materials 0.000 abstract 1
- 235000011152 sodium sulphate Nutrition 0.000 abstract 1
- 238000011084 recovery Methods 0.000 description 24
- 239000000047 product Substances 0.000 description 17
- 239000012065 filter cake Substances 0.000 description 14
- 239000007787 solid Substances 0.000 description 8
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 7
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 6
- QDOXWKRWXJOMAK-UHFFFAOYSA-N dichromium trioxide Chemical compound O=[Cr]O[Cr]=O QDOXWKRWXJOMAK-UHFFFAOYSA-N 0.000 description 6
- 238000004064 recycling Methods 0.000 description 5
- 229910052742 iron Inorganic materials 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 4
- 235000012239 silicon dioxide Nutrition 0.000 description 4
- LSGOVYNHVSXFFJ-UHFFFAOYSA-N vanadate(3-) Chemical compound [O-][V]([O-])([O-])=O LSGOVYNHVSXFFJ-UHFFFAOYSA-N 0.000 description 4
- DNWNZRZGKVWORZ-UHFFFAOYSA-N calcium oxido(dioxo)vanadium Chemical compound [Ca+2].[O-][V](=O)=O.[O-][V](=O)=O DNWNZRZGKVWORZ-UHFFFAOYSA-N 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 238000000605 extraction Methods 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 230000001376 precipitating effect Effects 0.000 description 3
- 229910000029 sodium carbonate Inorganic materials 0.000 description 3
- 229940001584 sodium metabisulfite Drugs 0.000 description 3
- 230000008901 benefit Effects 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- GRWVQDDAKZFPFI-UHFFFAOYSA-H chromium(III) sulfate Chemical compound [Cr+3].[Cr+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O GRWVQDDAKZFPFI-UHFFFAOYSA-H 0.000 description 2
- VQWFNAGFNGABOH-UHFFFAOYSA-K chromium(iii) hydroxide Chemical compound [OH-].[OH-].[OH-].[Cr+3] VQWFNAGFNGABOH-UHFFFAOYSA-K 0.000 description 2
- 239000012043 crude product Substances 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 239000011790 ferrous sulphate Substances 0.000 description 2
- 235000003891 ferrous sulphate Nutrition 0.000 description 2
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 description 2
- 229910000359 iron(II) sulfate Inorganic materials 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 description 1
- JZTPOMIFAFKKSK-UHFFFAOYSA-N O-phosphonohydroxylamine Chemical compound NOP(O)(O)=O JZTPOMIFAFKKSK-UHFFFAOYSA-N 0.000 description 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- ZCDOYSPFYFSLEW-UHFFFAOYSA-N chromate(2-) Chemical compound [O-][Cr]([O-])(=O)=O ZCDOYSPFYFSLEW-UHFFFAOYSA-N 0.000 description 1
- 229910001430 chromium ion Inorganic materials 0.000 description 1
- JOPOVCBBYLSVDA-UHFFFAOYSA-N chromium(6+) Chemical compound [Cr+6] JOPOVCBBYLSVDA-UHFFFAOYSA-N 0.000 description 1
- 238000005345 coagulation Methods 0.000 description 1
- 230000015271 coagulation Effects 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- PTMHPRAIXMAOOB-UHFFFAOYSA-N phosphoramidic acid Chemical compound NP(O)(O)=O PTMHPRAIXMAOOB-UHFFFAOYSA-N 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000010802 sludge Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 150000003681 vanadium Chemical class 0.000 description 1
- 229910001456 vanadium ion Inorganic materials 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F9/00—Multistage treatment of water, waste water or sewage
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G37/00—Compounds of chromium
- C01G37/02—Oxides or hydrates thereof
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B34/00—Obtaining refractory metals
- C22B34/20—Obtaining niobium, tantalum or vanadium
- C22B34/22—Obtaining vanadium
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B34/00—Obtaining refractory metals
- C22B34/30—Obtaining chromium, molybdenum or tungsten
- C22B34/32—Obtaining chromium
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
- C22B7/006—Wet processes
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/52—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
- C02F1/54—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using organic material
- C02F1/56—Macromolecular compounds
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/58—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
-
- 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
- C02F2101/22—Chromium or chromium compounds, e.g. chromates
-
- 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
Abstract
The invention relates to a method for recovering and separating vanadium and chromium in vanadium and chromium wastewater, belonging to the technical field of chemical industry. The method comprises the following steps: a. pretreating the chromium-vanadium sulfate wastewater by using a modified polyacrylamide solution, and then carrying out solid-liquid separation to obtain low-silicon vanadium-chromium sulfate wastewater; b. treating the low-silicon vanadium-chromium sulfate wastewater by adopting reduction, neutralization and precipitation processes to obtain a low-silicon vanadium-chromium precipitate; c. calcining the low-silicon vanadium-chromium precipitate to obtain chromium oxide and vanadium pentoxide anhydride; d. and washing the chromium oxide and vanadium pentoxide anhydrous substances by using a dilute hydrochloric acid solution, and carrying out solid-liquid separation to obtain a chromium oxide and vanadium solution. The method comprises the steps of pretreating chromium-vanadium wastewater to obtain vanadium-chromium wastewater mainly comprising sodium sulfate, ammonium sulfate, sodium vanadate and sodium chromate, then obtaining a vanadium-chromium composition by adopting a conventional reduction-precipitation process, calcining at high temperature, and washing with hydrochloric acid to obtain a chromium oxide and sodium vanadate solution. Solves the problems of difficult utilization of precipitates and low value caused by complex process and poor vanadium-chromium separation effect in the prior art.
Description
Technical Field
The invention relates to a method for recovering and separating vanadium and chromium in vanadium and chromium wastewater, belonging to the technical field of chemical industry.
Background
The application of vanadium in other fields such as chemical industry, vanadium batteries, aerospace and the like is continuously expanded, and the vanadium battery has a good development prospect. In the prior art, vanadium cannot be completely extracted in the extraction process, so that the vanadium-containing wastewater contains hexavalent chromium ions and pentavalent vanadium ions, and the direct discharge causes great harm to the environment and human bodies. In addition, the vanadium and chromium content in the vanadium-containing wastewater is high, and the direct discharge causes resource waste, so that the vanadium-containing wastewater needs to be treated to recover valuable elements. In the prior art, a direct reduction method, a vanadium precipitation method or an adsorption method is generally adopted to separate and recover vanadium and chromium elements in vanadium-containing wastewater.
Chinese patent, publication No. CN1073414A, entitled a method for separating and recovering vanadium and chromium from vanadium-chromium mixed wastewater and vanadium-chromium wastewater, which firstly uses ferric salt to precipitate and separate vanadium, thus obtaining ferric vanadate precipitate; then, after adjusting the pH value of the chromium solution, reducing chromium by using a reducing agent to obtain a chromium sulfate solution; further adjusting the pH value of the chromium sulfate solution to precipitate chromium hydroxide. The method separates vanadium, chromium, silicon and iron in the vanadium-chromium wastewater, but the obtained product iron vanadate and chromium hydroxide have you in many people, the separation coefficient is small, and simultaneously, silicate is always accompanied in the precipitate, so that the precipitate is difficult to use, and the use value is low.
The process recorded in the research on the process for recycling valuable elements in the vanadium-chromium-containing wastewater adopts an ion exchange process to separate vanadium and chromium in the wastewater; then separating vanadium by adopting a calcium vanadate precipitation method to obtain a calcium vanadate precipitate and a sodium chromate solution; evaporating and crystallizing the sodium chromate solution to obtain sodium chromate crystals; calcium vanadate is additionally treated, and sodium chromate crystals are used as products for export sales. The method has the advantages of incomplete removal of vanadium and chromium in the wastewater and high treatment cost.
The process recorded in the research on electrolytic treatment of vanadium-and chromium-containing wastewater utilizes an electrolytic oxidation anode method to obtain active iron ions, the essential process is a reduction precipitation method, sludge containing vanadium, chromium, silicon and iron is obtained, the utilization value is low, and the treatment is difficult; and the industrialization difficulty of the electrolysis process is high.
Chinese patent, publication No. CN110104834A, entitled treating method for vanadium-containing wastewater, which adopts ferrous sulfate and aminophosphoric acid resin to respectively obtain ferric vanadate precipitate and adsorb chromium-containing solution, thereby realizing the separation and extraction of sail and chromium. The method cannot remove silicon in the precipitate, and the introduction of ferrous sulfate and aminophosphonic acid resin causes cost rise.
Disclosure of Invention
The invention aims to solve the technical problems of complex process, poor vanadium-chromium separation effect, difficult utilization of precipitate and low value in the prior art.
The technical scheme adopted by the invention for solving the technical problems is as follows: the method for recovering and separating vanadium and chromium in the vanadium and chromium wastewater comprises the following steps:
a. pretreating the chromium-vanadium sulfate wastewater by using a modified polyacrylamide solution, and then carrying out solid-liquid separation to obtain low-silicon vanadium-chromium sulfate wastewater;
b. treating the low-silicon vanadium-chromium sulfate wastewater by adopting reduction, neutralization and precipitation processes to obtain a low-silicon vanadium-chromium precipitate;
c. calcining the low-silicon vanadium-chromium precipitate to obtain chromium oxide and vanadium pentoxide anhydride;
d. and washing the chromium oxide and vanadium pentoxide anhydrous substances by using a dilute hydrochloric acid solution, and carrying out solid-liquid separation to obtain a chromium oxide and vanadium solution.
In the method, the chromium-vanadium sulfate wastewater in the step a is sulfate wastewater obtained after vanadium slag/vanadium ore sodium roasting-water leaching-ammonium salt vanadium precipitation, and the chromium-vanadium sulfate wastewater has a silicon content of 0.5-3.0 g/L, a vanadium content of 0.15-0.50 g/L, a chromium content of 0.50-3.0 g/L, a sodium content of 20-50 g/L, an ammonium content of 8.0-10.0 g/L and a pH value of 2.5-3.5.
Wherein, the concentration of the modified polyacrylamide solution in the step a in the method is 0.05-0.25%.
Further, the water for preparing the modified polyacrylamide dilute solution in the step a in the method is sulfate wastewater after recovering vanadium and chromium.
In the method, the adding amount ratio of the vanadium-chromium sulfate wastewater to the modified polyacrylamide dilute solution for pretreatment in the step a is 100: 0.5-100: 1.5.
In the method, the treatment time of the modified polyacrylamide dilute solution for vanadium-chromium sulfate wastewater pretreatment in the step a is 1-3 hours.
Wherein, the vanadium-chromium reducing agent in the step b in the method is at least one of sodium sulfite, sodium bisulfite and sodium pyrosulfite.
Wherein, the precipitant in step b is at least one of sodium hydroxide, sodium carbonate and ammonium bicarbonate.
Wherein, in the step c of the method, the calcining temperature is 800-1500 ℃, and the calcining time is 1-3 hours.
Wherein, the hydrochloric acid in the step d in the method is diluted hydrochloric acid with water to prepare dilute hydrochloric acid with the concentration of 3-5%, and the washing time is 1-3 hours.
The invention has the beneficial effects that: the method for separating vanadium and chromium from the vanadium and chromium wastewater is simple and easy to implement, and the obtained vanadium and chromium product has high value and is easy to recycle. The method can be directly applied to all the sodium-modified vanadium extraction production, and has good popularization and utilization prospects. The chromium oxide can be sold as a product, and the vanadium solution can be precipitated by a traditional method to recover vanadium. Firstly removing silicon to obtain silicon slag; reducing and precipitating to obtain vanadium-chromium slag; calcining the vanadium-chromium slag at normal pressure to obtain a coarse chromium oxide product; and washing the crude chromium oxide product with hydrochloric acid to obtain a chromium oxide product and a sodium vanadate solution, and directly returning the chromium oxide product serving as the sodium vanadate solution for sale to a large-scale production system for recycling. Meanwhile, the method has simple silicon removal process in the vanadium-chromium wastewater and is convenient for industrial application; the vanadium-chromium separation effect in the vanadium-chromium wastewater is good; the vanadium-chromium filter cake is mature in normal-pressure calcination process and simple in equipment; the hydrochloric acid washing process for promoting the chromium oxide is simple and has good washing effect; the recycling process of the sodium vanadate solution is simple, and the sodium vanadate solution can be seamlessly connected with a large production system; the chromium oxide product has high value, large market demand and high economic benefit.
Detailed Description
The present invention will be further described with reference to the following examples.
The method for recovering and separating vanadium and chromium in the vanadium and chromium wastewater comprises the following steps:
a. pretreating the chromium-vanadium sulfate wastewater by using a modified polyacrylamide solution, and then carrying out solid-liquid separation to obtain low-silicon vanadium-chromium sulfate wastewater;
b. treating the low-silicon vanadium-chromium sulfate wastewater by adopting reduction, neutralization and precipitation processes to obtain a low-silicon vanadium-chromium precipitate;
c. calcining the low-silicon vanadium-chromium precipitate to obtain chromium oxide and vanadium pentoxide anhydride;
d. and washing the chromium oxide and vanadium pentoxide anhydrous substances by using a dilute hydrochloric acid solution, and carrying out solid-liquid separation to obtain a chromium oxide and vanadium solution. As can be understood by those skilled in the art, in the method, the raw water of the vanadium-chromium wastewater is directly added with a desiliconization agent, namely, a modified polyacrylamide solution is precipitated at normal temperature to remove silicon, so that desiliconized slag and desiliconized liquid are obtained; as a large amount of sulfate (sodium, ammonium), silicon, chromium and the like exist in the vanadium-chromium wastewater, silicic acid is condensed into silicic acid under an acidic condition and stably exists in a suspension state, and the silicic acid is in a negative charge, the suspended fine silicic acid particles can be coagulated by adopting cationic polyacrylamide. The modification aims to weaken the coagulation effect of polyacrylamide on chromate and vanadate. Reducing and precipitating vanadium and chromium by the silicon removing liquid according to a conventional industrial method to obtain a vanadium and chromium filter cake with VO (OH)2 and Cr (OH)3 as main components; calcining the vanadium-chromium filter cake to obtain a chromium oxide crude product; washing the crude product of the chromium oxide with hydrochloric acid to obtain a chromium oxide product and a sodium vanadate solution; the chromium oxide product is directly sold, and the sodium vanadate solution is returned to a large production system for recycling and recovering vanadium therein.
Preferably, in the step a of the method, the chromium-vanadium sulfate wastewater is sulfate wastewater obtained after vanadium slag/vanadium ore sodium salt roasting-water leaching-ammonium salt vanadium precipitation, and the chromium-vanadium sulfate wastewater has a silicon content of 0.5-3.0 g/l, a vanadium content of 0.15-0.50 g/l, a chromium content of 0.50-3.0 g/l, a sodium content of 20-50 g/l, an ammonium content of 8.0-10.0 g/l, and a pH value of 2.5-3.5. The technical personnel in the field can understand that the method only prefers the chromium-vanadium sulfate wastewater to be the sulfate wastewater after vanadium slag/vanadium ore sodium salt roasting-water leaching-ammonium salt vanadium precipitation, and can actually realize the problem of wastewater recycling. Further preferably, the silicon content is 0.5 to 3.0g/L, the vanadium content is 0.15 to 0.50g/L, the chromium content is 0.50 to 3.0g/L, the sodium content is 20 to 50g/L, the ammonium content is 8.0 to 10.0 g/L, and the pH value is 2.5 to 3.5.
Preferably, the concentration of the modified polyacrylamide solution in step a in the above method is 0.05% to 0.25%. As can be understood by those skilled in the art, in order to ensure the silicon removal effect, the method preferably has a concentration of 0.05% to 0.25% in the modified polyacrylamide solution, and actually, a concentration of 0.10% in the modified polyacrylamide solution may be further preferred.
Preferably, the water for preparing the modified polyacrylamide dilute solution in the step a in the method is sulfate wastewater after recovering vanadium and chromium. As can be understood by those skilled in the art, in order to reduce the cost and increase the wastewater treatment capacity, the method preferably uses the water for preparing the modified polyacrylamide dilute solution as the sulfate wastewater after recovering vanadium and chromium.
Preferably, the adding amount ratio of the vanadium-chromium sulfate wastewater to the modified polyacrylamide diluted solution for pretreatment in the step a in the method is 100: 0.5-100: 1.5. As can be understood by those skilled in the art, in order to ensure the silicon removal effect, the addition ratio of the vanadium-chromium sulfate wastewater to the modified polyacrylamide diluted solution for pretreatment is preferably 100: 0.5-100: 1.5, and actually, the addition ratio of the modified polyacrylamide diluted solution with 0.10% can be further preferably 100: 1.0.
Preferably, in the method, the treatment time of the modified polyacrylamide dilute solution for vanadium-chromium sulfate wastewater pretreatment in the step a is 1-3 hours. As can be understood by those skilled in the art, in order to ensure the reaction as far as possible, the method preferably treats the vanadium-chromium sulfate wastewater with the modified polyacrylamide dilute solution for 1-3 hours, and preferably treats the vanadium-chromium sulfate wastewater with the 0.10% modified polyacrylamide dilute solution for 2 hours.
Preferably, the vanadium-chromium reducing agent in step b in the above method is at least one of sodium sulfite, sodium bisulfite and sodium metabisulfite. It will be appreciated by those skilled in the art that the preferred vanadium chromium reducing agent is a commonly used inorganic reducing agent, specifically at least one of sodium sulfite, sodium bisulfite, sodium metabisulfite. In practice it may be preferred that the vanadium chromium reducing agent is sodium sulphite.
Preferably, in the above method, the precipitant in step b is at least one of sodium hydroxide, sodium carbonate and ammonium bicarbonate. It will be appreciated by those skilled in the art that the preferred precipitating agent is a commonly used basic substance, at least one of sodium hydroxide, sodium carbonate, ammonium bicarbonate, preferably sodium carbonate.
Preferably, in the step c of the method, the calcining temperature is 800-1500 ℃, and the calcining time is 1-3 hours. It will be appreciated by those skilled in the art that the calcination temperature is from 800 ℃ to 1500 ℃, preferably 1200 ℃. The calcination time is 1-3 hours, and the preferred calcination time is 2 hours at 1200 ℃.
Preferably, in the step d of the method, the hydrochloric acid is diluted by industrial hydrochloric acid water to prepare dilute hydrochloric acid with the concentration of 3-5%, the solid-to-solid ratio of the dilute hydrochloric acid washing solution is 1-3 ml/g, and the washing time is 1-3 hours. As can be understood by those skilled in the art, in order to reduce the cost, the method is preferably implemented by diluting hydrochloric acid which is commonly used industrial hydrochloric acid with water to prepare dilute hydrochloric acid, and further preferably washing the dilute hydrochloric acid for 2 hours, wherein the concentration of the dilute hydrochloric acid is 5 percent and the solid ratio is 2 ml/g.
Example 1
Taking 1000ml of vanadium-chromium sulfate wastewater (0.5 g/l of Si, 0.15g/l of V and 3.0g/l of Cr) and 15ml of 0.05 percent modified polyacrylamide dilute solution, treating for 3 hours at normal temperature, and carrying out solid-liquid separation to obtain 1001ml of low-silicon vanadium-chromium sulfate wastewater (0.05 g/l of Si, 0.145g/l of V and 2.95g/l of Cr); the V recovery rate is 96.75 percent, and the Cr recovery rate is 98.43 percent. Taking 1000ml of low-silicon vanadium-chromium sulfate wastewater, adding 5g of sodium sulfite for reduction treatment for 1h, adding sodium carbonate to adjust the pH value to 8.0, reacting for 2h, and carrying out solid-liquid separation to obtain 13g of filter cake (the water content of the filter cake is 50%, the Si content of the dry filter cake is 0.883%, the Na content is 1.538%, the V content is 2.218% and the Cr content is 44.904%); the V recovery rate is 99.43 percent, and the Cr recovery rate is 98.94 percent. Calcining 10g of filter cake at 1500 ℃ for 1h under normal pressure, treating the obtained solid with 5% hydrochloric acid according to a liquid-solid ratio of 2:1 for 1h, filtering and drying to obtain a chromium oxide product with the Cr2O3 content of 96.653%, the V content of 0.354% and the Si content of 1.269%; the V recovery rate is 89.18 percent, and the Cr recovery rate is 99.72 percent. In the whole process from the vanadium-chromium sulfate wastewater to the chromium oxide product, the total recovery rate of V is 85.80 percent, and the total recovery rate of Cr is 97.12 percent.
Example 2
Taking 1000ml of vanadium-chromium sulfate wastewater (Si 3.0g/l, V0.50 g/l and Cr 0.50g/l) and 5ml of 0.25% modified polyacrylamide dilute solution, treating at normal temperature for 1h, and carrying out solid-liquid separation to obtain 995ml of low-silicon vanadium-chromium sulfate wastewater (Si 0.01g/l, V0.485g/l and Cr 0.493 g/l); the V recovery rate is 96.52 percent, and the Cr recovery rate is 98.11 percent. Taking 800ml of low-silicon vanadium chromium sulfate wastewater, adding 3.5g of sodium metabisulfite for reduction treatment for 3h, adding sodium hydroxide to adjust the pH value to 9.0, reacting for 3h, and carrying out solid-liquid separation to obtain 4.22g of filter cake (the water content of the filter cake is 55%, the Si content of a dry filter cake is 0.369%, the Na content is 5.794%, the V content is 20.333% and the Cr content is 20.702%); the V recovery rate is 99.49 percent, and the Cr recovery rate is 99.65 percent. Calcining 4g of filter cake at 1300 ℃ for 2h under normal pressure, treating the obtained solid with 5% hydrochloric acid according to a liquid-solid ratio of 3:1 for 3h, filtering and drying, wherein the chromium oxide product contains 97.332% of Cr2O3, 0.539% of V and 0.539% of Si; the V recovery rate is 99.18 percent, and the Cr recovery rate is 99.56 percent. In the whole process from the vanadium-chromium sulfate wastewater to the chromium oxide product, the total recovery rate of V is 95.23 percent, and the total recovery rate of Cr is 97.33 percent.
Example 3
Taking 1000ml of vanadium-chromium sulfate wastewater (Si 2.0g/l, V0.35 g/l and Cr 1.50g/l) and 10ml of 0.10% modified polyacrylamide dilute solution, treating at normal temperature for 2h, and carrying out solid-liquid separation to obtain 998ml of low-silicon vanadium-chromium sulfate wastewater (Si 0.008g/l, V0.347 g/l and Cr 1.487 g/l); the V recovery rate is 98.95 percent and the Cr recovery rate is 98.94 percent. Taking 800ml of low-silicon vanadium-chromium sulfate wastewater, adding 4.0g of sodium bisulfite for reduction treatment for 2h, adding sodium hydroxide to adjust the pH value to 7.5, reacting for 2h, and carrying out solid-liquid separation to obtain 8.039g of filter cake (the filter cake contains 60% of water, 0.155% of Si, 3.141% of Na, 8.552% of V and 36.853% of Cr); the V recovery rate is 99.063 percent, and the Cr recovery rate is 99.613 percent. Calcining 8g of filter cake at 800 ℃ for 3h under normal pressure, treating the obtained solid with 5% hydrochloric acid according to a liquid-solid ratio of 1:1 for 3h, filtering and drying to obtain a chromium oxide product with the Cr2O3 content of 99.491%, the V content of 0.116% and the Si content of 0.058%; the V recovery rate is 99.269 percent, and the Cr recovery rate is 99.805 percent. In the whole process from vanadium-chromium sulfate wastewater to chromium oxide products, the total recovery rate of V is 97.30%, and the total recovery rate of Cr is 98.36%.
Claims (10)
1. The method for recovering and separating vanadium and chromium in the vanadium and chromium wastewater is characterized by comprising the following steps:
a. pretreating the chromium-vanadium sulfate wastewater by using a modified polyacrylamide solution, and then carrying out solid-liquid separation to obtain low-silicon vanadium-chromium sulfate wastewater;
b. treating the low-silicon vanadium-chromium sulfate wastewater by adopting reduction, neutralization and precipitation processes to obtain a low-silicon vanadium-chromium precipitate;
c. calcining the low-silicon vanadium-chromium precipitate to obtain chromium oxide and vanadium pentoxide anhydride;
d. and washing the chromium oxide and vanadium pentoxide anhydrous substances by using a dilute hydrochloric acid solution, and carrying out solid-liquid separation to obtain a chromium oxide and vanadium solution.
2. The method for recovering and separating vanadium and chromium from vanadium and chromium wastewater as claimed in claim 1, which is characterized in that: in the step a, the chromium-vanadium sulfate wastewater is sulfate wastewater obtained after vanadium slag/vanadium ore sodium salt roasting, water leaching and ammonium salt vanadium precipitation, and has a silicon content of 0.5-3.0 g/L, a vanadium content of 0.15-0.50 g/L, a chromium content of 0.50-3.0 g/L, a sodium content of 20-50 g/L, an ammonium content of 8.0-10.0 g/L and a pH value of 2.5-3.5.
3. The method for recovering and separating vanadium and chromium from vanadium and chromium wastewater as claimed in claim 1, which is characterized in that: the concentration of the modified polyacrylamide solution in the step a is 0.05-0.25%.
4. The method for recovering and separating vanadium and chromium from vanadium and chromium wastewater as claimed in claim 3, which is characterized in that: and (b) preparing water for the modified polyacrylamide dilute solution in the step a, wherein the prepared water is sulfate wastewater after vanadium and chromium are recovered.
5. The method for recovering and separating vanadium and chromium from vanadium and chromium wastewater as claimed in claim 1, which is characterized in that: the adding amount ratio of the vanadium-chromium sulfate wastewater to the modified polyacrylamide dilute solution for pretreatment in the step a is 100: 0.5-100: 1.5.
6. The method for recovering and separating vanadium and chromium from vanadium and chromium wastewater as claimed in claim 1, which is characterized in that: and (b) treating the vanadium-chromium sulfate wastewater in the step (a) with a modified polyacrylamide dilute solution for 1-3 hours.
7. The method for recovering and separating vanadium and chromium from vanadium and chromium wastewater as claimed in claim 1, which is characterized in that: in the step b, the vanadium-chromium reducing agent is at least one of sodium sulfite, sodium bisulfite and sodium pyrosulfite.
8. The method for recovering and separating vanadium and chromium from vanadium and chromium wastewater as claimed in claim 1, which is characterized in that: in the step b, the precipitator is at least one of sodium hydroxide, sodium carbonate and ammonium bicarbonate.
9. The method for recovering and separating vanadium and chromium from vanadium and chromium wastewater as claimed in claim 1, which is characterized in that: in the step c, the calcining temperature is 800-1500 ℃, and the calcining time is 1-3 hours.
10. The method for recovering and separating vanadium and chromium from vanadium and chromium wastewater as claimed in claim 1, which is characterized in that: in the step d, the hydrochloric acid is diluted by industrial hydrochloric acid water to prepare diluted hydrochloric acid with the concentration of 3-5%, and the washing time is 1-3 hours.
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