CN117385201A - Method for treating scheelite - Google Patents
Method for treating scheelite Download PDFInfo
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- CN117385201A CN117385201A CN202311333999.7A CN202311333999A CN117385201A CN 117385201 A CN117385201 A CN 117385201A CN 202311333999 A CN202311333999 A CN 202311333999A CN 117385201 A CN117385201 A CN 117385201A
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- acid
- acid leaching
- solution
- ammonium
- leaching
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- 238000000034 method Methods 0.000 title claims abstract description 69
- 238000002386 leaching Methods 0.000 claims abstract description 126
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims abstract description 112
- 239000002253 acid Substances 0.000 claims abstract description 86
- 229910052721 tungsten Inorganic materials 0.000 claims abstract description 71
- 239000010937 tungsten Substances 0.000 claims abstract description 71
- 239000002893 slag Substances 0.000 claims abstract description 24
- 239000007788 liquid Substances 0.000 claims abstract description 12
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 11
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000011575 calcium Substances 0.000 claims abstract description 7
- 229910052791 calcium Inorganic materials 0.000 claims abstract description 7
- 238000000926 separation method Methods 0.000 claims abstract description 6
- 238000005554 pickling Methods 0.000 claims abstract description 3
- 238000002425 crystallisation Methods 0.000 claims description 52
- 230000008025 crystallization Effects 0.000 claims description 52
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 43
- 229910017604 nitric acid Inorganic materials 0.000 claims description 43
- 239000012452 mother liquor Substances 0.000 claims description 32
- YIXJRHPUWRPCBB-UHFFFAOYSA-N magnesium nitrate Chemical group [Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O YIXJRHPUWRPCBB-UHFFFAOYSA-N 0.000 claims description 29
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 26
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 20
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 20
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 20
- 238000006243 chemical reaction Methods 0.000 claims description 20
- 239000003337 fertilizer Substances 0.000 claims description 18
- NGLMYMJASOJOJY-UHFFFAOYSA-O azanium;calcium;nitrate Chemical compound [NH4+].[Ca].[O-][N+]([O-])=O NGLMYMJASOJOJY-UHFFFAOYSA-O 0.000 claims description 17
- 239000012535 impurity Substances 0.000 claims description 13
- 229910021529 ammonia Inorganic materials 0.000 claims description 12
- 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 11
- 238000004090 dissolution Methods 0.000 claims description 11
- 239000011347 resin Substances 0.000 claims description 9
- 229920005989 resin Polymers 0.000 claims description 9
- 239000003795 chemical substances by application Substances 0.000 claims description 8
- 239000013078 crystal Substances 0.000 claims description 8
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 6
- XAYGUHUYDMLJJV-UHFFFAOYSA-Z decaazanium;dioxido(dioxo)tungsten;hydron;trioxotungsten Chemical compound [H+].[H+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.[O-][W]([O-])(=O)=O.[O-][W]([O-])(=O)=O.[O-][W]([O-])(=O)=O.[O-][W]([O-])(=O)=O.[O-][W]([O-])(=O)=O.[O-][W]([O-])(=O)=O XAYGUHUYDMLJJV-UHFFFAOYSA-Z 0.000 claims description 6
- 239000007787 solid Substances 0.000 claims description 5
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims description 4
- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 claims description 4
- 238000000746 purification Methods 0.000 claims description 4
- 238000005915 ammonolysis reaction Methods 0.000 claims description 3
- USFZMSVCRYTOJT-UHFFFAOYSA-N Ammonium acetate Chemical compound N.CC(O)=O USFZMSVCRYTOJT-UHFFFAOYSA-N 0.000 claims description 2
- 239000005695 Ammonium acetate Substances 0.000 claims description 2
- 229940043376 ammonium acetate Drugs 0.000 claims description 2
- 235000019257 ammonium acetate Nutrition 0.000 claims description 2
- 235000019270 ammonium chloride Nutrition 0.000 claims description 2
- ZXOKVTWPEIAYAB-UHFFFAOYSA-N dioxido(oxo)tungsten Chemical compound [O-][W]([O-])=O ZXOKVTWPEIAYAB-UHFFFAOYSA-N 0.000 claims description 2
- 229940098779 methanesulfonic acid Drugs 0.000 claims description 2
- 239000006227 byproduct Substances 0.000 abstract description 6
- 238000003723 Smelting Methods 0.000 abstract description 5
- 230000000694 effects Effects 0.000 abstract description 4
- -1 and in addition Substances 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 93
- 229910052698 phosphorus Inorganic materials 0.000 description 20
- 229910052785 arsenic Inorganic materials 0.000 description 17
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 16
- 238000001914 filtration Methods 0.000 description 16
- 239000011574 phosphorus Substances 0.000 description 16
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 description 15
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 14
- 238000011084 recovery Methods 0.000 description 14
- 229910052710 silicon Inorganic materials 0.000 description 14
- 239000010703 silicon Substances 0.000 description 14
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 12
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 12
- ZCCIPPOKBCJFDN-UHFFFAOYSA-N calcium nitrate Chemical compound [Ca+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ZCCIPPOKBCJFDN-UHFFFAOYSA-N 0.000 description 12
- 239000011591 potassium Substances 0.000 description 12
- 229910052700 potassium Inorganic materials 0.000 description 12
- 239000000047 product Substances 0.000 description 9
- 239000012141 concentrate Substances 0.000 description 7
- 230000003472 neutralizing effect Effects 0.000 description 7
- 230000035484 reaction time Effects 0.000 description 7
- 238000001179 sorption measurement Methods 0.000 description 7
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 230000032683 aging Effects 0.000 description 6
- 238000006386 neutralization reaction Methods 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 238000001704 evaporation Methods 0.000 description 5
- 239000002351 wastewater Substances 0.000 description 5
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 4
- 239000000654 additive Substances 0.000 description 4
- 230000000996 additive effect Effects 0.000 description 4
- 239000003513 alkali Substances 0.000 description 4
- XKMRRTOUMJRJIA-UHFFFAOYSA-N ammonia nh3 Chemical compound N.N XKMRRTOUMJRJIA-UHFFFAOYSA-N 0.000 description 4
- 230000001276 controlling effect Effects 0.000 description 4
- 238000000354 decomposition reaction Methods 0.000 description 4
- 239000011964 heteropoly acid Substances 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 3
- 238000000605 extraction Methods 0.000 description 3
- 238000001556 precipitation Methods 0.000 description 3
- 238000004064 recycling Methods 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 159000000000 sodium salts Chemical class 0.000 description 3
- CMPGARWFYBADJI-UHFFFAOYSA-L tungstic acid Chemical compound O[W](O)(=O)=O CMPGARWFYBADJI-UHFFFAOYSA-L 0.000 description 3
- 239000002699 waste material Substances 0.000 description 3
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 230000008020 evaporation Effects 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000010413 mother solution Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- 235000008733 Citrus aurantifolia Nutrition 0.000 description 1
- 229910017958 MgNH Inorganic materials 0.000 description 1
- 235000011941 Tilia x europaea Nutrition 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
- 239000000084 colloidal system Substances 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000005469 granulation Methods 0.000 description 1
- 230000003179 granulation Effects 0.000 description 1
- 239000002920 hazardous waste Substances 0.000 description 1
- 125000005842 heteroatom Chemical group 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 239000004571 lime Substances 0.000 description 1
- 238000005272 metallurgy Methods 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 235000021110 pickles Nutrition 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000012629 purifying agent Substances 0.000 description 1
- 230000002787 reinforcement Effects 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 238000005728 strengthening Methods 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- PBYZMCDFOULPGH-UHFFFAOYSA-N tungstate Chemical compound [O-][W]([O-])(=O)=O PBYZMCDFOULPGH-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- 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
- C22B34/36—Obtaining tungsten
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G41/00—Compounds of tungsten
-
- C—CHEMISTRY; METALLURGY
- C05—FERTILISERS; MANUFACTURE THEREOF
- C05C—NITROGENOUS FERTILISERS
- C05C1/00—Ammonium nitrate fertilisers
-
- 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
- C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
- C22B3/04—Extraction of metal compounds from ores or concentrates by wet processes by leaching
- C22B3/06—Extraction of metal compounds from ores or concentrates by wet processes by leaching in inorganic acid solutions, e.g. with acids generated in situ; in inorganic salt solutions other than ammonium salt solutions
- C22B3/065—Nitric acids or salts 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
- C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
- C22B3/04—Extraction of metal compounds from ores or concentrates by wet processes by leaching
- C22B3/06—Extraction of metal compounds from ores or concentrates by wet processes by leaching in inorganic acid solutions, e.g. with acids generated in situ; in inorganic salt solutions other than ammonium salt solutions
- C22B3/10—Hydrochloric acid, other halogenated acids or salts 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
- C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
- C22B3/04—Extraction of metal compounds from ores or concentrates by wet processes by leaching
- C22B3/16—Extraction of metal compounds from ores or concentrates by wet processes by leaching in organic solutions
- C22B3/1608—Leaching with acyclic or carbocyclic agents
- C22B3/1616—Leaching with acyclic or carbocyclic agents of a single type
- C22B3/165—Leaching with acyclic or carbocyclic agents of a single type with organic acids
-
- 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)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Manufacturing & Machinery (AREA)
- Inorganic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Environmental & Geological Engineering (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Geochemistry & Mineralogy (AREA)
- Geology (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
Abstract
The invention belongs to the field of tungsten ore smelting, and particularly discloses a method for treating scheelite, which comprises the steps of providing NH by scheelite and acid 4 + Acid leaching is assisted by an acid leaching auxiliary agent, and then solid-liquid separation is carried out, thus obtaining acid leaching slag enriched with tungsten and acid leaching slag enriched with calcium and NH 4 + Is prepared from the above-mentioned pickling solution. The process disclosed by the invention has an excellent acid leaching and enriching effect of tungsten, and in addition, byproducts in the smelting process can be effectively recycled.
Description
Technical Field
The invention relates to a tungsten extraction process in the field of wet metallurgy, in particular to a method for treating scheelite.
Background
The sodium hydroxide pressure boiling process is the main stream process for treating scheelite in China. Because the equilibrium constant of the reaction between sodium hydroxide and scheelite is very small, reinforcement means such as high temperature, high pressure, high alkali concentration and the like are needed to decompose scheelite efficiently. With the recent tightening of national environmental protection policies, the tungsten smelting production mode with high energy consumption, high alkali consumption and high alkaline reagent cost is subject to more serious environmental protection and economic pressure. In addition, the alkali boiling slag is classified as dangerous waste, special disposal is needed, a large amount of sodium salt and ammonia nitrogen wastewater can be generated in the subsequent ion exchange purification transformation process, the sodium salt and ammonia nitrogen wastewater is converted according to unit metal ton, and the discharge amount of the tungsten smelting wastewater is more than ten times that of other nonferrous metal smelting processes.
The foreign scheelite treatment mainly adopts a soda autoclaving method, and the reaction equilibrium constant of soda and scheelite is also very small, so that a strengthening means of high temperature and high pressure and high reagent dosage is also required, the soda dosage generally reaches 3 times of theoretical quantity, and laboratory researches in China need even 5-6 times. And the operating temperature is as high as about 225 ℃ and the equipment pressure is as high as 20atm. The problems of alkali brittleness and the like of the high-voltage equipment material bring a certain potential safety hazard to industrial production. Excess soda increases the cost of recovery and the leaching residue is also included as hazardous waste and requires special disposal. The subsequent connection is an acid extraction process, and the organic matters in the extraction process have heavy smell, poorer operation environment and high fireproof requirement. The raffinate needs to remove oil and COD and a large amount of sodium salt in the raffinate needs to be treated.
The reaction trend of hydrochloric acid, sulfuric acid, nitric acid and scheelite is very high, and the hydrochloric acid decomposition process is also a traditional process for treating scheelite. However, when hydrochloric acid is decomposed, tungstic acid is coated on the surface of undegraded white tungsten in yellow colloid, which is easy to cause incomplete decomposition, and hydrochloric acidAcid corrosion and volatilization problems are serious, the working environment is bad, and a large amount of residual hydrochloric acid mother liquor is finally neutralized into CaCl by lime 2 The solution is discharged and is basically abandoned at present. Because tungsten can form soluble heteropolyacid with hetero tungsten ratio of 1:6-1:12 with impurities such as phosphorus, arsenic and silicon (such as [ PW) 12 O 40 ] 3- ) A small amount of phosphorus can cause dispersion and loss of a large amount of tungsten in the hydrochloric acid decomposition process, so the hydrochloric acid decomposition process mainly treats high-grade scheelite concentrate (low phosphorus, arsenic and other impurities are required). Compared with hydrochloric acid, nitric acid has lower corrosiveness, and general stainless steel has good corrosion resistance to nitric acid. In recent years, researchers have proposed a technical scheme for decomposing scheelite by nitric acid, but impurities such as phosphorus, arsenic, silicon and the like associated with scheelite still cause a large amount of dispersion loss of tungsten in the decomposing process. In addition, the large amount of calcium nitrate wastewater generated is difficult to treat. The mother liquor of crystallization containing ammonium nitrogen generated in the process of ammonium paratungstate evaporation and crystallization also needs to be treated.
Disclosure of Invention
Aiming at the problems that the recovery rate of W in the conventional scheelite acid leaching is not ideal, calcium-containing leaching solution is difficult to utilize and the like, the first aim of the invention is to provide a method for treating scheelite, which aims at improving the acid leaching efficiency and recovery rate of scheelite and further realizing the full-effect utilization of materials in the treatment process.
The acid leaching treatment of scheelite is a main means for extracting W element, but the enrichment recovery rate of tungsten element in the existing acid leaching treatment is generally not ideal, especially for the scheelite with lower grade and higher impurity content such as P, si, the enrichment recovery rate of tungsten element is not ideal, and in addition, other byproducts in the treatment process are difficult to be effectively utilized, and aiming at the problems, the invention provides the following improvement ideas:
a method for treating scheelite comprises mixing scheelite with acid to provide NH 4 + Acid leaching is assisted by an acid leaching auxiliary agent, and then solid-liquid separation is carried out, thus obtaining acid leaching slag enriched with tungsten and acid leaching slag enriched with calcium and NH 4 + Is prepared from the above-mentioned pickling solution.
According to the invention, the research surprisingly shows that the acid leaching treatment is innovatively carried out under the assistance of the acid leaching auxiliary agent, so that the enrichment recovery rate of tungsten elements in slag can be effectively improved, the leaching efficiency is improved, the subsequent selective purification of tungsten is facilitated, and particularly, for lower-grade scheelite, the acid leaching auxiliary agent-assisted acid leaching method can obtain a better enrichment recovery effect of tungsten elements.
In the invention, the scheelite can be any mineral containing calcium tungstate in industry, and the scheelite is scheelite or black-white tungsten mixed ore in consideration of process efficiency and value; further, the scheelite grade WO 3 More than or equal to 20wt% and associated wolframite WO 3 Less than or equal to 10 weight percent. The technical scheme of the invention has good raw material adaptability to the treated scheelite, and can obtain good acid leaching recovery rate of tungsten, and in addition, when scheelite also exists in the scheelite, the scheelite can be efficiently enriched, and high-quality scheelite concentrate can be further produced as a byproduct.
In the invention, the scheelite grade WO takes the treatment value of the process into consideration 3 Can be 20 to 65wt%.
In the invention, the grade of the scheelite is not particularly required, for example, the total content of P, si and As in the scheelite is more than 0.5wt percent, and the method can be used for carrying out effective acid leaching, but the acid leaching enrichment recovery rate of tungsten can be excellent for the scheelite with relatively low grade (for example, the total content of P, si and As is more than 1 percent, particularly 5 to 10 percent) due to the advantage of the auxiliary acid leaching process, so that the method can obtain higher industrial value.
In the invention, the acid is at least one of nitric acid, hydrochloric acid, acetic acid and methanesulfonic acid, and is preferably nitric acid. According to the invention, the nitric acid is adopted as an acid leaching agent, and the nitric acid and the auxiliary agent can have better synergistic effect, so that better acid leaching enrichment effect can be shown, and the method is beneficial to realizing the high-efficiency recycling of byproducts in the production stage, is beneficial to reducing the output of three wastes and further improves the economy.
In the present invention, the acid leaching stage has an acid concentration of 1M or more, preferably 1 to 10M, and more preferably 3 to 7M. Under the preferable condition, the acid leaching additive can be further combined with the acid leaching additive, so that the acid leaching enrichment rate of tungsten of different grades of scheelite can be further improved.
In the invention, the acid leaching auxiliary agent is at least one of ammonium nitrate, ammonium chloride, ammonium acetate and ammonia water; ammonium nitrate is preferred.
Preferably, the molar ratio of acid to acid leaching aid is greater than or equal to 2, preferably from 3 to 10:1, more preferably 4 to 10:1. Under the preferable condition, the acid leaching additive can be further combined with the acid leaching additive, so that the acid leaching enrichment rate of tungsten of different grades of scheelite can be further improved.
In the present invention, the temperature of the acid leaching stage is not particularly required, for example, the temperature of the acid leaching process is 45 ℃ or higher, preferably 50 to 100 ℃;
preferably, the liquid-solid ratio of the acid leaching stage is 2:1-6:1 (mL/g);
preferably, the acid leaching time is more than 1h, preferably 1-6 h.
In the invention, the acid leaching residue and ammonia water can be mixed for ammonia dissolution treatment to obtain a crude ammonium tungstate solution.
Conditions for ammonia dissolution may be well known. For example, ammonia is 1.0 to 2.0 times the theoretical amount of W in the completely dissolved acid leaching slag;
preferably, the temperature of the ammonolysis process is above 35 ℃, preferably 40-80 ℃;
preferably, the ammonia dissolution time is 1 hour or more, and may be further 1 to 4 hours.
In the present invention, the desired W-containing product can be obtained from a crude ammonium tungstate solution based on known processes. For example, as a typical example, a crude ammonium tungstate solution and a purifying agent may be mixed and purified to obtain a purified ammonium tungstate solution;
in the present invention, as a typical example, magnesium nitrate is used as the impurity removing agent.
In the present invention, as a typical example, ammonium paratungstate is produced from a purified ammonium tungstate solution. The steps are as follows: regulating and controlling the pH value of the purified ammonium tungstate solution to 7.0-8.5 by adopting 15-35 wt% of nitric acid solution, performing crystallization treatment, and then performing solid-liquid separation to obtain ammonium paratungstate crystals and crystallization mother liquor;
preferably, the temperature of the crystallization process is 30-60 ℃, and the time of the crystallization reaction is 2-8 hours.
In the invention, the crystallization mother liquor is used as the acid leaching auxiliary agent and recycled to the acid leaching process. The process can realize high-value recycling of byproducts in the preparation process.
In the present invention, the obtained leachate containing ammonium and calcium can be recycled and used economically by conventional means, and for example, the leachate can be used to prepare a fertilizer. The pickle liquor is absorbed by weak base resin to adsorb tungsten, and then evaporated and granulated to prepare the ammonium nitrate calcium agricultural fertilizer.
A more typical method of treating scheelite according to the present invention comprises the steps of:
step (1):
the method comprises the steps of adopting nitric acid and acid leaching auxiliary ammonium nitrate (such as APT crystallization mother liquor containing ammonium nitrate in the step 2) to cooperatively leach tungsten ore, and then carrying out solid-liquid separation to obtain acid leaching liquid and leaching slag enriched with tungsten components such as tungstic acid;
the concentration of nitric acid is 1-10 mol/L when the tungsten ore is leached, the adding amount of the APT crystallization mother liquor is that the mol ratio of ammonium nitrogen contained in the APT crystallization mother liquor to nitrate nitrogen in the solution is 1:3-1:10, the temperature is above 45 ℃, the preferential temperature is 50-100 ℃, and the liquid-solid ratio is 2:1-6:1 (mL/g);
step (2): leaching residues are dissolved out by ammonia water to obtain an ammonium tungstate solution, and the ammonium tungstate solution is purified to prepare an ammonium paratungstate-APT product;
the dosage of ammonia water is 1.1-2.0 times of theoretical amount when the ammonia water is adopted to dissolve solid tungstic acid, the reaction temperature is above 35 ℃, preferably 40-80 ℃, the reaction time is above 1h, preferably 1-4 h, and crude ammonium tungstate solution is obtained;
adding soluble magnesium nitrate salt into the crude ammonium tungstate solution to generate indissolvable MgKXO 4 Or MgNH 4 XO 4 Precipitation (X is P, as) to obtain purified ammonium tungstate solution;
neutralizing the purified ammonium tungstate solution by using 15-35 wt% of nitric acid solution, controlling the pH value to 7.0-8.5, controlling the crystallization temperature to 30-60 ℃, reacting for 2-8 hours, and filtering after the reaction is finished to obtain an ammonium paratungstate crystal product and a crystal mother solution;
the crystallization mother liquor returns to the step 1 to be used as an acid leaching auxiliary agent;
and (3) adsorbing tungsten by adopting weak base resin in the leaching solution prepared in the step (1), and then evaporating and granulating to prepare the ammonium calcium nitrate agricultural fertilizer.
The invention has the advantages that:
(1) According to the invention, the research has surprisingly found that the acid leaching treatment is innovatively carried out with the aid of the acid leaching auxiliary agent, so that the enrichment recovery rate of the acid leached tungsten element can be effectively improved, the leaching efficiency is improved, and the subsequent selective purification of tungsten and the efficient recycling of byproducts are facilitated. In addition, compared with the prior art, the acid leaching method assisted by the acid leaching auxiliary agent can obtain better enrichment and recovery effects of tungsten element aiming at the scheelite with relatively low grade.
(2) The leaching process can essentially solve the problem of influence on leaching due to solid film wrapping, and realizes the efficient leaching of scheelite; in addition, ca (NO) in the leaching solution and the crystallization mother liquor can be regulated 3 ) 2 With NH 4 NO 3 The ammonium calcium nitrate agricultural fertilizer is prepared by adopting the modes of evaporation concentration and granulation, so that the utilization problem of leachate and crystallization mother liquor is solved, and the discharge amount of wastewater is greatly reduced;
(3) The ammonium calcium nitrate agricultural fertilizer is produced, and the value-added utilization of calcium is realized;
(4) The whole flow treatment equipment is simple, convenient to operate and easy to realize industrialization.
Detailed Description
The following examples are further described in connection with the present invention and are intended to illustrate the invention rather than to limit it.
Example 1
White tungsten concentrate (containing WO) 3 62.4%, P0.2%, si 0.6%, as 0.03%) and 1kg, are placed in a nitric acid solution (2L, wherein the concentration of nitric acid is 6.0mol/L, and the return amount of the crystallization mother liquor is controlled by the nitric acid in the solution and NH in the mother liquor) 4 NO 3 The molar ratio of the content is 10:1), the reaction temperature is 100 ℃, the reaction time is 1h, and the tungsten yield in the acid leaching slag is 99.3The tungsten loss rate in the leaching solution is 0.7 percent. The acid leaching slag is dissolved by adopting ammonia water with the concentration of 25 percent, the dosage of the ammonia water is 1.1 times of the theoretical amount, the reaction temperature is 80 ℃, and water is added after the ammonia dissolution time is 1h to obtain 250g/L of crude ammonium tungstate solution. Adding magnesium nitrate solution into the crude ammonium tungstate solution to remove phosphorus, arsenic, silicon, potassium and other impurities (the ratio of magnesium nitrate to the total molar weight of phosphorus, arsenic, silicon and potassium contained in the solution is 1.1:1), reacting for 1h at room temperature, and filtering. The purified ammonium tungstate solution is subjected to neutralization crystallization to prepare ammonium paratungstate-APT, namely 15wt% of nitric acid solution is used for neutralizing the ammonium tungstate solution to pH 7.0, aging is carried out for 8 hours at 30 ℃, and then APT crystallization product is obtained through filtration, wherein the crystallization rate is 95.2%. The crystallization mother liquor returns to the leaching process and nitric acid to prepare the leaching agent. The leaching solution adopts D301 resin to adsorb tungsten, and the concentration of WO3 in the leaching solution after tungsten adsorption is 0.06g/L. The leaching solution containing calcium nitrate and ammonium nitrate is then evaporated and granulated by adopting conventional technological parameters for preparing the ammonium nitrate calcium agricultural fertilizer to produce the ammonium nitrate calcium agricultural fertilizer.
Example 2
1kg of white tungsten concentrate (same as in example 1) was placed in a nitric acid solution (6L, wherein the concentration of nitric acid was 1.0 mol/L) containing APT crystallization mother liquor, and the return amount of the crystallization mother liquor was controlled by the nitric acid in the solution and NH in the mother liquor 4 NO 3 The molar ratio of the content is 3:1), the reaction temperature is 50 ℃, the reaction time is 6 hours, the yield of tungsten in acid leaching slag is 98.8%, and the loss rate of tungsten in leaching liquid is 1.2%. The acid leaching slag is dissolved by adopting ammonia water with the concentration of 25 percent, the dosage of the ammonia water is 2.0 times of the theoretical amount, the reaction temperature is 40 ℃, and water is added after the ammonia dissolution time is 4 hours to obtain 220g/L crude ammonium tungstate solution. Adding magnesium nitrate solution into the crude ammonium tungstate solution to remove phosphorus, arsenic, silicon, potassium and other impurities (the ratio of magnesium nitrate to the total molar weight of phosphorus, arsenic, silicon and potassium contained in the solution is 1.1:1), reacting for 1h at room temperature, and filtering. The purified ammonium tungstate solution is subjected to neutralization crystallization to prepare ammonium paratungstate-APT, namely 35wt% of nitric acid solution is used for neutralizing the ammonium tungstate solution to pH 8.5, ageing is carried out for 2 hours at 60 ℃, and then the APT crystallization product is obtained through filtration, wherein the crystallization rate is 94.3%. The crystallization mother liquor returns to the leaching process and nitric acid to prepare the leaching agent. The leaching solution adopts D314 resin to adsorb tungsten, and the concentration of WO3 in the leaching solution after tungsten adsorption is 0.07g/L. The leachate containing calcium nitrate and ammonium nitrate is then treated with conventional methodsThe process parameters for preparing the ammonium nitrate calcium agricultural fertilizer are evaporated and granulated to produce the ammonium nitrate calcium agricultural fertilizer.
Example 3
Mixed ore of black and white tungsten (containing WO) 3 46.8%, fe 8.2%, mn 2.1%, P0.7%, si 1.6%, as 0.1%) in a nitric acid solution (5L, wherein the nitric acid concentration is 4.0 mol/L) containing APT crystallization mother liquor, the return amount of the crystallization mother liquor being the control of nitric acid in the solution and NH in the mother liquor 4 NO 3 The molar ratio of the content is 5:1), the reaction temperature is 90 ℃, the reaction time is 4 hours, the yield of tungsten in acid leaching slag is 99.1%, and the loss rate of tungsten in leaching liquid is 0.9%. The acid leaching slag is dissolved by adopting ammonia water with the concentration of 25 percent, the dosage of the ammonia water is 1.5 times of the theoretical amount, the reaction temperature is 60 ℃, water is added after the ammonia dissolution time is 2 hours, 230g/L of crude ammonium tungstate solution is obtained, and the ammonia leaching slag is a high-quality black tungsten concentrate raw material (the WO3 content is 64.3%). Adding magnesium nitrate solution into the crude ammonium tungstate solution to remove phosphorus, arsenic, silicon, potassium and other impurities (the ratio of magnesium nitrate to the total molar weight of phosphorus, arsenic, silicon and potassium contained in the solution is 1.1:1), reacting for 1h at room temperature, and filtering. The purified ammonium tungstate solution is subjected to neutralization crystallization to prepare ammonium paratungstate-APT, namely 25wt% of nitric acid solution is used for neutralizing the ammonium tungstate solution to pH 7.5, aging is carried out for 6 hours at 50 ℃, and then the APT crystal product is obtained through filtration, wherein the crystallization rate is 95.4%. The crystallization mother liquor returns to the leaching process and nitric acid to prepare the leaching agent. The leaching solution adopts D301 resin to adsorb tungsten, and the concentration of WO3 in the leaching solution after tungsten adsorption is 0.05g/L. The leaching solution containing calcium nitrate and ammonium nitrate is then evaporated and granulated by adopting conventional technological parameters for preparing the ammonium nitrate calcium agricultural fertilizer to produce the ammonium nitrate calcium agricultural fertilizer.
Example 4
Low grade scheelite (containing WO) 3 22.7%, P5.4%, si 3.3%, as 0.5%) and 1kg in a nitric acid solution (5L, wherein the nitric acid concentration is 4.0mol/L, and the mother liquor is returned to control the nitric acid in the solution and NH in the mother liquor) 4 NO 3 The molar ratio of the content is 5:1), the reaction temperature is 50 ℃, the reaction time is 6 hours, the yield of tungsten in acid leaching slag is 98.7%, and the loss rate of tungsten in leaching liquid is 1.3%. The acid leaching slag is dissolved by ammonia water with the concentration of 25 percent, the dosage of the ammonia water is 1.5 times of the theoretical amount, and the reaction temperature is 60 DEG CAfter 2 hours of ammonia dissolution time, water is added to obtain 230g/L of crude ammonium tungstate solution. Adding magnesium nitrate solution into the crude ammonium tungstate solution to remove phosphorus, arsenic, silicon, potassium and other impurities (the ratio of magnesium nitrate to the total molar weight of phosphorus, arsenic, silicon and potassium contained in the solution is 1.1:1), reacting for 1h at room temperature, and filtering. The purified ammonium tungstate solution is subjected to neutralization crystallization to prepare ammonium paratungstate-APT, namely 25wt% of nitric acid solution is used for neutralizing the ammonium tungstate solution to pH 7.0, aging is carried out for 5 hours at 50 ℃, and then the ammonium paratungstate-APT crystal product is obtained through filtration, wherein the crystallization rate is 94.1%. The crystallization mother liquor returns to the leaching process and nitric acid to prepare the leaching agent. The leaching solution adopts D301 resin to adsorb tungsten, and the concentration of WO3 in the leaching solution after tungsten adsorption is 0.08g/L. The leaching solution containing calcium nitrate and ammonium nitrate is then evaporated and granulated by adopting conventional technological parameters for preparing the ammonium nitrate calcium agricultural fertilizer to produce the ammonium nitrate calcium agricultural fertilizer.
Comparative example 1
The difference compared with example 1 is that the scheelite leaching process does not add the crystallization mother liquor (ammonium nitrate is not introduced)
White tungsten concentrate (containing WO) 3 62.4%, P0.2%, si 0.6%, as 0.03%) 1kg, and placing in 2L nitric acid solution with concentration of 6.0mol/L, the reaction temperature is 100 ℃, the reaction time is 1h, the tungsten yield in acid leaching slag is 88.6%, and the tungsten loss rate in leaching liquid is 11.4%. The acid leaching slag is dissolved by adopting ammonia water with the concentration of 25 percent, the dosage of the ammonia water is 1.1 times of the theoretical amount, the reaction temperature is 80 ℃, and water is added after the ammonia dissolution time is 1h to obtain 250g/L of crude ammonium tungstate solution. Adding magnesium nitrate solution into the crude ammonium tungstate solution to remove phosphorus, arsenic, silicon, potassium and other impurities (the ratio of magnesium nitrate to the total molar weight of phosphorus, arsenic, silicon and potassium contained in the solution is 1.1:1), reacting for 1h at room temperature, and filtering. The purified ammonium tungstate solution is subjected to neutralization crystallization to prepare ammonium paratungstate-APT, namely 15wt% of nitric acid solution is used for neutralizing the ammonium tungstate solution to pH 7.0, aging is carried out for 8 hours at 30 ℃, and then APT crystallization product is obtained through filtration, wherein the crystallization rate is 95.0%. The leaching solution adopts D301 resin to adsorb tungsten, and the concentration of WO3 in the leaching solution after tungsten adsorption is 0.18g/L. And (3) mixing the calcium nitrate leaching solution and the crystallization mother solution, and then evaporating and granulating by adopting conventional process parameters for preparing the ammonium nitrate calcium agricultural fertilizer to produce the ammonium nitrate calcium agricultural fertilizer.
Compared with example 1, when only nitric acid leaching is adopted, the yield of W in the acid leaching stage is only 88.6%, and in addition, the pressure for recovering tungsten in the subsequent process is increased, and the recovery cost is increased.
Comparative example 2
The difference compared with example 1 is that only nitric acid leaching is adopted for scheelite (the conditions of the leaching process are the same as those of comparative example 1), and the APT crystallization mother liquor described in example 1 is added into the leaching solution after leaching.
White tungsten concentrate (containing WO) 3 62.4%, P0.2%, si 0.6%, as 0.03%) 1kg, and placing in 2L nitric acid solution with concentration of 6.0mol/L, the reaction temperature is 100 ℃, the reaction time is 1h, the tungsten yield in acid leaching slag is 88.6%, and the tungsten loss rate in leaching liquid is 11.4%.
Adding APT crystallization mother liquor into the leaching solution, wherein the adding amount of the crystallization mother liquor is controlled by controlling nitric acid in the solution and NH in the mother liquor 4 NO 3 The molar ratio of the content is 5:1, and the tungsten heteropolyacid ammonium crystals with fine and poor filtering performance are obtained after the reaction for 1h at 25 ℃, and the crystallization rate is 85.6%.
After the tungsten heteropolyacid ammonium crystallization and acid leaching slag are mixed, ammonia water with the concentration of 25% is adopted for dissolution, the dosage of the ammonia water is 1.1 times of the theoretical amount, the reaction temperature is 80 ℃, and water is added after the ammonia dissolution time is 1h, so that 250g/L of crude ammonium tungstate solution is obtained. Adding magnesium nitrate solution into the crude ammonium tungstate solution to remove phosphorus, arsenic, silicon, potassium and other impurities (the ratio of magnesium nitrate to the total molar weight of phosphorus, arsenic, silicon and potassium contained in the solution is 1.1:1), reacting for 1h at room temperature, and filtering. The purified ammonium tungstate solution is subjected to neutralization crystallization to prepare ammonium paratungstate-APT, namely 15wt% of nitric acid solution is used for neutralizing the ammonium tungstate solution to pH 7.0, aging is carried out for 8 hours at 30 ℃, and then the ammonium paratungstate-APT crystal product is obtained through filtration, wherein the crystallization rate is 94.8%. And the leaching solution after the tungsten heteropolyacid is precipitated adopts D301 resin to adsorb tungsten, and the concentration of WO3 in the leaching solution after the tungsten adsorption is 0.16g/L. Evaporating and granulating the solution after tungsten adsorption by adopting conventional technological parameters for preparing the ammonium nitrate calcium agricultural fertilizer to produce the ammonium nitrate calcium agricultural fertilizer.
Compared with the embodiment 1, the leaching process adds two working procedures of adding crystallization mother liquor to precipitate tungsten and filtering, and in the normal temperature tungsten precipitation process, the precipitation rate of tungsten is not high, and the crystallization filtering performance is poor. The process has complicated operation, low recovery rate and increased processing cost.
Compared with the traditional hydrochloric acid and nitric acid process, the process has the following advantages and characteristics:
as above, the process can better improve the acid leaching recovery rate of tungsten, and can well recycle the waste materials in the treatment process, so that the treatment cost and the value are better.
Claims (10)
1. A method for treating scheelite, characterized in that scheelite and acid are used for providing NH 4 + Acid leaching is assisted by an acid leaching auxiliary agent, and then solid-liquid separation is carried out, thus obtaining acid leaching slag enriched with tungsten and acid leaching slag enriched with calcium and NH 4 + Is prepared from the above-mentioned pickling solution.
2. The method for treating scheelite according to claim 1, wherein the scheelite grade WO 3 More than or equal to 20 percent, associated wolframite WO 3 ≤10％。
3. A method of treating scheelite according to claim 1, wherein the acid is at least one of nitric acid, hydrochloric acid, acetic acid, methanesulfonic acid, preferably nitric acid;
preferably, the acid leaching stage has a concentration of 1M or more, preferably 1 to 10M, and more preferably 3 to 7M.
4. The method for treating scheelite according to claim 1, wherein the acid leaching aid is at least one of ammonium nitrate, ammonium chloride, ammonium acetate, aqueous ammonia; preferably ammonium nitrate;
preferably, the molar ratio of acid to acid leaching aid is greater than or equal to 2, preferably from 3 to 10:1, more preferably 4 to 10:1.
5. A method of treating scheelite according to claim 1, wherein the temperature of the acid leaching process is above 45 ℃, preferably 50-100 ℃;
preferably, the liquid-solid ratio of the acid leaching stage is 2:1-6:1 (mL/g);
preferably, the acid leaching time is more than 1h, preferably 1-6 h.
6. The method for treating scheelite according to any one of claims 1 to 5, wherein the acid leaching residue is mixed with aqueous ammonia for ammonolysis treatment to obtain a crude ammonium tungstate solution;
preferably, the ammonia water is 1.1 to 2.0 times of the theoretical amount of W in the completely dissolved acid leaching slag;
preferably, the temperature of the ammonolysis process is above 35 ℃, preferably 40-80 ℃;
preferably, the ammonia dissolution time is 1h or more, preferably 1 to 4h.
7. The method for treating scheelite according to claim 6, wherein the crude ammonium tungstate solution is mixed with a impurity removing agent for purification treatment to obtain a purified ammonium tungstate solution;
preferably, the impurity removing agent is magnesium nitrate.
8. The method of treating scheelite according to claim 7, wherein the purified ammonium tungstate solution is used to prepare ammonium paratungstate;
preferably, adjusting and controlling the pH value of the purified ammonium tungstate solution to 7.0-8.5 by adopting 15-35 wt% of nitric acid solution, performing crystallization treatment, and then performing solid-liquid separation to obtain ammonium paratungstate crystals and crystallization mother liquor;
preferably, the temperature of the crystallization process is 30-60 ℃, and the time of the crystallization reaction is 2-8 hours.
9. The method for treating scheelite according to claim 8, wherein the mother liquor for crystallization is used as the acid leaching aid, and recycled to the acid leaching process.
10. The method for treating scheelite according to any one of claims 1 to 9, wherein the acid leaching solution is evaporated and granulated after adsorbing tungsten with a weak base resin to prepare the ammonium calcium nitrate agricultural fertilizer.
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