CN112941343A - Method for recovering tungsten from heteropoly acid slag containing silicon and tungsten - Google Patents
Method for recovering tungsten from heteropoly acid slag containing silicon and tungsten Download PDFInfo
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- CN112941343A CN112941343A CN202110126943.9A CN202110126943A CN112941343A CN 112941343 A CN112941343 A CN 112941343A CN 202110126943 A CN202110126943 A CN 202110126943A CN 112941343 A CN112941343 A CN 112941343A
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- tungsten
- heteropoly acid
- auxiliary material
- acid residues
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- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 title claims abstract description 90
- 229910052721 tungsten Inorganic materials 0.000 title claims abstract description 89
- 239000010937 tungsten Substances 0.000 title claims abstract description 89
- 239000011964 heteropoly acid Substances 0.000 title claims abstract description 52
- 238000000034 method Methods 0.000 title claims abstract description 51
- 229910052710 silicon Inorganic materials 0.000 title claims abstract description 23
- 239000010703 silicon Substances 0.000 title claims abstract description 23
- 239000002893 slag Substances 0.000 title description 20
- 239000000463 material Substances 0.000 claims abstract description 61
- 238000009835 boiling Methods 0.000 claims abstract description 36
- 239000000706 filtrate Substances 0.000 claims abstract description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 20
- 238000002156 mixing Methods 0.000 claims abstract description 14
- 238000000498 ball milling Methods 0.000 claims abstract description 13
- 238000001914 filtration Methods 0.000 claims abstract description 11
- CGFYHILWFSGVJS-UHFFFAOYSA-N silicic acid;trioxotungsten Chemical compound O[Si](O)(O)O.O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1.O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1.O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1.O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1 CGFYHILWFSGVJS-UHFFFAOYSA-N 0.000 claims abstract description 11
- 238000005406 washing Methods 0.000 claims abstract description 8
- 230000007935 neutral effect Effects 0.000 claims abstract description 6
- 238000003825 pressing Methods 0.000 claims abstract description 5
- PUZPDOWCWNUUKD-UHFFFAOYSA-M sodium fluoride Chemical compound [F-].[Na+] PUZPDOWCWNUUKD-UHFFFAOYSA-M 0.000 claims description 10
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 9
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 6
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 6
- 239000002002 slurry Substances 0.000 claims description 6
- 239000007788 liquid Substances 0.000 claims description 5
- 239000011775 sodium fluoride Substances 0.000 claims description 5
- 235000013024 sodium fluoride Nutrition 0.000 claims description 5
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 4
- 229910017604 nitric acid Inorganic materials 0.000 claims description 4
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 claims description 3
- 239000000920 calcium hydroxide Substances 0.000 claims description 3
- 229910001861 calcium hydroxide Inorganic materials 0.000 claims description 3
- 239000011780 sodium chloride Substances 0.000 claims description 3
- 229910052979 sodium sulfide Inorganic materials 0.000 claims description 3
- GRVFOGOEDUUMBP-UHFFFAOYSA-N sodium sulfide (anhydrous) Chemical compound [Na+].[Na+].[S-2] GRVFOGOEDUUMBP-UHFFFAOYSA-N 0.000 claims description 3
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims 2
- 235000017557 sodium bicarbonate Nutrition 0.000 claims 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 claims 1
- 238000000605 extraction Methods 0.000 abstract description 3
- 238000004090 dissolution Methods 0.000 description 14
- 238000006243 chemical reaction Methods 0.000 description 9
- 230000000694 effects Effects 0.000 description 6
- 238000010411 cooking Methods 0.000 description 5
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 4
- 239000002253 acid Substances 0.000 description 4
- 239000011575 calcium Substances 0.000 description 4
- 229910052791 calcium Inorganic materials 0.000 description 4
- 239000013078 crystal Substances 0.000 description 4
- 238000011084 recovery Methods 0.000 description 4
- 239000013049 sediment Substances 0.000 description 4
- PBYZMCDFOULPGH-UHFFFAOYSA-N tungstate Chemical compound [O-][W]([O-])(=O)=O PBYZMCDFOULPGH-UHFFFAOYSA-N 0.000 description 4
- 239000012535 impurity Substances 0.000 description 3
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 2
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 description 2
- 229910000831 Steel Inorganic materials 0.000 description 2
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 description 2
- 239000008139 complexing agent Substances 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- 239000008187 granular material Substances 0.000 description 2
- 238000002386 leaching Methods 0.000 description 2
- 239000012452 mother liquor Substances 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 239000011574 phosphorus Substances 0.000 description 2
- 229910052698 phosphorus Inorganic materials 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 239000010959 steel Substances 0.000 description 2
- CMPGARWFYBADJI-UHFFFAOYSA-L tungstic acid Chemical compound O[W](O)(=O)=O CMPGARWFYBADJI-UHFFFAOYSA-L 0.000 description 2
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonium chloride Substances [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000005325 percolation Methods 0.000 description 1
- 239000012716 precipitator Substances 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000000638 solvent extraction Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 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
- 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
- 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
- C22B7/04—Working-up slag
-
- 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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- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Environmental & Geological Engineering (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Geology (AREA)
- Processing Of Solid Wastes (AREA)
Abstract
The invention discloses a method for recovering tungsten from heteropoly acid residues containing silicon and tungsten, which comprises the following steps: (1) carrying out size mixing, filter pressing and water washing on heteropoly acid residues containing silicon and tungsten by using hot water until the heteropoly acid residues are neutral so as to leach out partial tungsten, and obtaining a first filtrate and a first filter residue; (2) ball-milling the first filter residue, adding a first auxiliary material and a second auxiliary material, boiling for the first time, and filtering to obtain a second filtrate and a second filter residue; and (3) adding a third auxiliary material into the second filter residue, performing second boiling and filtering to obtain a third filtrate and tailings. The method can effectively solve the problem of recovering tungsten from the heteropoly acid residues containing silicotungstic acid, so that the tungsten in the heteropoly acid containing silicotungstic acid precipitated in the extraction process can be timely recovered and returned to the process for use, and the tungsten loss is effectively reduced. The method has simple process, easy implementation and low cost.
Description
Technical Field
The invention belongs to the field of chemical industry, and particularly relates to a method for recovering tungsten from heteropoly acid residues containing silicon and tungsten.
Background
At present, tungsten mainly exists in a solution through phosphotungstic heteropoly acid and silicotungstic heteropoly acid in an acid leaching process, a process developer mainly cools and crystallizes the phosphotungstic heteropoly acid in an earlier stage, mother liquor is extracted to separate phosphorus and molybdenum, recovered phosphorus can return to a process, and ammonium tungstate solution obtained after the phosphotungstic heteropoly acid is crystallized through ammonia solution directly enters for evaporation. But in the actual production, the problems that impurity elements are difficult to control in the crystallization separation process, the requirement for crystallization residual acid is high and the like are found. The prior art is improved again, the specific organic solvent extraction and impurity removal of the phosphotungstic heteropoly acid is improved, the method has good impurity removal effect and is simple to control, but in order to protect the organic solvent, the extraction process cannot be heated, so the temperature of feed liquid can be reduced, the silicotungstic heteropoly acid and calcium sulfate are separated out in a crystal form and form complex mixed slag with part of tail slag of the percolation, and the tungsten loss is caused, so a feasible method for recovering tungsten in the slag is urgently needed to return to the process, and the prior method for recovering tungsten from the heteropoly acid slag containing silicotungstic heteropoly acid does not form a targeted method.
Disclosure of Invention
The present invention is directed to solving, at least to some extent, one of the technical problems in the related art. Therefore, one purpose of the invention is to provide a method for recovering tungsten from heteropoly acid residues containing silicotungsten, which can effectively solve the problem of recovering tungsten from heteropoly acid residues containing silicotungsten, and further timely recover tungsten in heteropoly acid of silicotungsten precipitated in the extraction process and return the heteropoly acid to the process for use, thereby effectively reducing the loss of tungsten. The method has simple process, easy implementation and low cost.
According to one aspect of the invention, the invention provides a method for recovering tungsten from heteropoly acid residues containing silicon and tungsten, which comprises the following steps:
(1) carrying out size mixing, filter pressing and water washing on heteropoly acid residues containing silicon and tungsten by using hot water until the heteropoly acid residues are neutral so as to leach out partial tungsten, and obtaining a first filtrate and a first filter residue;
(2) ball-milling the first filter residue, adding a first auxiliary material and a second auxiliary material, boiling for the first time, and filtering to obtain a second filtrate and a second filter residue;
(3) and adding a third auxiliary material into the second filter residue, boiling for the second time, and filtering to obtain a third filtrate and tailings.
According to the method for recovering tungsten from the heteropoly acid residues containing silicotungstic acid, provided by the embodiment of the invention, the heteropoly acid residues containing silicotungstic acid are subjected to size mixing and water washing by using hot water, so that the temperature can be increased, the acidity can be reduced, part of heteropoly silicotungstic acid is crystallized to become heteropoly acid solution of silicotungstic acid, and meanwhile, the acid is washed cleanly, so that the subsequent protection of a ball mill is facilitated. Further ball-milling the filter residue, can make the great sediment of granule attenuate, increase the surface area with the contact of supplementary material, and then improve the reaction efficiency of first boiling in-process and supplementary material and sediment. And finally, after the first boiling, the rest tungsten exists basically in the form of calcium tungstate, and a certain pH condition can be controlled by adding a third auxiliary material to convert the calcium tungstate into certain tungstic acid for dissolution. Therefore, the method of the embodiment of the invention has high tungsten dissolution rate and high recovery rate, and the tungsten content in the final tailings can be reduced to about 0.7%.
In addition, the method for recovering tungsten from heteropoly acid residues containing silicon and tungsten according to the embodiment of the invention can also have the following additional technical characteristics:
in some embodiments of the invention, in the step (1), the solid-liquid ratio of the slurry mixing is 1:2, the slurry mixing temperature is 90-100 ℃, and the temperature is kept for 1 h.
In some embodiments of the invention, in step (2), the filter residue is ball milled to no greater than 200 mesh.
In some embodiments of the present invention, the first auxiliary material is at least one selected from the group consisting of sodium fluoride, sodium chloride, and sodium sulfide, and the second auxiliary material is at least one selected from the group consisting of nitric acid, hydrochloric acid, and hydrofluoric acid.
In some embodiments of the invention, in step (2), the temperature of the first cooking is 90-100 degrees celsius for 2 hours.
In some embodiments of the present invention, step (2) further comprises: and adding part of the first auxiliary material in the ball milling process.
In some embodiments of the present invention, the third auxiliary material is at least one selected from the group consisting of sodium hydroxide, sodium bicarbonate, and calcium hydroxide.
In some embodiments of the invention, the mass ratio of the third auxiliary material to the second filter residue is 1: 1.
In some embodiments of the invention, in step (3), the temperature of the second cooking is 90-100 degrees celsius for 2 hours.
Detailed Description
The following detailed description of embodiments of the invention is intended to be illustrative, and is not to be construed as limiting the invention.
According to one aspect of the invention, the invention provides a method for recovering tungsten from heteropoly acid residues containing silicon and tungsten, which comprises the following steps:
(1) carrying out size mixing, filter pressing and water washing on heteropoly acid residues containing silicon and tungsten by using hot water until the heteropoly acid residues are neutral so as to leach out partial tungsten, and obtaining a first filtrate and a first filter residue;
(2) ball-milling the first filter residue, adding a first auxiliary material and a second auxiliary material, boiling for the first time, and filtering to obtain a second filtrate and a second filter residue;
(3) and adding a third auxiliary material into the second filter residue, boiling for the second time, and filtering to obtain a third filtrate and tailings.
According to the method for recovering tungsten from the heteropoly acid residues containing silicotungstic acid, provided by the embodiment of the invention, the heteropoly acid residues containing silicotungstic acid are subjected to size mixing and water washing by using hot water, so that the temperature can be increased, part of heteropoly silicotungstic acid can be crystallized to become heteropoly acid solution of silicotungstic acid, and meanwhile, the acid is washed cleanly, the acidity is reduced, and the subsequent protection of a ball mill is facilitated. Further ball-milling the filter residue, can make the great sediment of granule attenuate, increase the surface area with the contact of supplementary material, and then improve the reaction efficiency of first boiling in-process and supplementary material and sediment. And finally, after the first boiling, the rest tungsten exists basically in the form of calcium tungstate, and a certain pH condition can be controlled by adding a third auxiliary material to convert the calcium tungstate into certain tungstic acid for dissolution. Therefore, the method of the embodiment of the invention has high tungsten dissolution rate and high recovery rate, and the tungsten content in the final tailings can be reduced to about 0.7%.
The method for recovering tungsten from heteropoly acid residues containing silicon and tungsten according to the embodiment of the invention is described in detail below.
According to the specific embodiment of the invention, the heteropoly-acid residues containing silicon and tungsten are firstly mixed with hot water, washed to be neutral and filter-pressed so as to leach part of tungsten, and a first filtrate and a first filter residue are obtained.
According to the specific embodiment of the invention, in the step, hot water is used for size mixing, so that part of the silicotungstic heteropoly acid crystals can be dissolved out from the slag after being heated. Specifically, the temperature of hot water size mixing is 90-100 ℃, and the temperature is kept for 1 h. But also can further improve the dissolution rate of the silicotungstic heteropoly acid crystals.
According to a specific example of the invention, in the step, the solid-to-liquid ratio after the slurry mixing is 1:2, so that the silicotungstic heteropoly acid crystals are dissolved out from the slag after being heated, and the washing effect of the subsequent slag is facilitated. Finally, the slag amount of the heteropoly acid slag containing silicon and tungsten can be reduced by about 40 percent through the treatment of the step, and the dissolution rate of tungsten can reach about 58 percent.
According to the specific embodiment of the invention, secondly, the first filter residue is ball-milled, and then the first auxiliary material and the second auxiliary material are added for first boiling and filtering, so as to obtain a second filtrate and a second filter residue.
According to the specific embodiment of the invention, in this step, the first filter residue is ball-milled, so that the filter residue with larger particles becomes thinner, and the contact area between the filter residue and the auxiliary material is further increased, and specifically, the filter residue can be ball-milled to be not more than 200 meshes. Therefore, the reaction efficiency with the auxiliary materials and the slag in the first boiling process can be further improved.
According to an embodiment of the present invention, the first auxiliary material is at least one selected from the group consisting of sodium fluoride, sodium chloride, and sodium sulfide. Thus, the tungsten can be effectively eluted by adding the tungsten eluting agent. In addition, the adding amount of the first auxiliary material is based on that the rest amount of the first auxiliary material in the solution after the first cooking reaction is finished is 40-60 g/l.
According to a specific embodiment of the present invention, the second auxiliary material is a tungsten complexing agent, specifically at least one selected from nitric acid, hydrochloric acid, and hydrofluoric acid. Therefore, the dissolved tungsten can be stably existed in the solution by adding the tungsten complexing agent, and the tungsten dissolving effect is ensured. In addition, the adding amount of the second auxiliary material is based on the 2-5g/l of the rest of the second auxiliary material after the reaction in the solution.
According to the specific embodiment of the invention, in the step, the temperature for adding the first auxiliary material and the second auxiliary material to carry out the first cooking is 90-100 ℃ and the time is 2 hours. Whereby the dissolution rate of tungsten can be further improved. The first cook is preferably performed at 95 degrees celsius.
According to the specific embodiment of the present invention, the inventors found that a part of the first auxiliary material is previously added during the ball milling of the first residue. The ball mill steel ball guiding and protecting device can play a guiding and protecting role on a ball mill steel ball, meanwhile, part of first auxiliary materials are added in advance, and the fact that part of the first auxiliary materials and filter residues react in advance in the ball mill can be achieved, so that the reaction period of the first boiling process is saved. In addition, the inventor finds that the first auxiliary material and the second auxiliary material have to be kept at high temperature to have good reaction effect on the slag when acting simultaneously, and the temperature cannot be reached during ball milling, so that the second auxiliary material is not suitable for being added in advance simultaneously with the first auxiliary material, and in addition, the second auxiliary material is corrosive, so that the second auxiliary material is harmful to the ball milling after being added and is not suitable for being added in advance.
According to a specific example of the present invention, in the first boiling step, the dissolution rate of tungsten may reach about 80%.
According to a specific embodiment of the present invention, finally, in order to recover tungsten more deeply, the second residue remaining after the first boiling is subjected to a second boiling treatment, specifically, a third auxiliary material is added to the second residue, and the second residue is subjected to a second boiling and then filtered, so as to obtain a third filtrate and tailings.
According to a specific embodiment of the present invention, the third auxiliary material is at least one selected from the group consisting of sodium hydroxide, sodium bicarbonate, and calcium hydroxide. Whereby the soluble but difficult to wash part of the tungsten can be boiled out efficiently. In addition, the addition amount of the third auxiliary material is controlled so that the pH is controlled to be 9 after the addition. Thereby not only ensuring the dissolution effect, but also saving the consumption of the auxiliary materials.
According to the specific embodiment of the invention, the mass ratio of the third auxiliary material to the second filter residue is 1: 1. Further, the pH can be ensured to be in a proper range. Specifically, in this step, the pH is preferably controlled to 9, and the recovery rate of tungsten can be further improved.
According to the specific embodiment of the invention, in the step (3), the temperature of the second cooking is 90-100 ℃ and the time is 2 hours. Preferably, the temperature may be 95 degrees celsius. According to the embodiment of the invention, the second boiling can reach about 93% dissolution rate and the tungsten content in the slag can be reduced to about 0.7% based on the first boiling.
According to the specific embodiment of the invention, the concentration of tungsten in the third filtrate obtained in the step is low, so that the third filtrate can be recycled as the mother liquor of the next slag boiling, and the tungsten is circularly enriched to a certain concentration and then precipitated to be artificial white tungsten for back leaching, so that the consumption of a third auxiliary material and a tungsten precipitator is greatly reduced.
Therefore, by adopting the method of the embodiment of the invention, 99% of tungsten in the heteropoly acid residues containing silicon and tungsten can be effectively recovered, the recovered tungsten can be returned to the process in time, the recovery effect is good, and the feasibility is high.
Examples
(1) Mixing the heteropoly acid residues containing silicon and tungsten with hot water to obtain slurry (solid-to-liquid ratio is 1:2, temperature is about 95 ℃, and heat preservation is carried out for 1h), carrying out filter pressing, and washing with water to be neutral so as to leach out partial tungsten to obtain a first filtrate and a first filter residue;
(2) and ball-milling the first filter residue until the first filter residue completely passes through a 200-mesh screen, adding part of a first auxiliary material (sodium fluoride) in the ball-milling process, then adding the rest of the first auxiliary material (sodium fluoride) and a second auxiliary material (nitric acid) for first boiling, wherein the adding amount of the first auxiliary material is based on the concentration of the rest of the first auxiliary material in the solution after the reaction within the range of 40-60g/l, and the adding amount of the second auxiliary material is based on the concentration of the rest of the second auxiliary material in the solution after the reaction within the range of 2-5 g/l. The temperature of the first boiling is 95 ℃; the reaction time is 2 hours, and the second filtrate and the second filter residue are obtained by filtering;
(3) and adding a third auxiliary material with the mass ratio of 1:1 into the second filter residue, performing second boiling and filtering, wherein the temperature of the second boiling is 95 ℃, and the reaction time is 2 hours, so as to obtain a third filtrate and tailings.
The method is repeatedly executed for 20 times according to the embodiment method, and the tungsten content in the raw slag in each specific experiment, the tungsten content in the slag in the water boiling process, the first boiling process and the second boiling process, the residual slag amount and the dissolution rate are recorded for measurement, and the results are shown in table 1.
TABLE 1
And (4) conclusion: statistics of the examples 1 to 202 show that the slag amount is reduced by about 40% after water boiling, and the tungsten dissolution rate can reach about 58%; the tungsten dissolution rate reaches about 80 percent based on water boiling during the first boiling. The second boiling is based on the first boiling, the dissolution rate can reach about 93 percent, and the tungsten content in the slag can be reduced to about 0.7 percent.
In the description herein, references to the description of the term "one embodiment," "some embodiments," "an example," "a specific example," or "some examples," etc., mean that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the invention. In this specification, the schematic representations of the terms used above are not necessarily intended to refer to the same embodiment or example. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples. Furthermore, various embodiments or examples and features of different embodiments or examples described in this specification can be combined and combined by one skilled in the art without contradiction.
Although embodiments of the present invention have been shown and described above, it is understood that the above embodiments are exemplary and should not be construed as limiting the present invention, and that variations, modifications, substitutions and alterations can be made to the above embodiments by those of ordinary skill in the art within the scope of the present invention.
Claims (9)
1. A method for recovering tungsten from heteropoly acid residues containing silicon and tungsten is characterized by comprising the following steps:
(1) carrying out size mixing, filter pressing and water washing on heteropoly acid residues containing silicon and tungsten by using hot water until the heteropoly acid residues are neutral so as to leach out partial tungsten, and obtaining a first filtrate and a first filter residue;
(2) ball-milling the first filter residue, adding a first auxiliary material and a second auxiliary material, boiling for the first time, and filtering to obtain a second filtrate and a second filter residue; and
(3) and adding a third auxiliary material into the second filter residue, boiling for the second time, and filtering to obtain a third filtrate and tailings.
2. The method for recovering tungsten from heteropoly acid residues containing silicon and tungsten as claimed in claim 1, wherein in the step (1), the solid-to-liquid ratio of the slurry mixing is 1:2, the slurry mixing temperature is 90-100 ℃, and the temperature is kept for 1 h.
3. The method for recovering tungsten from heteropoly acid residues containing silicon and tungsten as claimed in claim 1, wherein in the step (2), the filter residues are ball-milled to be not more than 200 meshes.
4. The method for recovering tungsten from heteropoly acid residues containing silicotungsten as claimed in claim 1, wherein the first auxiliary material is at least one selected from sodium fluoride, sodium chloride and sodium sulfide; the second auxiliary material is at least one selected from nitric acid, hydrochloric acid and hydrofluoric acid.
5. The method for recovering tungsten from heteropoly acid residues containing silicon and tungsten as claimed in claim 1, wherein in the step (2), the temperature of the first boiling is 90-100 ℃ and the time is 2 hours.
6. The method for recovering tungsten from heteropoly acid residues containing silicon and tungsten as claimed in claim 1, wherein the step (2) further comprises: and adding part of the first auxiliary material in the ball milling process.
7. The method for recovering tungsten from heteropoly acid residues containing silicotungstic acid according to claim 1, characterized in that the third auxiliary material is at least one selected from sodium hydroxide, sodium bicarbonate and calcium hydroxide.
8. The method for recovering tungsten from heteropoly acid residues containing silicon and tungsten as claimed in claim 1, wherein the mass ratio of the third auxiliary material to the second filter residue is 1: 1.
9. The method for recovering tungsten from heteropoly acid residues containing silicon and tungsten as claimed in claim 1, wherein in the step (3), the temperature of the second boiling is 90-100 ℃ and the time is 2 hours.
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