CN108642308B - Method for decomposing high-tin tungsten ore under pressure by using sulfur-phosphorus mixed acid - Google Patents
Method for decomposing high-tin tungsten ore under pressure by using sulfur-phosphorus mixed acid Download PDFInfo
- Publication number
- CN108642308B CN108642308B CN201810332892.3A CN201810332892A CN108642308B CN 108642308 B CN108642308 B CN 108642308B CN 201810332892 A CN201810332892 A CN 201810332892A CN 108642308 B CN108642308 B CN 108642308B
- Authority
- CN
- China
- Prior art keywords
- tin
- wolframite
- mixed
- tungsten
- acid
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 title claims abstract description 81
- 229910052721 tungsten Inorganic materials 0.000 title claims abstract description 80
- 239000010937 tungsten Substances 0.000 title claims abstract description 80
- 238000000034 method Methods 0.000 title claims abstract description 44
- 239000002253 acid Substances 0.000 title claims abstract description 32
- QCJQWJKKTGJDCM-UHFFFAOYSA-N [P].[S] Chemical compound [P].[S] QCJQWJKKTGJDCM-UHFFFAOYSA-N 0.000 title description 3
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims abstract description 93
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 92
- ZXOKVTWPEIAYAB-UHFFFAOYSA-N dioxido(oxo)tungsten Chemical compound [O-][W]([O-])=O ZXOKVTWPEIAYAB-UHFFFAOYSA-N 0.000 claims abstract description 89
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims abstract description 50
- 238000006243 chemical reaction Methods 0.000 claims abstract description 47
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims abstract description 45
- 238000000605 extraction Methods 0.000 claims abstract description 15
- 230000008569 process Effects 0.000 claims abstract description 14
- 239000002994 raw material Substances 0.000 claims description 26
- 239000000706 filtrate Substances 0.000 claims description 21
- 239000002245 particle Substances 0.000 claims description 7
- 239000000203 mixture Substances 0.000 claims description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 2
- 150000002148 esters Chemical class 0.000 claims description 2
- 150000001412 amines Chemical class 0.000 claims 1
- 238000000354 decomposition reaction Methods 0.000 abstract description 20
- 239000012141 concentrate Substances 0.000 abstract description 12
- 239000002893 slag Substances 0.000 abstract description 9
- 238000004519 manufacturing process Methods 0.000 abstract description 5
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 abstract description 4
- 239000011575 calcium Substances 0.000 abstract description 4
- 229910052791 calcium Inorganic materials 0.000 abstract description 4
- 150000001875 compounds Chemical class 0.000 abstract description 4
- 229910052718 tin Inorganic materials 0.000 description 75
- 239000000843 powder Substances 0.000 description 14
- 239000003350 kerosene Substances 0.000 description 12
- 229910052500 inorganic mineral Inorganic materials 0.000 description 11
- 239000011707 mineral Substances 0.000 description 11
- 238000002386 leaching Methods 0.000 description 10
- 238000004364 calculation method Methods 0.000 description 6
- 238000001816 cooling Methods 0.000 description 6
- 238000001914 filtration Methods 0.000 description 6
- 238000002156 mixing Methods 0.000 description 6
- SJWFXCIHNDVPSH-UHFFFAOYSA-N octan-2-ol Chemical compound CCCCCCC(C)O SJWFXCIHNDVPSH-UHFFFAOYSA-N 0.000 description 6
- 239000012074 organic phase Substances 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- 230000001502 supplementing effect Effects 0.000 description 6
- KBPLFHHGFOOTCA-UHFFFAOYSA-N 1-Octanol Chemical group CCCCCCCCO KBPLFHHGFOOTCA-UHFFFAOYSA-N 0.000 description 4
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 4
- AWXLLPFZAKTUCQ-UHFFFAOYSA-N [Sn].[W] Chemical compound [Sn].[W] AWXLLPFZAKTUCQ-UHFFFAOYSA-N 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- 238000003723 Smelting Methods 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000002920 hazardous waste Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- YXJYBPXSEKMEEJ-UHFFFAOYSA-N phosphoric acid;sulfuric acid Chemical compound OP(O)(O)=O.OS(O)(=O)=O YXJYBPXSEKMEEJ-UHFFFAOYSA-N 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 239000011593 sulfur Substances 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 238000000498 ball milling Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- 239000008139 complexing agent Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 229910052602 gypsum Inorganic materials 0.000 description 1
- 239000010440 gypsum Substances 0.000 description 1
- 238000009854 hydrometallurgy Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- OTYNBGDFCPCPOU-UHFFFAOYSA-N phosphane sulfane Chemical compound S.P[H] OTYNBGDFCPCPOU-UHFFFAOYSA-N 0.000 description 1
- 150000003017 phosphorus Chemical class 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 230000036632 reaction speed Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 230000009466 transformation Effects 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
- C22B25/00—Obtaining tin
- C22B25/04—Obtaining tin by 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
- 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
-
- 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
Landscapes
- 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)
- Manufacture And Refinement Of Metals (AREA)
Abstract
The invention relates to a method for pressure decomposition of high-tin tungsten ore by mixed phosphoric and sulfuric acid, which is improved in that in the process of extracting tungsten from high-tin wolframite or mixed ore of high-tin wolframite and white wolframite by mixed acid of phosphoric acid and sulfuric acid, a reaction system is subjected to pressure treatment, and the temperature of the reaction system is 110-250 ℃. The decomposed slag after extracting tungsten can be directly used or can be subjected to a beneficiation procedure to obtain tin concentrate. According to the method, tungsten in the wolframite or the wolframite-wolframite mixed ore can be directly extracted by pressurizing without additionally adding a calcium-containing compound to convert the wolframite in the tungsten extraction process, and meanwhile, tin concentrate is obtained, so that the production process is simplified, and the production cost is reduced.
Description
Technical Field
The invention belongs to the field of hydrometallurgy and relates to extraction of metal tungsten, in particular to a method for decomposing high-tin tungsten ore by pressurization.
Background
In China, the tungsten ore containing tin is an important tungsten ore resource and also contains high-value tin. Generally, tin is associated with wolframite or wolframite mixture in the form of cassiterite. The traditional beneficiation and tungsten smelting methods cannot efficiently separate and recover tin in the tungsten ore. Chinese patent inventions 201010605095.1, 201010605107.0, 201010605103.2, 201010605110.2 and 201010605094.7 propose a novel method for decomposing tungsten ore by adopting sulfuric acid-phosphoric acid, efficiently realize the decomposition of scheelite and provide a brand new smelting process for the scheelite. However, when the wolframite and the wolframite mixed ore are directly leached by adopting the sulfuric acid-phosphoric acid synergistic decomposition technology, the leaching rate of the tungsten is difficult to achieve the decomposition effect of the scheelite. This is mainly due to wolframite (Fe/MnWO)4) The structure is compared with that of scheelite (CaWO)4) More stable and difficult to be directly decomposed by acid even if phosphoric acid is used as a strong complexing agent of tungstate radical. For this reason, chinese patents 201510243382.5, 201510241154.4, 201510242275.0 and 201710313207.8 propose various methods for decomposing wolframite or wolframite by mixed sulfur and phosphorus acids. In these patents, some processes convert wolframite into scheelite by mechanical ball milling by adding a calcium-containing compound to the wolframite or mixed wolframite and scheelite oreThere is also a method of converting wolframite into scheelite by adding a calcium-containing compound to the wolframite or the mixed wolframite and scheelite to be burned or smelted at a high temperature, and recovering tin by volatilizing it by blowing. After the transformation by the measures, the mixed acid of sulfur and phosphorus is added to decompose the wolframite or the mixed wolframite and scheelite. From the reported data, the measures can actually and effectively promote the decomposition of the wolframite or the wolframite and wolframite mixed ore.
However, the measures taken in the above patents undoubtedly increase the tungsten ore treatment process and production equipment, and also increase the tungsten ore decomposition cost. Therefore, it is necessary to develop a new technology for directly decomposing wolframite or wolframite mixed ore by mixed sulfuric-phosphoric acid to facilitate the recovery of tungsten and tin.
The sulfur-phosphorus mixed acid has several advantages in the treatment of scheelite: the first is that the decomposition rate of tungsten ore is high; secondly, no hazardous waste decomposition slag is generated; thirdly, the low-cost sulfuric acid is adopted for decomposition, so that the decomposition cost is low; and fourthly, the decomposition can be realized only under the normal pressure condition. The subject group has been based on the advantages of decomposing tungsten ores including wolframite and wolframite-wolframite mixture. However, when the mineral containing wolframium nigrum is decomposed, the mineral cannot be directly decomposed.
Disclosure of Invention
The invention aims to provide a method for decomposing high-tin tungsten ore under pressure by using mixed phosphoric and sulfuric acid, which is mainly improved in that the temperature of a reaction system is increased to 110-250 ℃ by pressurizing in the process of extracting tungsten from the high-tin wolframite or the mixed ore of high-tin wolframite and white wolframite by using the mixed acid of phosphoric acid and sulfuric acid.
According to the method, the tungsten in the wolframite or the wolframite and wolframite mixed ore can be directly extracted through the phosphorus-sulfur method under the condition that no calcified substance is added through pressurizing the system, no additional treatment process is needed, the tin concentrate can be obtained from the decomposition slag directly or through a concentrating process, the operation is simplified, and the decomposition of the wolframite and the recovery cost of the tin are reduced.
Preferably, the WO in the high-tin wolframite or the high-tin wolframite-black-white mixed ore3The grade of (A) is 10-70%.
Preferably, the grade of tin in the high-tin wolframite or the high-tin wolframite mixture is 0.5-20%.
Preferably, in the mixed acid, the concentration of phosphoric acid is 20-250 g/L;
preferably, the raw material is the high-tin wolframite, the concentration of phosphoric acid is 60-200 g/L, and the raw material is the mixed ore of the high-tin wolframite and the high-tin wolframite, the concentration of the phosphoric acid is 30-160 g/L;
preferably, the concentration of the phosphoric acid is 120-175 g/L when the raw material is the high-tin wolframite, and the concentration of the phosphoric acid is 100-160 g/L when the raw material is the mixed ore of the high-tin wolframite and the white wolframite;
preferably, the concentration of sulfuric acid in the mixed acid is 50-500 g/L;
preferably, the raw material is the high-tin wolframite, the concentration of sulfuric acid is 100-250 g/L, and the raw material is the mixed ore of the high-tin wolframite and the white wolframite, the concentration of the sulfuric acid is 60-220 g/L;
preferably, the raw material is the high-tin wolframite, the concentration of sulfuric acid is 180-240 g/L, and the raw material is the mixed ore of the high-tin wolframite and the white wolframite, the concentration of the sulfuric acid is 180-200 g/L;
preferably, the raw material is the high-tin wolframite, the temperature of the reaction system is 130-230 ℃, and the raw material is the mixed ore of the high-tin wolframite and the high-tin wolframite, and the temperature of the reaction system is 120-200 ℃.
Further preferably, the raw material is the high-tin wolframite, the temperature of the reaction system is 200-230 ℃, and the raw material is the mixed ore of the high-tin wolframite and the white wolframite, and the temperature of the reaction system is 150-200 ℃.
Preferably, the raw material is the wolframite, the pressure of the reaction system is 0.54-3.0 Mpa, and the raw material is the mixed ore of the wolframite and the scheelite, the pressure of the reaction system is 0.21-1.85 Mpa.
Preferably, the mass volume ratio of the high-tin gold wolframite or the high-tin black scheelite mixed ore to the mixed acid is 1: 3-10.
Preferably, the grain size of the high-tin wolframite or the high-tin scheelite and white wolframite mixed ore is less than 300 mu m.
Preferably, after the reaction is finished, the reaction system is filtered, and tungsten in the filtrate is extracted by one or more of ester extractant, alcohol extractant or anion extractant.
Further preferably, the extractant is 25% TBP + 10% sec-octanol + kerosene, 40% sec-octanol + kerosene, 30% N235+ kerosene or 30% N235+ kerosene.
The percentages in the above-mentioned extractant are volume percentages, such as 25% TBP + 10% sec-octanol + kerosene, which means that the volume fraction of TBP is 25%, the volume fraction of sec-octanol is 10%, and the remainder is kerosene.
The filtrate can be recycled after the consumed phosphoric acid and sulfuric acid are supplemented after extraction.
After the tungsten in the extraction liquid is extracted, if the high-tin tungsten ore is wolframite, the decomposition slag is tin concentrate which can be used as a raw material for extracting tin; if the high-tin tungsten ore is a mixed black-white tungsten ore, the filter residue is gypsum and tin dioxide, and tin is extracted into tin concentrate through a beneficiation process.
Preferably, the method of the present invention comprises the steps of:
in the process of extracting tungsten from high-tin wolframite by using mixed acid of phosphoric acid and sulfuric acid, selecting the high-tin wolframite with the granularity of 50-250 um, wherein the grade of tin is 0.5-20%, adding the mixed acid of phosphoric acid and sulfuric acid to fully dissolve the wolframite, pressurizing a reaction system to ensure that the temperature of the system is 200-230 ℃, adjusting the concentration of phosphoric acid to be 120-175 g/L in the extraction process, and adjusting the concentration of sulfuric acid to be 180-240 g/L.
In the process of extracting tungsten from wolframite by using mixed acid of phosphoric acid and sulfuric acid, mixed ore of high-tin wolframite with the granularity of 50-150 mu m is selected as a raw material, wherein the grade of tin is 0.5-20%, the mixed acid of phosphoric acid and sulfuric acid is added to fully dissolve the wolframite, a reaction system is subjected to pressurization treatment, the temperature of the system is 150-200 ℃, the concentration of phosphoric acid is adjusted to be 100-160 g/L in the extraction process, and the concentration of sulfuric acid is adjusted to be 180-200 g/L.
The invention has the following beneficial effects:
1) according to the invention, through pressurization, the tungsten in the tin-rich wolframite or the tin-rich wolframite-black-white mixed ore can be directly extracted without additionally adding a calcium-containing compound to convert the wolframite in the tungsten extraction process, so that the production process is simplified, and the production cost is reduced.
2) The tin in the tungsten ore can be directly recovered from the tungsten ore decomposition slag or can be recovered in the form of tin concentrate through a concentrating process.
3) Compared with the existing non-pressurized method, the method still has the advantages of high decomposition rate, no generation of hazardous waste decomposition slag and low decomposition cost, and can accelerate the reaction speed after pressurization.
Detailed Description
The following examples are intended to illustrate the invention but are not intended to limit the scope of the invention.
The units of mass to volume ratios referred to in the examples are units of mass to volume corresponding to the order of magnitude of the volume, such as g/mL or kg/L.
Example 1
The embodiment relates to a method for extracting tungsten from tin-rich wolframite, which comprises the following steps:
1) the particle size is 100 mu m, WO3Mixing the wolframite powder with the grade of 62 percent and the tin with the grade of 1.2 percent with mixed acid of phosphoric acid and sulfuric acid according to the mass volume ratio of 1:5, wherein the concentration of the phosphoric acid in the mixed acid solution is 175g/L, and the concentration of the sulfuric acid is 240g/L, uniformly stirring the reaction system, pressurizing the system to 2.6MPa, maintaining the temperature of the reaction system at 230 ℃, stopping pressurizing after reacting for 4.0h, and cooling the reaction system to room temperature;
2) and (2) filtering the reacted system to obtain a filtrate, extracting the filtrate at 40 ℃ for 10 minutes by adopting 25% of TBP, 10% of secondary octanol and kerosene as organic phases, extracting tungsten in the filtrate, supplementing consumed phosphoric acid and sulfuric acid into the residual solution after extraction, and returning the residual solution to the step 1) for reuse. According to calculation, the leaching rate of tungsten is 99.3%, and the grade of the obtained tin concentrate is 12%.
Example 2
The embodiment relates to a method for extracting tungsten from tin-rich wolframite, which comprises the following steps:
1) the particle size is 150 mu m, WO3The grade of the tungsten black ore powder is 50 percent, the grade of the tin is 3.2 percent, and the weight ratio of the tungsten black ore powder to the mixed acid of phosphoric acid and sulfuric acid is 1: 6, mixing, wherein the concentration of phosphoric acid in the mixed acid liquid is 160g/L, the concentration of sulfuric acid is 220g/L, uniformly stirring the reaction system, pressurizing the system to 2.2MPa, maintaining the temperature of the reaction system at 220 ℃, stopping pressurizing after reacting for 4.0h, and cooling the reaction system to room temperature;
2) filtering the reacted system to obtain a filtrate, extracting the filtrate at 40 ℃ for 10 minutes by adopting 40% of sec-octanol and kerosene as organic phases, extracting tungsten in the filtrate, supplementing consumed phosphoric acid and sulfuric acid into the residual solution after extraction, and returning the residual solution to the step 1) for reuse. According to calculation, the leaching rate of tungsten is 99.3%, and the grade of the obtained tin concentrate is 26.5%.
Example 3
The embodiment relates to a method for extracting tungsten from tin-rich wolframite, which comprises the following steps:
1) the particle size is 60 mu m, WO3The grade of the tungsten black ore powder is 34 percent, the grade of the tin is 16.5 percent, and the weight ratio of the tungsten black ore powder to the mixed acid of phosphoric acid and sulfuric acid is 1: 8, mixing, wherein the concentration of phosphoric acid in the mixed acid liquor is 120g/L, the concentration of sulfuric acid is 180g/L, uniformly stirring the reaction system, pressurizing the system to 1.85MPa, maintaining the temperature of the reaction system at 200 ℃, stopping pressurizing after reacting for 6.0h, and cooling the reaction system to room temperature;
2) filtering the reacted system to obtain a filtrate, extracting the filtrate at 50 ℃ for 10 minutes by adopting 30% of N235+ kerosene as an organic phase, extracting tungsten in the filtrate, supplementing consumed phosphoric acid and sulfuric acid into the residual solution after extraction, and returning the residual solution to the step 1) for reuse. According to calculation, the leaching rate of tungsten is 99.2%, and the grade of the obtained tin concentrate is 55%.
Example 4
The embodiment relates to a method for extracting tungsten from tin-rich black-white tungsten mixed ore, which comprises the following steps:
the raw materials in the embodiment are tin-rich black-white tungsten mixed mineral powder, wherein the mass percentage of the black tungsten mineral powder is 30%.
1) The particle size is 100 mu m, WO3Mixed tungsten ore powder with the grade of 52 percent and tin with the grade of 6.5 percent and mixed acid of phosphoric acid and sulfuric acid are mixed according to the mass-volume ratio of 1: 6, mixing, namely, the concentration of phosphoric acid in the mixed acid liquor is 160g/L, the concentration of sulfuric acid is 200g/L, uniformly stirring the reaction system, pressurizing the system to 1.85MPa, maintaining the temperature of the reaction system at 200 ℃, stopping pressurizing after reacting for 4.0, and cooling the reaction system to room temperature;
2) and (2) filtering the reacted system to obtain a filtrate, extracting the filtrate at 40 ℃ for 10 minutes by adopting 25% of TBP, 10% of secondary octanol and kerosene as organic phases, extracting tungsten in the filtrate, supplementing consumed phosphoric acid and sulfuric acid into the residual solution after extraction, and returning the residual solution to the step 1) for reuse. According to calculation, the leaching rate of tungsten is 99.6%, and the grade of tin concentrate obtained by the mineral separation process is 45.8%.
Example 5
The embodiment relates to a method for extracting tungsten from tin-rich black-white tungsten mixed ore, which comprises the following steps:
the raw materials in the embodiment are tin-rich black-white tungsten mixed mineral powder, wherein the mass percentage of the black tungsten mineral powder is 10%.
1) The particle size is 150 mu m, WO3The mixed tungsten ore powder with the grade of 45 percent and the grade of tin of 18.5 percent is mixed with the mixed acid of phosphoric acid and sulfuric acid according to the mass-volume ratio of 1: 4, mixing, namely uniformly stirring the reaction system, pressurizing to 1.25MPa after the concentration of phosphoric acid in the mixed acid liquid is 100g/L and the concentration of sulfuric acid is 180g/L, maintaining the temperature of the reaction system at 180 ℃, stopping pressurizing after reacting for 4.0h, and cooling the reaction system to room temperature;
2) and (2) filtering the reacted system to obtain a filtrate, extracting the filtrate at 40 ℃ for 10 minutes by using 30% N1923+ kerosene as an organic phase to obtain tungsten in the filtrate, and supplementing consumed phosphoric acid and sulfuric acid into the residual solution after extraction and then returning the residual solution to the step 1) for reuse. According to calculation, the leaching rate of tungsten is 99.4%, and the grade of tin concentrate obtained by the mineral separation process is 62.6%.
Example 6
The embodiment relates to a method for extracting tungsten from tin-rich black-white tungsten mixed ore, which comprises the following steps:
the raw materials in the embodiment are tin-rich black-white tungsten mixed mineral powder, wherein the mass percentage of the black tungsten mineral powder is 55%.
1) The particle size is 50 μm, WO3The mixed tungsten ore powder with the grade of 39.6 percent and the grade of tin of 1.5 percent is mixed with the mixed acid of phosphoric acid and sulfuric acid according to the mass-volume ratio of 1: 8, mixing, wherein the concentration of phosphoric acid in the mixed acid liquor is 140g/L, the concentration of sulfuric acid is 200g/L, uniformly stirring the reaction system, pressurizing the system to 0.56MPa, maintaining the temperature of the reaction system at 150 ℃, stopping pressurizing after reacting for 6.0h, and cooling the reaction system to room temperature;
2) filtering the reacted system to obtain a filtrate, extracting the filtrate at 40 ℃ for 10 minutes by adopting 40% of sec-octanol and kerosene as organic phases, extracting tungsten in the filtrate, supplementing consumed phosphoric acid and sulfuric acid into the residual solution after extraction, and returning the residual solution to the step 1) for reuse. According to calculation, the leaching rate of tungsten is 99.2%, and the grade of tin concentrate obtained by the mineral separation process is 43.6%.
Comparative example 1
Compared with the example 1, the difference is that the reaction system is not pressurized, the reaction temperature is 90 ℃, the leaching rate of tungsten is 80.6 percent after the reaction is finished, the obtained decomposition slag is tungsten-tin mixed ore, and the grade of tin is 4.5 percent.
Comparative example 2
Compared with the example 2, the difference is that the system is pressurized, the temperature of the reaction system is controlled to be 106 ℃, the leaching rate of tungsten is 91.5 percent after the reaction is finished, the obtained decomposition slag is tungsten-tin mixed ore, and the grade of tin is 8.5 percent.
Comparative example 3
The difference from example 2 is that the concentration of phosphoric acid and sulfuric acid in the system was controlled to 50g/L and 100g/L, and the leaching rate of tungsten was 86.5% after the reaction was completed, and the obtained decomposed slag was a tungsten-tin mixed ore with a tin grade of 6.6%.
Although the invention has been described in detail hereinabove by way of general description, specific embodiments and experiments, it will be apparent to those skilled in the art that many modifications and improvements can be made thereto based on the invention. Accordingly, such modifications and improvements are intended to be within the scope of the invention as claimed.
Claims (8)
1. A method for decomposing high-tin tungsten ore under pressure by using mixed sulfuric and phosphoric acid is characterized in that in the process of extracting tungsten from the high-tin wolframite or the mixed ore of high-tin wolframite and white wolframite by using the mixed acid of phosphoric acid and sulfuric acid;
the raw material is the high-tin wolframite, the concentration of phosphoric acid is 60-200 g/L, the concentration of sulfuric acid is 100-250 g/L, and the reaction system is pressurized to ensure that the temperature of the system is 200-230 ℃;
the raw material is the mixed ore of the high-tin black and white tungsten, and the concentration of phosphoric acid is 30-160 g/L; the concentration of sulfuric acid is 60-220 g/L, and the reaction system is pressurized to ensure that the temperature of the system is 150-200 ℃;
the mass volume ratio of the high-tin wolframite or the high-tin wolframite mixture to the mixed acid is 1: 3-10.
2. The method according to claim 1, wherein the WO is in the mixed ore of high-tin wolframite or high-tin wolframite3The grade of (A) is 10-70%.
3. The method according to claim 1 or 2, wherein the grade of tin in the high-tin wolframite or the high-tin scheelite-scheelite mixed ore is 0.5 to 20%.
4. The method according to claim 1 or 2, wherein the pressure of the reaction system is 0.54 to 3.0Mpa when the raw material is the high-tin wolframite, and the pressure of the reaction system is 0.21 to 1.85Mpa when the raw material is the mixed ore of the high-tin wolframite and the scheelite.
5. The method according to claim 3, wherein the pressure of the reaction system is 0.54-3.0 MPa when the raw material is the high-tin wolframite, and the pressure of the reaction system is 0.21-1.85 MPa when the raw material is the mixed ore of the high-tin wolframite and the scheelite.
6. The method according to claim 1, wherein the particle size of the high tin wolframite or the mixed ore of high tin wolframite is less than 300 μ ι η.
7. The method of claim 1, wherein the reaction system is filtered after the reaction is completed, and the tungsten in the filtrate is extracted by one or more of an ester extractant, an alcohol extractant or an amine extractant.
8. Method according to claim 1 or 5, characterized in that it comprises the following steps:
in the process of extracting tungsten from the high-tin wolframite by using mixed acid of phosphoric acid and sulfuric acid, selecting the high-tin wolframite with the granularity of 50-250 um, wherein the grade of tin is 0.5-20%, adding the mixed acid of phosphoric acid and sulfuric acid to fully dissolve the wolframite, pressurizing a reaction system to ensure that the temperature of the system is 200-230 ℃, adjusting the concentration of phosphoric acid to be 120-175 g/L in the extraction process, and adjusting the concentration of sulfuric acid to be 180-240 g/L;
in the process of extracting tungsten from the high-tin black and white tungsten mixed ore by using mixed acid of phosphoric acid and sulfuric acid, the high-tin black and white tungsten mixed ore with the granularity of 50-150 mu m is selected as a raw material, wherein the grade of tin is 0.5-20%, the mixed acid of phosphoric acid and sulfuric acid is added to fully dissolve the black tungsten ore, a reaction system is subjected to pressurization treatment, the temperature of the system is 150-200 ℃, the concentration of phosphoric acid is adjusted to be 100-160 g/L in the extraction process, and the concentration of sulfuric acid is adjusted to be 180-200 g/L.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810332892.3A CN108642308B (en) | 2018-04-13 | 2018-04-13 | Method for decomposing high-tin tungsten ore under pressure by using sulfur-phosphorus mixed acid |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810332892.3A CN108642308B (en) | 2018-04-13 | 2018-04-13 | Method for decomposing high-tin tungsten ore under pressure by using sulfur-phosphorus mixed acid |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN108642308A CN108642308A (en) | 2018-10-12 |
| CN108642308B true CN108642308B (en) | 2020-11-10 |
Family
ID=63746086
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201810332892.3A Expired - Fee Related CN108642308B (en) | 2018-04-13 | 2018-04-13 | Method for decomposing high-tin tungsten ore under pressure by using sulfur-phosphorus mixed acid |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN108642308B (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112899502B (en) * | 2021-01-20 | 2021-12-28 | 中南大学 | Method for treating high-calcium black-white tungsten mixed ore |
| CN113106251B (en) * | 2021-03-10 | 2023-03-10 | 湖南柿竹园有色金属有限责任公司 | Chemical beneficiation method for producing tin middling from high-tin wolframite or wolframite and wolframite mixed ore |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1414120A (en) * | 2002-11-15 | 2003-04-30 | 自贡硬质合金有限责任公司 | Method of producing tungstic acid by closed type hydrochloric acid decompose tunstite |
| CN101608257A (en) * | 2009-04-09 | 2009-12-23 | 厦门钨业股份有限公司 | Technology for far infrared thermocompression decomposition of tungsten mineral raw material |
| CN102021329A (en) * | 2010-12-24 | 2011-04-20 | 中南大学 | Method for extracting tungsten from scheelite and producing high-quality calcined gypsum |
| CN104805314A (en) * | 2015-05-13 | 2015-07-29 | 中南大学 | Method for extracting tungsten from raw materials containing wolframite |
| CN106282608A (en) * | 2016-08-29 | 2017-01-04 | 中南大学 | A kind of method decomposing Scheelite-Wolframite Mixed Mine |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2013204068A (en) * | 2012-03-27 | 2013-10-07 | Cmc Gijutsu Kaihatsu Kk | Method for recovering tungsten or cobalt from cemented carbide powder |
| JP2018062691A (en) * | 2016-10-13 | 2018-04-19 | Ｊｘ金属株式会社 | Method for collecting tungsten concentrate from cobalt-tungsten raw material |
-
2018
- 2018-04-13 CN CN201810332892.3A patent/CN108642308B/en not_active Expired - Fee Related
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1414120A (en) * | 2002-11-15 | 2003-04-30 | 自贡硬质合金有限责任公司 | Method of producing tungstic acid by closed type hydrochloric acid decompose tunstite |
| CN101608257A (en) * | 2009-04-09 | 2009-12-23 | 厦门钨业股份有限公司 | Technology for far infrared thermocompression decomposition of tungsten mineral raw material |
| CN102021329A (en) * | 2010-12-24 | 2011-04-20 | 中南大学 | Method for extracting tungsten from scheelite and producing high-quality calcined gypsum |
| CN104805314A (en) * | 2015-05-13 | 2015-07-29 | 中南大学 | Method for extracting tungsten from raw materials containing wolframite |
| CN106282608A (en) * | 2016-08-29 | 2017-01-04 | 中南大学 | A kind of method decomposing Scheelite-Wolframite Mixed Mine |
Non-Patent Citations (1)
| Title |
|---|
| 硫磷混酸浸出黑钨矿动力学;杨凯华等;《中国有色金属学报》;20180131;第28卷(第1期);第175-181页 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN108642308A (en) | 2018-10-12 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN108642278B (en) | Method for extracting tungsten by pressure decomposition of wolframite or wolframite and wolframite mixed ore through sulfur and phosphorus mixed acid | |
| CN110004309B (en) | Method for acid-base combined extraction of tungsten from tungsten mineral | |
| CN106636689B (en) | A kind of method of Extraction of rare earth in precipitation slag from RE waste water pond | |
| CN110885090A (en) | Method for preparing battery-grade lithium carbonate by using lepidolite as raw material through one-step method | |
| CN108642307B (en) | Method for extracting tungsten by decomposing wolframite or wolframite and wolframite mixed ore under pressure by hydrochloric acid-phosphoric acid | |
| CN108707765B (en) | Method for decomposing scheelite by phosphorus-sulfur mixed acid under pressure | |
| CA2798357A1 (en) | Method for producing raw material for ferronickel smelting from low grade nickel oxide ore | |
| CN108642279B (en) | Method for decomposing wolframite by pressurizing and countercurrent sulfur and phosphorus mixed acid | |
| CN108425010A (en) | A kind of method that acid decomposes high seyrigite extraction tungsten | |
| CN112662877A (en) | Method for preparing high-purity nickel sulfate from electrolytic manganese sulfide slag | |
| CN110066920B (en) | Method for selectively leaching and separating vanadium and iron from stone coal vanadium ore | |
| CN108642308B (en) | Method for decomposing high-tin tungsten ore under pressure by using sulfur-phosphorus mixed acid | |
| CN114058853B (en) | Method for recovering titanium, vanadium and tungsten from waste SCR denitration catalyst | |
| CN112662878B (en) | Method for preparing high-purity cobalt sulfate from electrolytic manganese sulfide slag | |
| CN111004917A (en) | Process for comprehensively recovering arsenic sulfide slag | |
| CN108425011A (en) | A method of extracting tungsten from high seyrigite | |
| CN114622102A (en) | Method for comprehensively extracting valuable metals from laterite-nickel ore | |
| CN114561547A (en) | Method for comprehensively recovering valuable metals in high-zinc copper smelting smoke dust | |
| CN109763003B (en) | Method for extracting tungsten and molybdenum by decomposing high-molybdenum scheelite by electrooxidation method | |
| CN105274352A (en) | Method for separating copper, cobalt and manganese from mixture of copper, manganese, cobalt, calcium and zinc carbonate | |
| CN113186399B (en) | Method for extracting tantalum and niobium | |
| CN116002736B (en) | Method for preparing aluminum hydroxide by pressure leaching and separating aluminum and lithium from clay lithium ore | |
| CN109338112B (en) | Method for purifying vanadium pentoxide | |
| CN115109931B (en) | Method for recycling multiple metals from tungsten-molybdenum waste residues | |
| CN114606388B (en) | Method for leaching arsenic-containing copper smelting smoke dust and synchronously removing arsenic |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20201110 |
|
| CF01 | Termination of patent right due to non-payment of annual fee |