CN112899501A - Method for treating low-grade black-white tungsten mixed ore - Google Patents
Method for treating low-grade black-white tungsten mixed ore Download PDFInfo
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- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 title claims abstract description 85
- 229910052721 tungsten Inorganic materials 0.000 title claims abstract description 85
- 239000010937 tungsten Substances 0.000 title claims abstract description 85
- 238000000034 method Methods 0.000 title claims abstract description 38
- 239000002253 acid Substances 0.000 claims abstract description 101
- 238000000354 decomposition reaction Methods 0.000 claims abstract description 48
- 238000005406 washing Methods 0.000 claims abstract description 42
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 41
- 239000002893 slag Substances 0.000 claims abstract description 36
- 238000000605 extraction Methods 0.000 claims abstract description 35
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 33
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims abstract description 30
- 239000007788 liquid Substances 0.000 claims abstract description 26
- 238000003756 stirring Methods 0.000 claims abstract description 20
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 19
- 239000003513 alkali Substances 0.000 claims abstract description 18
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims abstract description 15
- 238000002386 leaching Methods 0.000 claims abstract description 12
- 229910052602 gypsum Inorganic materials 0.000 claims abstract description 11
- 239000010440 gypsum Substances 0.000 claims abstract description 11
- 239000012074 organic phase Substances 0.000 claims abstract description 11
- 238000005554 pickling Methods 0.000 claims abstract description 11
- 238000010411 cooking Methods 0.000 claims abstract description 9
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 6
- PBYZMCDFOULPGH-UHFFFAOYSA-N tungstate Chemical compound [O-][W]([O-])(=O)=O PBYZMCDFOULPGH-UHFFFAOYSA-N 0.000 claims abstract description 3
- 238000001914 filtration Methods 0.000 claims description 32
- ZXOKVTWPEIAYAB-UHFFFAOYSA-N dioxido(oxo)tungsten Chemical compound [O-][W]([O-])=O ZXOKVTWPEIAYAB-UHFFFAOYSA-N 0.000 claims description 30
- 239000007787 solid Substances 0.000 claims description 18
- 238000002156 mixing Methods 0.000 claims description 10
- 230000001502 supplementing effect Effects 0.000 claims description 10
- 238000006243 chemical reaction Methods 0.000 claims description 7
- 239000000706 filtrate Substances 0.000 claims description 7
- 239000003350 kerosene Substances 0.000 claims description 7
- BYMMIQCVDHHYGG-UHFFFAOYSA-N Cl.OP(O)(O)=O Chemical compound Cl.OP(O)(O)=O BYMMIQCVDHHYGG-UHFFFAOYSA-N 0.000 claims description 6
- 239000000654 additive Substances 0.000 claims description 2
- 230000000996 additive effect Effects 0.000 claims description 2
- 239000011575 calcium Substances 0.000 abstract description 10
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 abstract description 4
- 239000002585 base Substances 0.000 abstract description 4
- 229910052791 calcium Inorganic materials 0.000 abstract description 4
- 238000009835 boiling Methods 0.000 description 5
- 230000008901 benefit Effects 0.000 description 4
- 238000004140 cleaning Methods 0.000 description 4
- 238000003723 Smelting Methods 0.000 description 2
- 230000001133 acceleration Effects 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000005484 gravity Effects 0.000 description 2
- 238000000713 high-energy ball milling Methods 0.000 description 2
- 229910052500 inorganic mineral Inorganic materials 0.000 description 2
- 239000011707 mineral Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 238000004064 recycling Methods 0.000 description 2
- 239000002351 wastewater Substances 0.000 description 2
- 235000017166 Bambusa arundinacea Nutrition 0.000 description 1
- 235000017491 Bambusa tulda Nutrition 0.000 description 1
- 235000011511 Diospyros Nutrition 0.000 description 1
- 244000236655 Diospyros kaki Species 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- 240000002853 Nelumbo nucifera Species 0.000 description 1
- 235000006508 Nelumbo nucifera Nutrition 0.000 description 1
- 235000006510 Nelumbo pentapetala Nutrition 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 244000082204 Phyllostachys viridis Species 0.000 description 1
- 235000015334 Phyllostachys viridis Nutrition 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- QCJQWJKKTGJDCM-UHFFFAOYSA-N [P].[S] Chemical compound [P].[S] QCJQWJKKTGJDCM-UHFFFAOYSA-N 0.000 description 1
- 229910052785 arsenic Inorganic materials 0.000 description 1
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 description 1
- 239000011425 bamboo Substances 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 238000009854 hydrometallurgy Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 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
- 239000011574 phosphorus Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000009469 supplementation Effects 0.000 description 1
- 239000002699 waste material Substances 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
- 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
-
- 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
- C22B3/08—Sulfuric acid, other sulfurated 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
- C22B3/12—Extraction of metal compounds from ores or concentrates by wet processes by leaching in inorganic alkaline 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
Abstract
The invention discloses a method for processing low-grade tungsten mixed ore, which comprises the following steps of carrying out acid pickling on the low-grade tungsten mixed ore to obtain pickling solution and pickling slag; adding the acid-washing slag into mixed acid of hydrochloric acid and phosphoric acid, and stirring and reacting for 1-5 h at 70-95 ℃ to obtain acid decomposition slag and acid decomposition liquid; placing the acid decomposition residues in a high-pressure kettle, and performing alkali cooking by using sodium hydroxide as a decomposing agent to obtain an alkali leaching solution and alkali cooking residues; adding concentrated sulfuric acid into the acid decomposition liquid to react to obtain high-purity gypsum residue and a tungsten-containing solution; extracting tungsten in the tungsten-containing solution by using a TBP extraction system to obtain a loaded organic phase and raffinate, and performing back extraction on the loaded organic phase by using an alkali leaching solution as a back extraction agent to obtain an alkaline tungstate solution for subsequent extraction of tungsten. According to the invention, the low-grade black-white tungsten mixed ore is treated in an acid-base combined manner, so that on one hand, the high-efficiency extraction of tungsten resources can be realized, and on the other hand, calcium in the tungsten ore is converted into gypsum, and the discharge of alkaline cooking slag is greatly reduced.
Description
Technical Field
The invention belongs to the field of hydrometallurgy and relates to extraction of rare metal tungsten, in particular to a method for treating low-grade black-white tungsten mixed ore.
Background
China is a big tungsten resource country, and the total reserve of tungsten accounts for more than 50% of the total reserve of the whole world. With the continuous development and utilization of tungsten resources, the easy-to-smelt wolframine resources are gradually consumed, and the tungsten smelting raw materials are mainly low-grade wolframine or scheelite. Most of wolframite and scheelite resources have poor natural endowment, the associated relationship is very complex, impurities such as molybdenum, phosphorus, arsenic, silicon, fluorine and the like are mostly associated, the embedded particle size is fine, the grade is low (the grade is less than 0.4 percent and accounts for more than 80 percent), and the existing tungsten smelting process is difficult to digest the tungsten mineral with low grade and complex components. Lotus mountain WO3The decomposition rate of the low-grade tungsten ore with the content of 24.1 percent can reach more than 96 percent by adopting the NaOH dosage 3.5 times of the theoretical amount; and persimmon bamboo garden WO3The NaOH consumption required by the refractory wolframite and black wolframite mixed ore with the content of 27.35 percent is more than 4 times of the theoretical quantity, only 64.48 percent of decomposition rate is obtained under the conditions of 160 ℃ and 1.5h, and the slag contains WO3Up to 13.5%. Researchers also develop a method (2015102433825) for decomposing the wolframite and wolframite mixed ore by a sulfur-phosphorus mixed acid method, the wolframite and alkaline calcium-containing substances are ball-milled under the condition of 10 times of gravity acceleration, part of the wolframite is converted into scheelite, and meanwhile, the activity of the unconverted wolframite is greatly improved by high-energy ball milling, so that the acid decomposition of the wolframite is promoted. However, even if the method is carried out under the condition of 10 times of gravity acceleration, the industrialization difficulty is very high, the energy consumption of high-energy ball milling is very high, and the method is used for mixing low-grade black and white tungstenThe decomposition effect of the ore combination is poor, and 28.9 percent of WO is treated3When the tungsten content is the black and white tungsten mixed ore, the leaching rate of tungsten is only 97.4 percent. Therefore, how to realize the efficient extraction of the tungsten resource in the low-grade complex wolframite and wolframite mixed ore is particularly important for the sustainable development of the tungsten industry.
Disclosure of Invention
In order to solve the problems in the prior art, the invention aims to provide a method for treating low-grade black-white tungsten mixed ore, which treats the low-grade black-white tungsten mixed ore in an acid-base combined mode, on one hand, the high-efficiency extraction of tungsten resources can be realized, on the other hand, calcium in the tungsten ore is converted into gypsum, the discharge of alkaline cooking slag is greatly reduced, and meanwhile, the reagent consumption and the wastewater discharge are reduced in an acid supplementing circulating mode, so that the method has remarkable ecological benefit and economic benefit.
In order to achieve the technical purpose, the invention adopts the following technical scheme:
a method for processing low-grade black-white tungsten mixed ore comprises the following steps:
(1) adding the low-grade wolframite and wolframite mixed ore into dilute hydrochloric acid for acid washing, filtering to obtain a pickling solution and pickling slag, supplementing concentrated sulfuric acid into the obtained pickling solution, and filtering, wherein the filtrate is circularly used for acid washing;
(2) adding the acid washing slag obtained in the step (1) into hydrochloric acid-phosphoric acid mixed acid, stirring and reacting for 1-5 h at 70-95 ℃, and filtering to obtain acid decomposition slag and acid decomposition liquid;
(3) putting the acid decomposition residue obtained in the step (2) into a high-pressure kettle, and performing alkali cooking by using sodium hydroxide as a decomposing agent to obtain an alkali leaching solution and alkali cooking residue;
(4) adding concentrated sulfuric acid into the acid decomposition liquid obtained in the step (2) for reaction, and filtering to obtain high-purity gypsum residue and a tungsten-containing solution; extracting tungsten in the tungsten-containing solution by using a TBP extraction system to obtain a loaded organic phase and raffinate, and returning the raffinate to the step (2) for reuse after supplementing hydrochloric acid and phosphoric acid; and (4) performing back extraction on the loaded organic phase by using the alkali leaching solution obtained in the step (3) as a back extraction agent, and using the obtained alkaline tungstate solution for subsequent extraction of tungsten.
Further, the method can be used for preparing a novel materialIn the step (1), WO is contained in the low-grade black-white tungsten mixed ore3The content is 15-45 wt%.
Furthermore, in the low-grade wolframite and wolframite mixed ore, the wolframite content accounts for 10-50 wt% of the total wolframite.
Further, in the step (1), the liquid-solid ratio of the low-grade wolframite and wolframite mixture ore to the dilute hydrochloric acid is 1-5 mL/g, and the concentration of the dilute hydrochloric acid is 10-50 g/L.
Further, in the step (1), the acid washing process comprises the following steps: stirring and reacting for 10-60 min at room temperature.
Furthermore, in the step (1), the volume ratio of the addition amount of concentrated sulfuric acid to the pickling solution is 1: 8-12.
Further, in the step (2), the liquid-solid ratio of the acid washing slag to the hydrochloric acid-phosphoric acid mixed acid is 1-5 mL/g.
Furthermore, in the hydrochloric acid-phosphoric acid mixed acid, the concentration of the hydrochloric acid is 50-150g/L, and the concentration of the phosphoric acid is 20-100 g/L.
Further, in the step (4), the concentrated sulfuric acid is adjusted according to Ca in the acid decomposition solution2+And H2SO4In a molar ratio of 1: 0.95-1 of the additive.
Further, in the step (4), the TBP extraction system is a mixed system of TBP with volume fraction of 40-80% and kerosene with volume fraction of 20-60%, the extraction ratio is 1:1-2, and the mixing time is 5-10 min.
The invention has the advantages that:
1. the acid-base combined mode is adopted to treat the low-grade black-white tungsten mixed ore, so that WO in the slag can be treated3The content is reduced to below 1 percent, and the high-efficiency recovery of tungsten resources is realized;
2. compared with the traditional process, the acid-base combined process greatly reduces the consumption of NaOH and reduces the production cost;
3. the acid supplementation circulation can reduce reagent consumption and wastewater discharge, save cost, convert calcium in minerals into gypsum output, greatly reduce the discharge of dangerous waste alkali cooking slag, and has remarkable economic and ecological benefits.
Detailed Description
In order to explain the present invention in more detail, the following examples are given for illustration, but the present invention is not limited to these examples.
Example 1
(1) Mixing WO at the ratio of 1:1(mL/g) to solid3Adding 30 wt% of black-white tungsten mixed ore (wherein the black tungsten accounts for 10 wt%) into 50g/L diluted hydrochloric acid for acid washing, stirring at room temperature for reaction for 10min, filtering to obtain acid washing liquid and acid washing slag, supplementing concentrated sulfuric acid into the acid washing liquid according to the volume ratio of 10:1, and filtering again, wherein the filtrate is recycled for acid washing;
(2) adding the acid-washing slag into mixed acid with the hydrochloric acid concentration of 150g/L and the phosphoric acid concentration of 50g/L according to the liquid-solid ratio of 5:1(mL/g), stirring and reacting for 1h at 95 ℃, and filtering to obtain acid decomposition slag and acid decomposition liquid;
(3) adding acid decomposition residue into autoclave, pressure boiling with NaOH at liquid-solid ratio of 1:1(mL/g), reacting at 150 deg.C for 3 hr, filtering to obtain alkaline leachate and alkaline decoction residue, and adding WO3The content is 0.59 wt%;
(4) according to Ca in the acid decomposition liquid2+And H2SO4In a molar ratio of 1: 0.95, adding concentrated sulfuric acid into the acid decomposition solution, stirring for 10min, and filtering to obtain high-purity gypsum residue (99.2 wt%) and a tungsten-containing solution; extracting tungsten in the tungsten-containing solution at room temperature by using a kerosene system with the volume fraction of 50-50% of TBP (tunnel boring process) for 5min, wherein the extraction rate of tungsten is 99.2% compared with 1:1, and the raffinate is supplemented with hydrochloric acid and phosphoric acid and then returned to be used for mixed acid decomposition of acid washing slag; and then carrying out back extraction on the loaded organic phase by using an alkali leaching solution, wherein the back extraction rate of tungsten is 99%.
Example 2
(1) Mixing WO at the ratio of liquid to solid being 5:1(mL/g)3Adding the 20 wt% black-white tungsten mixed ore (wherein the black tungsten accounts for 30 wt%) into 10g/L diluted hydrochloric acid for acid washing, stirring at room temperature for reaction for 60min, filtering to obtain acid washing liquid and acid washing slag, supplementing concentrated sulfuric acid into the acid washing liquid according to the volume ratio of 10:1, and filtering again, wherein the filtrate is recycled for acid washing;
(2) adding the acid-washing slag into mixed acid with the hydrochloric acid concentration of 100g/L and the phosphoric acid concentration of 100g/L according to the liquid-solid ratio of 1:1(mL/g), stirring and reacting for 5 hours at 70 ℃, and filtering to obtain acid decomposition slag and acid decomposition liquid;
(3) adding acid decomposition residue into autoclave, pressure boiling with NaOH at liquid-solid ratio of 1.2:1(mL/g), reacting at 160 deg.C for 2 hr, filtering to obtain alkaline leachate and alkaline decoction residue, and adding WO3The content is 0.81%;
(4) according to Ca in the acid decomposition liquid2+And H2SO4In a molar ratio of 1:1, adding concentrated sulfuric acid into the acid decomposition solution, stirring for 5min, and filtering to obtain high-purity gypsum residue (99.3 wt%) and a tungsten-containing solution; extracting tungsten in the tungsten-containing solution at room temperature by using a kerosene system with the volume fraction of 80-20% of TBP (tunnel boring process) for 8min, wherein the extraction rate of tungsten is 99.5% compared with 1:1.5, and the raffinate is supplemented with hydrochloric acid and phosphoric acid and then returned to be used for mixed acid decomposition of acid washing slag; and then carrying out back extraction on the loaded organic phase by using an alkali leaching solution, wherein the back extraction rate of tungsten is 99.2%.
Example 3
(1) Mixing WO at the ratio of 3:1(mL/g) to solid3Adding 45 wt% of black-white tungsten mixed ore (wherein the black tungsten accounts for 50 wt%) into 20g/L dilute hydrochloric acid for acid washing, stirring at room temperature for reaction for 20min, filtering to obtain acid washing liquid and acid washing slag, supplementing concentrated sulfuric acid into the acid washing liquid according to the volume ratio of 10:1, and filtering again, wherein the filtrate is recycled for acid washing;
(2) adding the acid-washing slag into mixed acid with the hydrochloric acid concentration of 50g/L and the phosphoric acid concentration of 100g/L according to the liquid-solid ratio of 2:1(mL/g), stirring and reacting for 4 hours at 80 ℃, and filtering to obtain acid decomposition slag and acid decomposition liquid;
(3) adding acid decomposition residue into autoclave, pressure boiling with NaOH at liquid-solid ratio of 1.2:1(mL/g), reacting at 160 deg.C for 3 hr, filtering to obtain alkaline leachate and alkaline decoction residue, and adding WO3The content is 0.72%;
(4) according to Ca in the acid decomposition liquid2+And H2SO4In a molar ratio of 1:1, adding concentrated sulfuric acid into the acid decomposition solution, stirring for 5min, and filtering to obtain high-purity gypsum residue (99.5 wt%) and a tungsten-containing solution; the volume fraction of the kerosene system is 40 percent TBP-60 percentExtracting tungsten in the tungsten-containing solution at room temperature, mixing for 10min, wherein the extraction rate of tungsten is 99.4% compared with 1:1, and the raffinate is supplemented with hydrochloric acid and phosphoric acid and then returned to be used for mixed acid decomposition of acid washing slag; and then carrying out back extraction on the loaded organic phase by using an alkali leaching solution, wherein the back extraction rate of tungsten is 99.2%.
Example 4
(1) Mixing WO at the ratio of 1:1(mL/g) to solid3Adding the mixed black-white tungsten ore with the content of 15 wt% (wherein the black tungsten accounts for 10 wt%) into 50g/L diluted hydrochloric acid for acid washing, stirring at room temperature for reaction for 30min, filtering to obtain acid washing liquid and acid washing slag, supplementing concentrated sulfuric acid into the acid washing liquid according to the volume ratio of 10:1, filtering again, and recycling the filtrate for acid washing;
(2) adding the acid-washing slag into mixed acid with the hydrochloric acid concentration of 150g/L and the phosphoric acid concentration of 20g/L according to the liquid-solid ratio of 2:1(mL/g), stirring and reacting for 5 hours at 95 ℃, and filtering to obtain acid decomposition slag and acid decomposition liquid;
(3) adding acid decomposition residue into autoclave, pressure boiling with NaOH at liquid-solid ratio of 1.2:1(mL/g), reacting at 150 deg.C for 3 hr, filtering to obtain alkaline leachate and alkaline decoction residue, and adding WO3The content is 0.43 percent;
(4) according to Ca in the acid decomposition liquid2+And H2SO4In a molar ratio of 1: 0.95, adding concentrated sulfuric acid into the acid decomposition solution, stirring for 5min, and filtering to obtain high-purity gypsum residue (99.2 wt%) and a tungsten-containing solution; extracting tungsten in the tungsten-containing solution at room temperature by using a kerosene system with the volume fraction of 80-20% of TBP (tunnel boring process), mixing for 5min, wherein the extraction rate of tungsten is 99.5% compared with 1:1, and returning raffinate to be used for mixed acid decomposition of acid washing slag after supplementing hydrochloric acid and phosphoric acid; and then carrying out back extraction on the loaded organic phase by using an alkali leaching solution, wherein the back extraction rate of tungsten is 99.1%.
Example 5
(1) Mixing WO at the ratio of 2:1(mL/g) to obtain a mixture3Adding 40 wt% of mixed wolframite and wolframite ore (wherein the wolframite accounts for 30 wt%) into 50g/L dilute hydrochloric acid for acid cleaning, stirring at room temperature for reaction for 10min, filtering to obtain acid cleaning solution and acid cleaning slag, adding concentrated sulfuric acid into the acid cleaning solution according to the volume ratio of 10:1Filtering again, and recycling filtrate for acid washing;
(2) adding the acid-washing slag into mixed acid with the hydrochloric acid concentration of 50g/L and the phosphoric acid concentration of 100g/L according to the liquid-solid ratio of 1:1(mL/g), stirring and reacting for 3h at 95 ℃, and filtering to obtain acid decomposition slag and acid decomposition liquid;
(3) adding acid decomposition residue into autoclave, pressure boiling with NaOH at liquid-solid ratio of 1.2:1(mL/g), reacting at 150 deg.C for 3 hr, filtering to obtain alkaline leachate and alkaline decoction residue, and adding WO3The content is 0.51%;
(4) according to Ca in the acid decomposition liquid2+And H2SO4In a molar ratio of 1:1, adding concentrated sulfuric acid into the acid decomposition solution, stirring for 5min, and filtering to obtain high-purity gypsum residue (99.4 wt%) and a tungsten-containing solution; extracting tungsten in the tungsten-containing solution at room temperature by using a kerosene system with the volume fraction of 70-30% of TBP (tunnel boring process) for 5min, wherein the extraction rate of tungsten is 99.2% compared with 1:1, and the raffinate is supplemented with hydrochloric acid and phosphoric acid and then returned to be used for mixed acid decomposition of acid washing slag; and then carrying out back extraction on the loaded organic phase by using an alkali leaching solution, wherein the back extraction rate of tungsten is 99%.
Claims (10)
1. The method for treating the low-grade black-white tungsten mixed ore is characterized by comprising the following steps of:
(1) adding the low-grade wolframite and wolframite mixed ore into dilute hydrochloric acid for acid washing, filtering to obtain a pickling solution and pickling slag, supplementing concentrated sulfuric acid into the obtained pickling solution, and filtering, wherein the filtrate is circularly used for acid washing;
(2) adding the acid washing slag obtained in the step (1) into hydrochloric acid-phosphoric acid mixed acid, stirring and reacting for 1-5 h at 70-95 ℃, and filtering to obtain acid decomposition slag and acid decomposition liquid;
(3) putting the acid decomposition residue obtained in the step (2) into a high-pressure kettle, and performing alkali cooking by using sodium hydroxide as a decomposing agent to obtain an alkali leaching solution and alkali cooking residue;
(4) adding concentrated sulfuric acid into the acid decomposition liquid obtained in the step (2) for reaction, and filtering to obtain high-purity gypsum residue and a tungsten-containing solution; extracting tungsten in the tungsten-containing solution by using a TBP extraction system to obtain a loaded organic phase and raffinate, and returning the raffinate to the step (2) for reuse after supplementing hydrochloric acid and phosphoric acid; and (4) performing back extraction on the loaded organic phase by using the alkali leaching solution obtained in the step (3) as a back extraction agent, and using the obtained alkaline tungstate solution for subsequent extraction of tungsten.
2. The method for treating the low-grade black-white tungsten mixed ore according to claim 1, wherein the method comprises the following steps: in the step (1), WO is contained in the low-grade black-white tungsten mixed ore3The content is 15-45 wt%.
3. The method for treating the low-grade black-white tungsten mixed ore according to claim 2, wherein the method comprises the following steps: in the low-grade wolframite and wolframite mixed ore, the wolframite content accounts for 10-50 wt% of the total wolframite.
4. The method for treating the low-grade black-white tungsten mixed ore according to claim 1, wherein the method comprises the following steps: in the step (1), the liquid-solid ratio of the low-grade wolframite and wolframite mixed ore to the dilute hydrochloric acid is 1-5 mL/g, and the concentration of the dilute hydrochloric acid is 10-50 g/L.
5. The method for treating the low-grade black-white tungsten mixed ore according to claim 1, wherein the method comprises the following steps: in the step (1), the acid washing process comprises the following steps: stirring and reacting for 10-60 min at room temperature.
6. The method for treating the low-grade black-white tungsten mixed ore according to claim 1, wherein the method comprises the following steps: in the step (1), the volume ratio of the addition amount of concentrated sulfuric acid to the pickling solution is 1: 8-12.
7. The method for treating the low-grade black-white tungsten mixed ore according to claim 1, wherein the method comprises the following steps: in the step (2), the liquid-solid ratio of the acid washing slag to the hydrochloric acid-phosphoric acid mixed acid is 1-5 mL/g.
8. The method for treating the low-grade black-white tungsten mixed ore according to claim 7, wherein the method comprises the following steps: in the hydrochloric acid-phosphoric acid mixed acid, the concentration of hydrochloric acid is 50-150g/L, and the concentration of phosphoric acid is 20-100 g/L.
9. The method for treating the low-grade black-white tungsten mixed ore according to claim 1, wherein the method comprises the following steps: in the step (4), concentrated sulfuric acid is used according to Ca in the acid decomposition liquid2+And H2SO4In a molar ratio of 1: 0.95-1 of the additive.
10. The method for treating the low-grade black-white tungsten mixed ore according to claim 1, wherein the method comprises the following steps: in the step (4), the TBP extraction system is a mixed system of TBP with the volume fraction of 40-80% and kerosene with the volume fraction of 20-60%, the extraction ratio is 1:1-2, and the mixing time is 5-10 min.
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