阅读说明：本技术 一种处理低品位黑白钨混合矿的方法 (Method for treating low-grade black-white tungsten mixed ore ) 是由 刘旭恒 赵中伟 陈星宇 李江涛 何利华 孙丰龙 于 2021-01-20 设计创作，主要内容包括：本发明公开了一种处理低品位黑白钨混合矿的方法,将低品位黑白钨混合矿进行酸洗得到酸洗液和酸洗渣；将酸洗渣加入到盐酸-磷酸混酸中,在70～95℃下搅拌反应1～5h得到酸分解渣和酸分解液；将酸分解渣置于高压釜中,用氢氧化钠作为分解剂进行碱煮,得到碱浸出液和碱煮渣；将浓硫酸加入到酸分解液中反应得到高纯石膏渣和含钨溶液；用TBP萃取体系萃取含钨溶液中的钨,得到负载有机相和萃余液,用碱浸出液作为反萃剂对负载有机相进行反萃,得到的碱性钨酸盐溶液用于后续钨的提取。本发明通过酸碱联合的方式来处理低品位黑白钨混合矿,一方面可以实现钨资源的高效提取,另一方面,将钨矿中的钙转化为石膏,大幅减少碱煮渣的排放。(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.)

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.

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%.