阅读说明：本技术 一种处理高钙黑白钨混合矿的方法 (Method for treating high-calcium 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高钙黑白钨混合矿的方法,将高钙黑白钨混合矿、硫酸钠和浓硫酸混合均匀后于300～500℃下进行熟化得到熟料；将所得的熟料加入到水中,搅拌反应后过滤得到滤液和滤渣,滤液冷却结晶后得到的硫酸钠晶体返回用于高钙黑白钨混合矿的熟化,所得的结晶母液返回用于熟料的水浸；将所得滤渣与磷酸溶液混合搅拌反应,固液分离后得到含钨溶液和酸浸出渣。本发明采用硫酸熟化-磷酸浸出的方式处理高钙黑白钨混合矿,克服钙含量高对于传统冶炼工艺的影响,保证高钙黑白钨混合矿的高效分解的同时,实现了分解渣的资源化利用,为高钙黑白钨混合矿的资源高效利用提供了一条新的途径。(The invention discloses a method for treating high-calcium wolframite and wolframite mixed ore, which comprises the steps of uniformly mixing the high-calcium wolframite and wolframite mixed ore, sodium sulfate and concentrated sulfuric acid, and curing at 300-500 ℃ to obtain clinker; adding the obtained clinker into water, stirring for reaction, filtering to obtain filtrate and filter residue, cooling and crystallizing the filtrate to obtain sodium sulfate crystals, returning the sodium sulfate crystals to the aging of the high-calcium wolframite and wolframite mixed ore, and returning the obtained crystallization mother liquor to the water leaching of the clinker; mixing the obtained filter residue and phosphoric acid solution, stirring and reacting, and carrying out solid-liquid separation to obtain a tungsten-containing solution and acid leaching residue. The method adopts a sulfuric acid curing-phosphoric acid leaching mode to treat the high-calcium black-white tungsten mixed ore, overcomes the influence of high calcium content on the traditional smelting process, realizes the resource utilization of the decomposed slag while ensuring the high-efficiency decomposition of the high-calcium black-white tungsten mixed ore, and provides a new way for the high-efficiency utilization of the resources of the high-calcium black-white tungsten mixed ore.)

1. The method for treating the high-calcium black-white tungsten mixed ore is characterized by comprising the following steps of:

(1) uniformly mixing the high-calcium tungsten mixed ore, sodium sulfate and concentrated sulfuric acid, and curing at 300-500 ℃ to obtain clinker;

(2) adding the clinker obtained in the step (1) into water, stirring for reaction, filtering to obtain filtrate and filter residue, cooling and crystallizing the filtrate to obtain sodium sulfate crystals, returning the sodium sulfate crystals to the step (1) for curing the high-calcium black-white tungsten mixed ore, and returning the obtained crystallization mother liquor to water leaching of the clinker;

(3) mixing and stirring the filter residue obtained in the step (2) with a phosphoric acid solution for reaction, and carrying out solid-liquid separation to obtain a tungsten-containing solution and acid leaching residue.

2. The method for treating the high-calcium wolframite and black-white wolframite mixed ore according to claim 1, characterized in that: in the step (1), the Ca content in the high-calcium black-white tungsten mixed ore is 15-20 wt%.

3. The method for treating the high-calcium wolframite and black-white wolframite mixed ore according to claim 1, characterized in that: in the step (1), WO is added into the high-calcium black-white tungsten mixed ore₃The content is 25 to 50 wt%.

4. The method for treating the high-calcium wolframite and black-white wolframite mixed ore according to claim 1, characterized in that: in the step (1), the weight ratio of the high-calcium wolframite and wolframite mixed ore to the sodium sulfate to the concentrated sulfuric acid is 5-20: 2-10: 1, the mass fraction of the concentrated sulfuric acid is more than or equal to 85 wt%.

5. The method for treating the high-calcium wolframite and black-white wolframite mixed ore according to claim 1, characterized in that: in the step (1), the curing time is 1-5 h.

6. The method for treating the high-calcium wolframite and black-white wolframite mixed ore according to claim 1, characterized in that: in the step (2), the liquid-solid ratio of the clinker to the water is 1-5 mL/g, the stirring reaction temperature is 50-90 ℃, and the stirring reaction time is 15-60 min.

7. The method for treating the high-calcium wolframite and black-white wolframite mixed ore according to claim 1, characterized in that: in the step (3), the liquid-solid ratio of the filter residue to the phosphoric acid solution is 1-3 mL/g, and the concentration of the phosphoric acid solution is 50-150 g/L; the stirring reaction temperature is 50-90 ℃, and the time is 1-5 h.

Technical Field

The invention belongs to the extraction of rare metal tungsten in the field of extraction metallurgy, and particularly relates to a method for treating high-calcium tungsten mixed ore.

Background

Along with the development and utilization of tungsten resources, the tungsten resources have gradually poor endowment, more lean ores, less rich ores and complex components, the content of associated impurities such as calcium, phosphorus, silicon and the like is higher and higher, and particularly the increase of the content of calcium brings remarkable adverse effects on a tungsten smelting process. The research carried out by researchers on the influence of the calcium content on the tungsten ore decomposition process shows that when the calcium content in the tungsten ore is 0.85 percent, the WO in the alkali decomposition slag₃The content is only 0.75%, when the calcium content is increased to 3.15%, the slag contains WO under the same conditions₃Reaching 6.14 percent. When processing persimmon bamboo garden WO₃27.4 percent of black-white tungsten mixed ore and Ca9.54 percent of black-white tungsten mixed ore, when the amount of NaOH is 4 times of the theoretical amount, the slag contains WO₃Still up to 13.5%. In order to improve the decomposition efficiency of the high-calcium wolframite/wolframite mixed ore, some researchers add Na₃PO₄To improve the decomposition effect and convert calcium into Ca₅(PO₄)₃OH to increase the decomposition rate. Adding Na₃PO₄The alkali decomposition effect of the mixed ore of the black and white tungsten can be improved to a certain extent, but the cost is higher. When the calcium content in the mixed ore of black and white tungsten is higher (15-20%), Na₃PO₄The consumption of the soda ash is very large, the produced soda ash is greatly increased, the decomposition effect is obviously deteriorated, and WO in the slag₃The content is more than 2 percent and is far higher than the current industrial production level. Some researchers develop a method (2015102433825) for decomposing the scheelite and wolframine mixed ore by a sulfur-phosphorus mixed acid method, but the method needs to be carried out under the condition of 10 times of gravity acceleration, the energy consumption of high-energy ball milling is very high, and the industrialization difficulty is very large. Especially when high calcium tungsten mineral is treated, because of large amount of calcium sulfateThe generation of the tungsten oxide is serious in raw material wrapping, a compact blocking film is formed, the decomposition of tungsten minerals is blocked, and the recovery rate of tungsten is obviously reduced.

Disclosure of Invention

Aiming at the problems in the current tungsten smelting process, the invention aims to provide a method for treating high-calcium black-white tungsten mixed ore, which adopts a sulfuric acid curing-phosphoric acid leaching mode to treat the high-calcium black-white tungsten mixed ore, overcomes the influence of high calcium content on the traditional smelting process, realizes the resource utilization of decomposition slag while ensuring the high-efficiency decomposition of the high-calcium black-white tungsten mixed ore, and provides a new way for the high-efficiency utilization of the resources of the high-calcium black-white tungsten mixed ore.

In order to achieve the technical purpose, the invention adopts the following technical scheme:

a method for treating high-calcium black-white tungsten mixed ore comprises the following steps:

(1) uniformly mixing the high-calcium tungsten mixed ore, sodium sulfate and concentrated sulfuric acid, and curing at 300-500 ℃ to obtain clinker;

(2) adding the clinker obtained in the step (1) into water, stirring for reaction, filtering to obtain filtrate and filter residue, cooling and crystallizing the filtrate to obtain sodium sulfate crystals, returning the sodium sulfate crystals to the step (1) for curing the high-calcium black-white tungsten mixed ore, and returning the obtained crystallization mother liquor to water leaching of the clinker;

(3) mixing and stirring the filter residue obtained in the step (2) with a phosphoric acid solution for reaction, and carrying out solid-liquid separation to obtain a tungsten-containing solution and acid leaching residue.

Further, in the step (1), the Ca content in the high-calcium wolframite and black-white wolframite mixed ore is 15-20 wt%.

Further, in the step (1), in the high-calcium black-white tungsten mixed ore, WO₃The content is 25 to 50 wt%.

Further, in the step (1), the weight ratio of the high-calcium wolframite and wolframite mixed ore to the sodium sulfate to the concentrated sulfuric acid is 5-20: 2-10: 1, the mass fraction of the concentrated sulfuric acid is more than or equal to 85 wt%.

Further, in the step (1), the curing time is 1-5 h.

Further, in the step (2), the liquid-solid ratio of the clinker to the water is 1-5 mL/g, the stirring reaction temperature is 50-90 ℃, and the time is 15-60 min.

Further, in the step (3), the liquid-solid ratio of the filter residue to the phosphoric acid solution is 1-3 mL/g, and the concentration of the phosphoric acid solution is 50-150 g/L; the stirring reaction temperature is 50-90 ℃, and the time is 1-5 h.

The invention has the following beneficial effects:

1. the sulfuric acid curing treatment greatly improves the reaction activity of the high-calcium tungsten mixed ore, promotes the efficient leaching of tungsten, and the slag contains WO₃Can be as low as 0.2%;

2. compared with the traditional alkali pressure cooking process, the acid leaching slag produced by the method can be used as a raw material for cement production, so that the resource utilization of smelting slag is realized;

3. the process flow is simple and easy for industrial production.

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) With WO₃Uniformly mixing 40 wt% of black-white tungsten mixed ore with 15 wt% of Ca as a raw material according to the weight ratio of 5:2:1 to 5:2:1 of tungsten mineral, sodium sulfate and sulfuric acid (85 wt%), and curing in a rotary kiln at the curing temperature of 300 ℃ for 2 hours;

(2) adding the clinker into water according to the liquid-solid ratio of 1:1(mL/g), stirring and reacting at 90 ℃ for 30min, filtering to obtain filtrate and filter residue, cooling and crystallizing the filtrate to obtain sodium sulfate crystals, recycling the sodium sulfate crystals for a sulfuric acid curing process, and recycling the obtained crystallization mother liquor for leaching the clinker;

(3) adding the filter residue into 150g/L phosphoric acid solution according to the liquid-solid ratio of 3:1(mL/g), stirring and reacting for 3h at 90 ℃, performing solid-liquid separation to obtain tungsten-containing solution and acid leaching residue, and adding WO in the obtained acid leaching residue₃The content was 0.43 wt%.

Example 2

(1) With WO₃The mixed ore of black and white tungsten with 50 wt% and 16.8 wt% Ca content is used as raw material, and the tungsten mineral comprises sodium sulfate and sulfuric acid (98 wt%)) Uniformly mixing the components in a ratio of 20:5:1, and curing in a rotary kiln at the curing temperature of 400 ℃ for 1 h;

(2) adding the clinker into water according to the liquid-solid ratio of 3:1(mL/g), stirring and reacting at 50 ℃ for 60min, filtering to obtain filtrate and filter residue, cooling and crystallizing the filtrate to obtain sodium sulfate crystals, recycling the sodium sulfate crystals for a sulfuric acid curing process, and recycling the obtained crystallization mother liquor for leaching the clinker;

(3) adding the filter residue into 150g/L phosphoric acid solution according to the liquid-solid ratio of 1:1(mL/g), stirring and reacting for 3h at 70 ℃, performing solid-liquid separation to obtain tungsten-containing solution and acid leaching residue, and adding WO in the obtained acid leaching residue₃The content was 0.67 wt%.

Example 3

(1) With WO₃Taking 25 wt% of black-white tungsten mixed ore with 20 wt% of Ca as a raw material, uniformly mixing the raw material according to the weight ratio of 20:10:1 to 20: 98 wt% of tungsten mineral, and curing in a rotary kiln at the curing temperature of 300 ℃ for 2 hours;

(2) adding the clinker into water according to the liquid-solid ratio of 5:1(mL/g), stirring and reacting at 50 ℃ for 30min, filtering to obtain filtrate and filter residue, cooling and crystallizing the filtrate to obtain sodium sulfate crystals, recycling the sodium sulfate crystals for a sulfuric acid curing process, and recycling the obtained crystallization mother liquor for leaching the clinker;

(3) adding the filter residue into 50g/L phosphoric acid solution according to the liquid-solid ratio of 5:1(mL/g), stirring and reacting for 5h at 50 ℃, performing solid-liquid separation to obtain tungsten-containing solution and acid leaching residue, and adding WO in the obtained acid leaching residue₃The content was 0.81 wt%.

Example 4

(1) With WO₃Taking 35 wt% of black-white tungsten mixed ore with 18 wt% of Ca as a raw material, uniformly mixing the raw material according to the weight ratio of 20:5:1 to 20:5 of tungsten mineral, sodium sulfate and sulfuric acid (85 wt%), and curing in a rotary kiln at 500 ℃ for 1 h;

(2) adding the clinker into water according to the liquid-solid ratio of 1:1(mL/g), stirring and reacting at 90 ℃ for 15min, filtering to obtain filtrate and filter residue, cooling and crystallizing the filtrate to obtain sodium sulfate crystals, recycling the sodium sulfate crystals for a sulfuric acid curing process, and recycling the obtained crystallization mother liquor for leaching the clinker;

(3) adding the filter residue into 100g/L phosphoric acid solution according to the liquid-solid ratio of 2:1(mL/g), stirring and reacting for 3h at 90 ℃, performing solid-liquid separation to obtain tungsten-containing solution and acid leaching residue, and adding WO in the obtained acid leaching residue₃The content was 0.20 wt%.