阅读说明：本技术 一种基于硫化铋矿相转化的提铋方法 (Bismuth extraction method based on phase transformation of bismuth sulfide ore ) 是由 王恒辉 陈永明 周晓源 邓鑫杰 何醒民 杨声海 何静 于 2019-09-04 设计创作，主要内容包括：本发明涉及一种基于硫化铋矿相转化的提铋方法,先将转相剂与硫化铋矿混合调浆,获得混合浆料；其中,所述转相剂包含磺酸；优选地,所述硫化铋矿为硫化铋精矿；将所述混合浆料置于反应釜中,进行氧压转相反应处理后,固液分离,获得转相渣和转相液；对所述转相渣进行酸性浸出处理,然后进行固液分离,获得浸出液和浸出渣。本发明的提铋方法可实现铋的选择性浸出,降低浸出液中铁、铅、硅等杂质元素的净化负担,简化了后续中和水解、电沉积等铋产品回收的工艺流程。(The invention relates to a bismuth extraction method based on bismuth sulfide ore phase transformation, which comprises the steps of mixing a phase transfer agent and bismuth sulfide ore, and pulping to obtain mixed slurry; wherein the phase inversion agent comprises a sulfonic acid; preferably, the bismuth sulfide ore is bismuth sulfide concentrate; placing the mixed slurry in a reaction kettle, carrying out oxygen pressure phase inversion reaction treatment, and carrying out solid-liquid separation to obtain phase inversion slag and phase inversion liquid; and carrying out acid leaching treatment on the phase inversion slag, and then carrying out solid-liquid separation to obtain a leaching solution and leaching slag. The bismuth extraction method can realize selective leaching of bismuth, reduce the purification burden of impurity elements such as iron, lead, silicon and the like in the leaching solution, and simplify the subsequent process flow of bismuth product recovery such as neutralization hydrolysis, electrodeposition and the like.)

1. A bismuth extraction method based on phase inversion of bismuth sulfide ore is characterized by comprising the following steps:

s1, mixing the phase transfer agent and the bismuth sulfide ore, and carrying out size mixing to obtain mixed size;

wherein the phase inversion agent comprises a sulfonic acid; preferably, the bismuth sulfide ore is bismuth sulfide concentrate;

s2, placing the mixed slurry obtained in the step S1 in a reaction kettle, carrying out oxygen pressure phase inversion reaction treatment, and then carrying out solid-liquid separation to obtain phase inversion slag and phase inversion liquid;

and S3, performing acidic leaching treatment on the phase inversion slag obtained in the S2, and performing solid-liquid separation to obtain a leaching solution and leaching slag.

2. The bismuth extraction method according to claim 1, further comprising a step of grinding bismuth sulfide ore before S1, preferably, the grain size of the ground bismuth sulfide ore is less than 50 μm to 97 wt%.

3. The method for extracting bismuth according to claim 1, wherein in S1, the concentration of sulfonic acid in the phase transfer agent is 5-240g/L, preferably 20-200g/L, and the phase transfer agent preferably further contains iron, generally, the concentration of iron is 0.5 ~ 40g/L, preferably 4 ~ 20 g/L.

4. The method of claim 1, wherein in S1, the sulfonic acid comprises methanesulfonic acid.

5. The bismuth extraction method according to claim 1, wherein in S1, the liquid-solid mass ratio of the mixed slurry is 3-10: 1.

6. the method for extracting bismuth as claimed in claim 1, wherein in S2, the temperature in the reaction vessel is controlled to be 100-180 ℃, the oxygen partial pressure is 1.1-2MPa, and the reaction time is 0.5-5h during the oxygen pressure phase inversion reaction; preferably, a surfactant is added into the reaction kettle during the oxygen pressure phase inversion reaction, and further preferably, the surfactant comprises at least one of lignosulfonate, o-phenylenediamine and m-phenylenediamine.

7. The method for extracting bismuth according to any one of claims 1 to 6, wherein the phase-inversion liquid obtained in S2 is returned to step S1 as one of the slurrying raw materials.

8. The bismuth extraction method according to any one of claims 1 to 6, wherein before S3, the method further comprises a step of wet grinding the phase inversion slag, preferably, the particle size of the phase inversion slag after wet grinding is 3 to 100 μm.

9. A bismuth extraction method according to any one of claims 1 to 6, wherein in the S3, during the acid leaching treatment, the leaching agent contains one or more of methanesulfonic acid, fluosilicic acid, hydrochloric acid, nitric acid and borosilicate, preferably, the total concentration of acid in the leaching agent is 0.5mol/L ~ 5mol/L, and preferably, the leaching temperature is 40-90 ℃.

10. The method for extracting bismuth according to any one of claims 1 to 6, wherein the bismuth sulfide ore contains 10 to 30 mass% of bismuth, 10 to 30 mass% of sulfur, and 10 to 30 mass% of iron.

Technical Field

The invention relates to a bismuth extraction method based on bismuth sulfide ore phase transformation, in particular to a two-stage bismuth extraction method based on bismuth sulfide ore phase transformation, and belongs to the technical field of non-ferrous metal hydrometallurgy.

Background

The wet bismuth smelting process is suitable for bismuth-containing materials with low grade and complex components, and the main procedures comprise leaching, purification and impurity removal (Chinese patent CN 106978538A), neutralization and hydrolysis (Chinese patent CN 108557881A) or electrodeposition (Chinese patent CN 101775619A) and the like. Acid leaching is generally adopted for bismuth oxide ores, most of bismuth is leached into solution in a chloride system through oxidation leaching for bismuth sulfide ores, and the used oxidants comprise oxygen and FeCl₃、Cl₂Chlorate, nitric acid, and the like. After the bismuth leachate is purified and decontaminated by methods such as replacement, sulfuration precipitation and the like, a neutralizing agent can be added for neutralization and hydrolysis to produce bismuth oxychloride which is used as a raw material for smelting bismuth by a pyrogenic process, and metal bismuth can also be produced by diaphragm electrodeposition. Although the methods can realize the leaching of bismuth, the methods also have a plurality of defects, such as serious equipment corrosion, bad operation environment and the like, and particularly, iron in raw materials is easy to enter a solution together, so that the leaching solution is difficult to filter, and the production is not facilitated; in the process of diaphragm electrodeposition, the unstable valence state of iron ions can cause low current efficiency and large electric energy consumption; iron often enters the bismuth oxychloride slag during bismuth chloride hydrolysis, so that the subsequent treatment difficulty is increased.

For example, chinese patent CN1140209 discloses a bismuth sulfide ore hydrometallurgy method, which is characterized in that bismuth sulfide ore is leached in an anode area with a diaphragm, sulfur is oxidized into elemental sulfur, bismuth enters into an electrolyte in an ionic state, bismuth ions in the electrolyte are separated out on a cathode through the diaphragm, and metal bismuth powder is obtained. The method has short flow and high metal recovery rate, but the chlorine gas easily produced by the anode is easy to escape, the operation environment is deteriorated, and the iron is enriched in the solution and is difficult to treat.

Disclosure of Invention

Aiming at increasingly severe environmental protection requirements and certain defects of the existing bismuth extraction process, one of the purposes of the invention is to provide a two-stage bismuth leaching extraction method based on bismuth sulfide ore phase transformation, the method is simple to operate, bismuth can be efficiently dissolved out, the obtained leachate has low impurity element content, and SO is not generated₂And the environmental protection advantage is obvious.

In order to solve the technical problems, the technical scheme of the invention is as follows:

a bismuth extraction method based on phase inversion of bismuth sulfide ore comprises the following steps:

s1, mixing the phase transfer agent and the bismuth sulfide ore, and carrying out size mixing to obtain mixed size;

wherein the phase inversion agent comprises a sulfonic acid; preferably, the bismuth sulfide ore is bismuth sulfide concentrate;

s2, placing the mixed slurry obtained in the step S1 in a reaction kettle, carrying out oxygen pressure phase inversion reaction treatment, and then carrying out solid-liquid separation to obtain phase inversion slag and phase inversion liquid; preferably, the reaction kettle is an autoclave;

and S3, performing acidic leaching treatment on the phase inversion slag obtained in the S2, and performing solid-liquid separation to obtain a leaching solution and leaching slag.

Optionally, before S1, the method further comprises grinding the bismuth sulfide ore, preferably, grinding until 97wt% of bismuth sulfide ore has a particle size of less than 50 μm.

Optionally, in S1, the concentration of the sulfonic acid in the phase transfer agent is 5-240g/L, preferably 20-200g/L, and preferably, the phase transfer agent further contains iron, typically, the concentration of iron is 0.5 ~ 40g/L, preferably 4 ~ 20 g/L.

Alternatively, in S1, the sulfonic acid comprises methanesulfonic acid, preferably methanesulfonic acid.

The methanesulfonic acid is organic strong acid, has good thermal stability and has higher solubility to bismuth. The methanesulfonic acid can be biodegraded, the recycling rate can reach 80%, and the environmental protection advantage is obvious.

Optionally, in S1, the liquid-solid mass ratio of the mixed slurry is 3 to 10:1, generally from 3 to 9:1, preferably from 3 to 8: 1.

Optionally, in S2, in the process of the oxygen pressure phase inversion reaction, the temperature in the reaction kettle is controlled to be 100-.

Preferably, a surfactant is added into the reaction kettle during the oxygen pressure phase inversion reaction, and further preferably, the surfactant comprises at least one of lignosulfonate, o-phenylenediamine and m-phenylenediamine. The addition of the surfactant can activate the particle surface, avoid the particle from being wrapped and reduce the reaction effect.

Optionally, the surfactant is used in an amount of 0.1 ~ 0.9.9% by mass of the bismuth sulfide ore.

Optionally, the phase transfer liquid obtained in S2 is returned to step S1 as one of the size mixing raw materials, so as to improve the utilization rate of the phase transfer agent.

Optionally, before S3, a step of wet-grinding the phase inversion residue is further included, and preferably, after the wet grinding, the particle size of the phase inversion residue is 3-100 μm.

Optionally, in the step S3, during the acidic leaching treatment, the leaching agent contains one or more of methanesulfonic acid, fluosilicic acid, hydrochloric acid, nitric acid and borosilicate, preferably, the total concentration of the acid in the leaching agent is 0.5mol/L ~ 5mol/L, and preferably, the leaching temperature is 40-90 ℃.

Preferably, stirring is kept during the acid leaching treatment, and the stirring speed is generally 100-1200 rpm to promote mass transfer and accelerate the reaction.

Further, in S3, the amount of acid added is determined according to the bismuth content in the slag, and generally, 1 ~ 1.5.5 times of the theoretical amount of acid is added.

Alternatively, in S3, the acid leaching treatment time is 0.1-5h, preferably 0.5-3 h.

Further, in the bismuth sulfide ore, the mass percentage of bismuth is 10-30%, the mass percentage of sulfur is 10-30%, and the mass percentage of iron is 10-30%.

A bismuth extraction method based on phase inversion of bismuth sulfide ore comprises the following steps:

1) carrying out fine grinding treatment on the bismuth sulfide ore by using a vertical grinding machine, and then drying the materials;

2) mixing the phase transfer agent and the pretreated sulfide concentrate, adding the mixture into a high-pressure kettle, and stirring;

3) heating the ore pulp to a set temperature under the condition of keeping stirring, introducing oxygen, starting oxygen pressure phase inversion reaction, carrying out solid-liquid separation after the reaction is carried out for 0.5 ~ 5 hours, and obtaining phase inversion slag and phase inversion liquid;

4) wet grinding the phase inversion slag by a vertical mill, then mixing the wet-ground phase inversion slag with a leaching agent, adding the mixture into a reaction kettle, adding an additive at the same time, and stirring;

5) heating the ore pulp to a set temperature under the condition of keeping stirring, starting leaching reaction, carrying out solid-liquid separation after the reaction is carried out for 0.1 ~ 3 hours, and obtaining leachate and leaching residues.

The leachate after the bismuth is extracted by the wet method needs to enter subsequent purification, impurity removal and electrodeposition processes, and because the electrodeposition process of bismuth has higher requirement on the content of Fe ions, in order to reduce the influence of Fe ions on cathode bismuth precipitation in the electrodeposition process, the leachate should reduce the content of Fe ions as much as possible so as to reduce the subsequent purification load and ensure that the bismuth electrodeposition process is smoothly implemented. The leaching solution obtained by the method can well meet the requirement of bismuth electrodeposition.

Aiming at the problem that the purification and impurity removal of leachate are difficult due to the fact that a large amount of associated minerals such as pyrite and chalcopyrite are dissolved in the existing process of directly leaching bismuth from bismuth sulfide, the invention provides a method for converting bismuth sulfide into easily soluble compounds (existing in phase-inversion slag) such as bismuth hydroxide, bismuth oxide and basic sulfate by combining a bismuth sulfide ore phase conversion and acid leaching process, and converting iron into an iron vitriol slag phase (existing in phase-inversion slag), and dissolving the iron with a proper amount of dilute acid exceeding the theoretical amount of bismuth, so that the efficient dissolution of bismuth is realized, the leachate with high bismuth concentration and low concentration of other impurities such as iron is obtained, and iron is still retained in leached slag.

Compared with the prior art, the bismuth extraction method can realize selective leaching of bismuth, reduce the purification burden of impurity elements such as iron, lead, silicon and the like in the leaching solution, and simplify the subsequent process flow of bismuth product recovery such as neutralization hydrolysis, electrodeposition and the like; specifically, the leaching rate of bismuth can reach more than 94wt%, and the concentration of iron in the leaching solution is low and can be as low as 0.2 g/L.

Drawings

FIG. 1 is a flow chart of the bismuth extraction method of the present invention.

FIG. 2 is an XRD analysis pattern of the phase-change slag in example 1.

Detailed Description

The following description describes alternative embodiments of the invention to teach one of ordinary skill in the art how to make and use the invention.