阅读说明：本技术 一种砷菱铅矾的电化学处理方法 (Electrochemical treatment method of arsenopyrite ) 是由 康金星 宋磊 王鑫 于传兵 郭素红 王传龙 刘志国 王亚运 于 2020-05-30 设计创作，主要内容包括：本发明公开了一种砷菱铅矾的电化学处理方法,包括：a将砷菱铅矾与酸性电解液混合作为电解质置于电化学反应装置阳极室内,阴极室内充填活性炭；b向阴阳极间输入电压,使所述电解质进行电化学催化溶解反应和电化学沉积反应,砷在阳极沉积,铅在活性炭上沉积；c将步骤b得到的阳极沉积产物、活性碳电沉积铅产物与电解液分别过滤分离回收。本发明的砷菱铅矾的电化学处理方法,能够充分回收利用砷菱铅矾中的铅,铅与砷分离效率高,无污染、工艺简单,并且能耗低。(The invention discloses an electrochemical treatment method of arsenopyrite, which comprises the following steps: a, mixing arsenopyrite with an acidic electrolyte to be used as an electrolyte, placing the electrolyte in an anode chamber of an electrochemical reaction device, and filling activated carbon in a cathode chamber; b, inputting voltage between the cathode and the anode to enable the electrolyte to perform electrochemical catalytic dissolution reaction and electrochemical deposition reaction, wherein arsenic is deposited on the anode, and lead is deposited on the activated carbon; c, respectively filtering, separating and recycling the anode deposition product, the activated carbon electro-deposition lead product and the electrolyte obtained in the step b. The electrochemical treatment method of arsenopyrite can fully recycle lead in arsenopyrite, and has the advantages of high lead and arsenic separation efficiency, no pollution, simple process and low energy consumption.)

1. An electrochemical treatment method of arsenopyrite is characterized by comprising the following steps:

a, mixing arsenopyrite with an acidic electrolyte to be used as an electrolyte, placing the electrolyte in an anode chamber of an electrochemical reaction device, and filling activated carbon in a cathode chamber;

b, inputting voltage between the cathode and the anode to enable the electrolyte to perform electrochemical catalytic dissolution reaction and electrochemical deposition reaction, wherein arsenic is deposited on the anode, and lead is deposited on the activated carbon;

and c, filtering and separating the anode deposition product, the activated carbon electro-deposition lead product and the electrolyte obtained in the step b respectively.

2. The method of claim 1, wherein in step a, the acidic electrolyte is selected from hydrochloric acid or nitric acid and their corresponding Al-containing solutions³⁺Or Ca²⁺The metal cation salt is composed of an acid electrolyte with pH of 1-3 and Al³⁺Or Ca²⁺The mass percentage of the salt is 0.1-10%.

3. The method of claim 2, wherein in step a, the molar ratio of the sum of the molar amounts of the metal cations and Fe in arsenopyrite to As in arsenopyrite is 1.5.

4. The electrochemical treatment method of arsenopyrite according to claim 1, wherein in the step a, the liquid-solid ratio of the acidic electrolyte to the arsenopyrite is 0.5-10: 1.

5. The process according to claim 1, characterized in that in step b, the cathodic potential is: -0.6 to-2.0V, and the potential difference between the anode chamber and the cathode chamber is 0.6 to 2.8V.

6. The process of claim 5, wherein the cathodic potential is: -1.2 to-1.6V, and the potential difference between the anode chamber and the cathode chamber is 1.2 to 2V.

7. The process of claim 1, wherein in step b, the cathode compartment is separated from the anode compartment by a permeable membrane, graphite felt or inert mesh.

8. The method of claim 1, wherein in step b, the acid electrolyte flows from the anode chamber to the three-dimensional activated carbon cathode chamber of the electrochemical reactor in a circulating countercurrent manner, and then flows from the cathode chamber back to the anode chamber through an external circulating pipeline.

9. The method of claim 1, wherein the arsenopyrite is selected from at least one of a raw arsenopyrite ore, a material containing arsenopyrite, or a plumbite containing arsenic.

10. An electrochemical treatment method of gold ore containing arsenopyrite is characterized by comprising the following steps:

mixing gold ore and acid electrolyte as electrolyte, placing the mixture into an anode chamber of an electrochemical reaction device, filling activated carbon into a cathode chamber, wherein the concentration of hydrochloric acid in the acid electrolyte is 0.1-0.2M, the mass concentration of aluminum hypochlorite is 3-6%, and the liquid-solid ratio of the acid electrolyte to the gold ore is 3-5: 1;

b, inputting voltage between the cathode and the anode, wherein the cathode potential is as follows: -1.6 to-2.0V, the potential difference between the anode chamber and the cathode chamber is 1.6 to 2.4V, the electrolyte is subjected to electrochemical catalytic dissolution reaction and electrochemical deposition reaction, arsenic is deposited on the anode, and gold and lead are deposited on the activated carbon;

c, filtering, separating and recycling the anode deposition product, the activated carbon electrodeposition product and the electrolyte obtained in the step b respectively.

Technical Field

The invention belongs to the technical field of hydrometallurgy of arsenopyrite, and particularly relates to an electrochemical treatment method of arsenopyrite.

Background

Arsenopyrite is a mineral of arsenite and has a standard chemical formula of PbFe₃[AsO₄][SO₄](OH)₆Theoretical lead content of 29.1% and arsenic content of 10.5%, found in the oxidation zone of certain high-arsenic polymetallic oxidic or sulfidic deposits, are also distributed as harmful impurities in certain iron-capped limonites, or may be present as harmful substances in the electrochemical processing of certain materials. The research on arsenopyrite began to be reported in China at the end of the last 90 s, but the research contents are mostly limited to mineralogy and geological significance of the cause. The reported mineral properties of arsenopyrite show that lead and arsenic in the mineral are closely related, the mineral has poor crystallinity, and the mineral has structures of a fine vein shape, a net vein shape, a dip-dyeing shape and the like and is closely related to other minerals. For example, in Fujian iron cap type limonite with an iron grade of 46.10%, the content of lead and arsenic in the ore reaches 2.54% and 1.99% respectively, and the content of lead and arsenic in the iron ore concentrate directly influences the reasonable development of the ore. And the content of arsenopyrite mineral is up to 50 percent like gold-containing oxidized ore in southern Anhui Ling Lv mountain area. Compared with domestic and foreign arsenopyrite, the distribution of the arsenopyrite is relatively more, for example, lead minerals in Anbouran oxidized lead-zinc ore deposits in northwest of Iran are mainly white lead ore, arsenopyrite and arsenopyrite, and part of the high-arsenopyrite in Soruim copper-lead-zinc polymetallic projects developed by African Congo (cloth) is the Chinese goldLead resource of content. The reasonable development and utilization process of these resources faces the separation and disposal problem of arsenic and lead.

Arsenopyrite exists in the oxidation zone of certain polymetallic oxidized ore or sulfide ore, contains higher lead and is an important potential resource of the lead; however, since the arsenic content is high at the same time, the recovery and utilization of the arsenic-containing component should be properly treated at the same time. At present, few reports are reported on the processing and utilizing technology of the arsenopyrite, the mined high-grade arsenopyrite-containing material is basically stockpiled, or the quality of other concentrate products is influenced by low-grade associated components serving as difficult-to-process components, and the high-grade arsenopyrite-containing material is not reasonably utilized or separated.

As the arsenopyrite has large difficulty coefficient in beneficiation, enrichment and recovery, the surface of the arsenopyrite is easy to hydrate, the floatability is poor, the sulfuration flotation is difficult, and particularly the flotation process is obviously influenced by metal ions, such as a very small amount of Fe³⁺Flotation is obviously deteriorated; in addition, arsenopyrite has a specific gravity and a susceptibility similar to that of limonite and is generally difficult to separate from certain iron concentrates by physical means.

The lead is recovered from the arsenopyrite with high content or enriched arsenopyrite, and the lead still needs to be treated and recovered by a wet method or a pyrogenic method.

In pyrogenic processing of arsenopyrite, a reducing agent is usually added to reduce the arsenic-containing material to As₂O₃The post-volatilized and collected white arsenic has small market, but the problem that 1) the environmental pressure caused by arsenic-containing flue gas generated by roasting is very large; 2) after roasting, part of As still remains in the slag phase and is difficult to fully treat; 3) because more OH-is preferentially removed in the roasting process of the minerals, the treatment energy consumption is very high; 4) the fixed investment cost of the pyrogenic process is relatively large.

In the wet separation process of some materials containing lead and arsenic, arsenic is mostly dissolved in solution as alkali arsenate by using an alkaline solution, for example, a sodium hydroxide leaching system dissolves arsenic as sodium arsenite, and lead remains in a slag phase, but for arsenopyrite, the leaching efficiency of arsenic is generally low because iron hydroxide and lead alum components are difficult to destroy and decompose by using alkali treatment.

Therefore, there is an urgent need to develop a treatment method capable of effectively recovering lead from arsenopyrite.

Disclosure of Invention

The present invention is based on the discovery and recognition by the inventors of the following facts and problems:

arsenopyrite behaves like a plumbite (PbSO) in terms of elemental and compound composition₄) Iron arsenate (FeAsO)₄) And iron hydroxide (Fe (OH)₃) The physicochemical properties of the mixture of the three. At present, the reports about the treatment processes of the three substances relate to mineral separation and enrichment, hydrometallurgy and pyrometallurgical treatment, but are difficult to apply to the recovery of arsenopyrite.

When the beneficiation enrichment method is adopted, the arsenopyrite has good hydration characteristics, is poor in natural floatability and difficult to be vulcanized, and although certain reagents with stronger oxidized mineral collecting capacity, such as hydroximic acid in a water sample, have certain flotation capacity on the arsenopyrite, the arsenopyrite flotation process is influenced by pH and Pb²⁺、Fe³⁺The plasma dissolution state influence is very obvious, especially on Fe²⁺/Fe³⁺The ion response is particularly strong, and related technologies such as "influence research of metal ions on floatability of lead vitriol under CSY collecting system" and "Fe" of Torrei et al²⁺/Fe³⁺The influence of hydroximic acid on collecting plumbite in a water sample indicates that a small amount of Fe³⁺The floating of the lead alum can be strongly inhibited. Therefore, the flotation method for enriching the arsenopyrite is difficult to achieve the ideal effect.

When lead, iron and arsenic in arsenopyrite are separated by pyrogenic process, the arsenic-containing material is reduced to As by adding a reducing agent₂O₃The white arsenic is collected after the post-volatilization, but on one hand, the environmental pressure brought by the arsenic-containing flue gas generated by roasting is large, and part of As still remains in the slag phase after the roasting, and the treatment is insufficient, on the other hand, because more OH-is preferentially removed in the roasting process of the minerals, the treatment energy consumption is very high, and in addition, the fixed investment of the pyrogenic treatment is relatively large. Thus, pyrogenic treatment of such minerals is not ideal.

CN108570684A discloses an electrochemical treatment method of arsenic-containing soot, which adopts a sodium hydroxide/potassium hydroxide leaching system to leach arsenic-containing soot and copper substances in advanceArsenic in the material is used to obtain a soluble sodium arsenate product, and lead and other noble metals are left in the slag, so that the arsenic and the lead are separated by a wet method; but Fe (OH) in arsenopyrite₃、PbSO₄Is difficult to be corroded and damaged by alkali, so that the arsenic leaching rate is not high, and an alkali metal leaching system is not well applicable to arsenopyrite. Some acid systems, such as hydrochloric acid-chloride systems, can corrode and destroy the arsenopyrite structure, so that most of lead and arsenic are dissolved into solution as ions, and then arsenic and lead are separated, but the problem of fixation of arsenic in the solution is still difficult. Many researches show that iron and salts thereof can be used for arsenic-containing waste water, waste residue and waste gas to fix arsenic, and are effective stabilizers, and although iron salts and oxidants can be used for stably fixing arsenic into ferric arsenate precipitates under neutral conditions, the iron salts and the oxidants have poor treatment effect under acidic conditions.

In view of the above, the inventors believe that in order to obtain a suitable arsenic and lead leaching rate, an acidic leaching system should be used to decompose and destroy the ferric hydroxide. However, although the acid leaching system can obtain good leaching rate of lead and arsenic, the difficulty problem is the stable solidification problem of arsenic. Therefore, how to dissolve arsenopyrite, separate lead from arsenic, and stably solidify arsenic is the key for wet development and utilization of arsenopyrite.

The present invention is directed to solving, at least to some extent, one of the technical problems in the related art. Therefore, the embodiment of the first aspect of the invention provides an electrochemical treatment method of arsenopyrite, which can fully recycle lead in the arsenopyrite, and has the advantages of high lead and arsenic separation efficiency, no pollution, simple process and low energy consumption.

The electrochemical treatment method of arsenopyrite according to the embodiment of the invention comprises the following steps:

a, mixing arsenopyrite with an acidic electrolyte to be used as an electrolyte, placing the electrolyte in an anode chamber of an electrochemical reaction device, and filling activated carbon in a cathode chamber;

b, inputting voltage between the cathode and the anode to enable the electrolyte to perform electrochemical catalytic dissolution reaction and electrochemical deposition reaction, wherein arsenic is deposited on the anode, and lead is deposited on the activated carbon;

c, respectively filtering, separating and recycling the anode deposition product, the activated carbon electro-deposition lead product and the electrolyte obtained in the step b.

The electrochemical treatment method of the arsenopyrite according to the embodiment of the first aspect of the invention has the beneficial effects that: 1. according to the method provided by the embodiment of the invention, an acidic electrolyte solution is adopted to carry out electrochemical treatment on the arsenopyrite, so that arsenic, iron and lead in the arsenopyrite are dissolved and leached in the solution, activated carbon is filled in a cathode chamber to serve as a three-dimensional electrode cathode and an adsorbing material serving as metal ions, lead is dissolved in an ion form by acid, electrodeposition is carried out after the lead is selectively transferred to the cathode, lead metal is recovered, the recovery rate of lead reaches more than 96.0%, arsenic is fully leached in an anode chamber, arsenic-containing anions are selectively enriched in an anode reaction chamber, and are subjected to coprecipitation with high-valence cations in the electrolyte solution to be stably solidified at an anode, and the recovery rate of arsenic reaches more than 99.5%; 2. the method of the embodiment of the invention can greatly improve the ecological compatibility of the utilization of the arsenic-containing material, the arsenic is leached in the anode space of the feeding material, the stable solidification of the arsenic is completed in the same step, the dissolution leaching and the precipitation solidification of the arsenic-containing component are synchronously performed, the arsenic is not required to be secondarily stably fixed, the precipitation of lead is performed in the three-dimensional cathode filled with the activated carbon particles, the leaching of lead and the precipitation thereof in the three-dimensional filled cathode are simultaneously performed in the same step, and the treatment efficiency is improved; 3. the method of the embodiment of the invention improves the efficiency of wet lead extraction in arsenopyrite, can process a large amount of arsenopyrite materials at one time, and can recycle the electrolyte after being processed, thereby effectively improving the working efficiency, and reducing the energy consumption and the extraction time; 4. the method of the embodiment of the invention has simple process, convenient maintenance and repair and easy implementation.

According to the electrochemical treatment method of arsenopyrite, in the step a, the acid electrolyte is hydrochloric acid or nitric acid and corresponding Al-containing electrolyte³⁺Or Ca²⁺The metal cation salt is composed of an acid electrolyte with pH of 1-3 and Al³⁺Or Ca²⁺The mass percentage of the salt is 0.1-10%.

According to the electrochemical treatment method of the arsenopyrite, provided by the embodiment of the invention, in the step a, the molar ratio of the sum of the molar amounts of the metal cations and Fe in the arsenopyrite to As in the arsenopyrite is 1.5.

According to the electrochemical treatment method of arsenopyrite, provided by the embodiment of the invention, in the step a, the liquid-solid ratio of the acidic electrolyte to the arsenopyrite is 0.5-10: 1.

According to the electrochemical treatment method of arsenopyrite in the embodiment of the invention, in the step b, the cathode potential is as follows: -0.6 to-2.0V, and the potential difference between the anode chamber and the cathode chamber is 0.6 to 2.8V.

According to the electrochemical treatment method of arsenopyrite, provided by the embodiment of the invention, the cathode potential is as follows: -1.2 to-1.6V, and the potential difference between the anode chamber and the cathode chamber is 1.2 to 2V.

According to the electrochemical treatment method of the arsenopyrite, in the step b, the cathode chamber is separated from the anode chamber by a permeable membrane, a graphite felt or an inert screen.

According to the electrochemical treatment method of the arsenopyrite, in the step b, the acid electrolyte is made to flow from the anode chamber to the three-dimensional activated carbon cathode chamber of the electrochemical reaction device in a circulating countercurrent mode, and then flows out from the cathode chamber and returns to the anode chamber through an external circulating pipeline.

According to the electrochemical treatment method of the arsenopyrite, provided by the embodiment of the invention, the arsenopyrite is selected from at least one of raw arsenopyrite ore, arsenopyrite-containing material or arsenopyrite-containing plumbite.

The embodiment of the second aspect of the invention also provides an electrochemical treatment method of gold ore containing arsenopyrite, which comprises the following steps:

mixing gold ore and acid electrolyte as electrolyte, placing the mixture into an anode chamber of an electrochemical reaction device, filling activated carbon into a cathode chamber, wherein the concentration of hydrochloric acid in the acid electrolyte is 0.1-0.2M, the mass concentration of aluminum hypochlorite is 3-6%, and the liquid-solid ratio of the acid electrolyte to the gold ore is 3-5: 1;

b, inputting voltage between the cathode and the anode, wherein the cathode potential is as follows: -1.6 to-2.0V, the potential difference between the anode chamber and the cathode chamber is 1.6 to 2.4V, the electrolyte is subjected to electrochemical catalytic dissolution reaction and electrochemical deposition reaction, arsenic is deposited on the anode, and gold and lead are deposited on the activated carbon;

c, filtering, separating and recycling the anode deposition product, the activated carbon electrodeposition product and the electrolyte obtained in the step b respectively.

The electrochemical treatment method for the gold ore containing the arsenopyrite has the advantages that the method can be used for dissolving and leaching arsenic, iron, lead and gold in the gold ore containing the arsenopyrite into a solution by adopting an electrochemical method in an acid environment, the lead and the gold are dissolved by acid in an ionic form and directionally deposited on a cathode, the arsenic is fully leached in an anode chamber and then precipitated and solidified, the lead recovery rate can reach 97.8%, the gold recovery rate can reach 99.8%, and the arsenic recovery rate can reach 99.8%.

Drawings

FIG. 1 is a process flow diagram of a method of electrochemical treatment of arsenopyrite in accordance with an embodiment of the present invention;

FIG. 2 is a schematic diagram illustrating the electrochemical reaction principle of the method for electrochemical treatment of arsenopyrite according to the embodiment of the present invention.

Detailed Description

Reference will now be made in detail to embodiments of the present invention, examples of which are illustrated in the accompanying drawings. The embodiments described below with reference to the drawings are illustrative and intended to be illustrative of the invention and are not to be construed as limiting the invention.

As shown in fig. 1 and 2, an electrochemical treatment method of arsenopyrite according to an embodiment of the present invention includes:

a, mixing arsenopyrite with an acidic electrolyte to be used as an electrolyte, placing the electrolyte in an anode chamber of an electrochemical reaction device, and filling activated carbon in a cathode chamber;

b, inputting voltage between the cathode and the anode to enable the electrolyte to perform electrochemical catalytic dissolution reaction and electrochemical deposition reaction, wherein arsenic is deposited on the anode, and lead is deposited on the activated carbon;

c, respectively filtering, separating and recycling the anode deposition product, the activated carbon electro-deposition lead product and the electrolyte obtained in the step b.

According to the electrochemical treatment method of arsenopyrite provided by the embodiment of the invention, the acid dissolution reaction in the anode chamber in the treatment process is as follows:

PbSO₄·FeAsO₄·Fe(OH)_3(s)+3H⁺ _(aq)→Pb²⁺ _(aq)+SO₄ ^2- _(aq)+AsO₄ ^3- _(aq)+3Fe³⁺ _(aq)+3H₂O

the stable arsenic curing reaction in the anode chamber is as follows:

Al³⁺(Fe³⁺,Ca²⁺)_(aq)+AsO₄ ^3- _(aq)→Al(Fe³⁺,Ca²⁺)AsO_4(s)↓

the chemical reaction of the activated carbon cathode for adsorbing and depositing the lead comprises the following steps:

Pb²⁺+2e→Pb

the electrochemical catalytic dissolution reaction means that arsenic and lead are dissolved into Pb from solid compounds containing arsenic and lead²⁺And AsO₄ ^3-Ionic states, facilitating migration movement in an electric field.

The electrochemical deposition reaction refers to that arsenic-containing anions are enriched in the anode chamber and then undergo a complexing precipitation reaction with certain metal cations in the electrolyte, wherein the metal cations are preferably Al in the acidic electrolyte³⁺，Ca²⁺And Fe dissolved in the material itself^{3 +}The resulting precipitate was AlAsO₄、Ca₃(AsO₄)₂、FeAsO₄(ii) a Dissolved cation Pb²⁺The directional migration is generated under the action of the electric field force, the movement is migrated to the surface of the cathode of the active carbon, and the Pb is enriched on the surface of the active carbon²⁺Is electrolyzed into simple substance Pb under the action of electric field force and is deposited on the surface of the activated carbon to form an activated carbon electro-deposition lead product.

The electrochemical treatment method of the arsenopyrite according to the embodiment of the first aspect of the invention has the beneficial effects that: 1. according to the method provided by the embodiment of the invention, an acidic electrolyte solution is adopted to carry out electrochemical treatment on the arsenopyrite, so that arsenic, iron and lead in the arsenopyrite are dissolved and leached in the solution, activated carbon is filled in a cathode chamber to serve as a three-dimensional electrode cathode and an adsorbing material serving as metal ions, lead is dissolved in an ion form by acid, electrodeposition is carried out after the lead is selectively transferred to the cathode, lead metal is recovered, the recovery rate of lead reaches more than 96.0%, arsenic is fully leached in an anode chamber, arsenic-containing anions are selectively enriched in an anode reaction chamber, and are subjected to coprecipitation with high-valence cations in the electrolyte solution to be stably solidified at an anode, and the recovery rate of arsenic reaches more than 99.5%; 2. the method of the embodiment of the invention can greatly improve the ecological compatibility of the utilization of the arsenic-containing material, the arsenic is leached in the anode space of the feeding material, the stable solidification of the arsenic is completed in the same step, the dissolution leaching and the precipitation solidification of the arsenic-containing component are synchronously performed, the arsenic is not required to be secondarily stably fixed, the precipitation of lead is performed in the three-dimensional cathode filled with the activated carbon particles, the leaching of lead and the precipitation thereof in the three-dimensional filled cathode are simultaneously performed in the same step, and the treatment efficiency is improved; 3. the method of the embodiment of the invention improves the efficiency of wet lead extraction in arsenopyrite, can process a large amount of arsenopyrite materials at one time, and can recycle the electrolyte after being processed, thereby effectively improving the working efficiency, and reducing the energy consumption and the extraction time; 4. the method of the embodiment of the invention has simple process, convenient maintenance and repair and easy implementation.

According to the electrochemical treatment method of arsenopyrite, in the step a, the acid electrolyte is hydrochloric acid or nitric acid and corresponding Al-containing electrolyte³⁺Or Ca²⁺The metal cation salt is composed of an acid electrolyte with pH of 1-3 and Al³⁺Or Ca²⁺The mass percentage of the salt is 0.1-10%. In the embodiment of the invention, hydrochloric acid or nitric acid with pH of 1-3 and corresponding Al-containing acid are adopted³⁺、Ca²⁺The salt of the metal cation is used as a leaching system, so that the lead ions can be efficiently dissolved out by acid, the migration efficiency of lead is improved, arsenic-containing compounds can be effectively fixed on the anode by arsenic-containing anions, and the iron hydroxide structure can be rapidly dissolved and decomposed, so that the efficient and stable solidification of arsenic-containing phases and the selective separation and extraction of lead are realized at the same time.

According to the electrochemical treatment method of the arsenopyrite, provided by the embodiment of the invention, in the step a, the molar ratio of the sum of the molar amounts of the metal cations and Fe in the arsenopyrite to As in the arsenopyrite is 1.5. In the embodiment of the invention, the molar ratio of metal cations to arsenic anions in the acidic electrolyte solution is optimized, the lead recovery rate can reach 98.9%, and the arsenic recovery rate can reach 99.8%.

According to the electrochemical treatment method of arsenopyrite, provided by the embodiment of the invention, in the step a, the liquid-solid ratio of the acidic electrolyte to the arsenopyrite is 0.5-10: 1. In the embodiment of the invention, the liquid-solid ratio of the acid electrolyte to the arsenopyrite is optimized, so that the extraction rate of lead is improved, and the treatment method can economically and effectively recover lead.

According to the electrochemical treatment method of arsenopyrite in the embodiment of the invention, in the step b, the cathode potential is as follows: -0.6 to-2.0V, preferably-1.2 to-1.6V, and the potential difference between the anode chamber and the cathode chamber is 0.6 to 2.8V, preferably 1.2 to 2V. In the embodiment of the invention, the input voltage in the electrochemical reaction device is provided with the electrochemical reaction driving force to control the anion AsO₄ ^-And the cation Pb²⁺Such that the anion AsO₄ ^-After the anode is enriched to a certain concentration, the Fe is mixed with the existing Fe³⁺、Al³⁺Or Ca²⁺A precipitation reaction is carried out, the lead ions are selectively precipitated at the anode, and the directional movement of the lead ions, Pb, can be controlled by inputting voltage²⁺Is driven to move towards the cathode based on the potential difference, is electrolyzed and recovered as Pb, and can generate PbO, PbS and PbO in the processing process₂Etc. can be electrolyzed to Pb. The embodiment of the invention preferably selects cathode potential and potential difference, if the potential is too low and the voltage difference is too small in the electrolytic process, AsO^4-Can not be effectively enriched in the anode chamber, can not effectively separate arsenic, seriously influences the separation effect, and if the potential is too high, the voltage difference is too large, and the H of the cathode⁺Electrolytic problems may also occur, hydrogen gas is produced, and Fe³⁺Electrolysis may also occur, resulting in poor electrolysis and reduced recovery of lead and arsenic. It should be noted that the negative sign in the embodiment of the present invention represents the cathode electrodeA bit.

According to the electrochemical treatment method of the arsenopyrite, in the step b, the cathode chamber is separated from the anode chamber by a permeable membrane, a graphite felt or an inert screen. In the embodiment of the invention, the cathode chamber and the anode chamber are separated, so that the cathode product and the anode product are respectively filtered, the separation is convenient, and the working efficiency is improved.

According to the electrochemical treatment method of the arsenopyrite, in the step b, the acid electrolyte is made to flow from the anode chamber to the three-dimensional activated carbon cathode chamber of the electrochemical reaction device in a circulating countercurrent mode, and then flows out from the cathode chamber and returns to the anode chamber through an external circulating pipeline. In the embodiment of the invention, the acid electrolyte adopts a circulating countercurrent mode, and the circulating countercurrent can return electrolyte-containing solution after lead is deposited at the cathode to the anode for recycling, namely the electrolyte (such as H) can be saved⁺\Al³⁺\Ca²⁺Etc.), and can realize that the components to be separated are subjected to multiple circulating electrocatalytic reactions in the system, thereby fully realizing the separation.

According to the electrochemical treatment method of the arsenopyrite, provided by the embodiment of the invention, the arsenopyrite is selected from at least one of raw arsenopyrite ore, arsenopyrite-containing material or arsenopyrite-containing plumbite. The method provided by the embodiment of the invention has no limitation on the raw materials to be treated, and is suitable for any material containing lead and arsenic.

The electrochemical treatment method of arsenopyrite according to the embodiment of the present invention is not particularly limited, and any electrolytic and electrodeposition device that can implement the present invention may be used. Preferably, the electrochemical reaction device comprises an electrolytic cell, a working anode, an activated carbon three-dimensional cathode and a counter electrode, further preferably, the electrolytic cell is a counter-flow normal-pressure electrolytic cell, the three-dimensional electrode cathode in the cell body is separated from an anode chamber for placing the original arsenic-lead-alum-containing material by a net or a membrane, so that the cathode product and the anode product can be conveniently and respectively filtered and separated; the working anode is selected from carbon materials and inert metal electrodes, and is rod-shaped or plate-shaped independently; the activated carbon three-dimensional cathode is selected from activated carbon, graphene or other carbon powder materials with larger specific surface area; the counter electrode is selected from inert electrodes. Preferably, the electrochemical reaction device further comprises a real-time potential regulation and control device, wherein the electrode potential of the electrochemical reaction device is regulated and controlled in real time by introducing a reference electrode, and the reference electrode is an electrode suitable for electrolyte system reference.

According to the electrochemical treatment method of arsenopyrite, provided by the embodiment of the invention, the separated activated carbon electro-deposition lead product can be recovered by any roasting or wet lead recovery method for lead separation from activated carbon adsorption, preferably nitric acid is adopted to dissolve the lead into lead nitrate, and the lead nitrate is recycled to be used as a three-dimensional activated carbon cathode after the activated carbon is subjected to deleading activation; the anode deposition product is AsO-containing₄ ^3-Preferably for purifying arsenic chemicals, e.g. As pesticides or for purifying As by electrochemical reduction₂O₃(ii) a The electrolyte obtained by separation can be purified to remove part of metal ions which are difficult to treat, preferably, the metal ions are precipitated after the pH is adjusted to be alkaline, and the treated electrolyte can be returned to the electrochemical treatment device of the embodiment of the invention.

The embodiment of the second aspect of the invention also provides an electrochemical treatment method of gold ore containing arsenopyrite, which comprises the following steps:

mixing gold ore and acid electrolyte as electrolyte, placing the mixture into an anode chamber of an electrochemical reaction device, filling activated carbon into a cathode chamber, wherein the concentration of hydrochloric acid in the acid electrolyte is 0.1-0.2M, the mass concentration of aluminum hypochlorite is 3-6%, and the liquid-solid ratio of the acid electrolyte to the gold ore is 3-5: 1;

b, inputting voltage between the cathode and the anode, wherein the cathode potential is as follows: -1.6 to-2.0V, the potential difference between the anode chamber and the cathode chamber is 1.6 to 2.4V, the electrolyte is subjected to electrochemical catalytic dissolution reaction and electrochemical deposition reaction, arsenic is deposited on the anode, and gold and lead are deposited on the activated carbon;

c, filtering, separating and recycling the anode deposition product, the activated carbon electrodeposition product and the electrolyte obtained in the step b respectively.

The electrochemical treatment method for the gold ore containing the arsenopyrite has the advantages that the method can be used for dissolving and leaching arsenic, iron, lead and gold in the gold ore containing the arsenopyrite into a solution by adopting an electrochemical method in an acid environment, the lead and the gold are dissolved by acid in an ionic form and directionally deposited on a cathode, the arsenic is fully leached in an anode chamber and then precipitated and solidified, the lead recovery rate can reach 97.8%, the gold recovery rate can reach 99.8%, and the arsenic recovery rate can reach 99.8%.