阅读说明：本技术 一种贵金属硫化矿矿浆电解提取的方法 (Method for electrolytic extraction of precious metal sulfide ore pulp ) 是由 柯柏友 于 2021-05-27 设计创作，主要内容包括：本发明公开了一种贵金属硫化矿矿浆电解提取的方法,涉及贵金属冶金领域。本发明针对贵金属硫化矿,采用磨机磨矿后经调浆加入矿浆电解槽的阳极区,矿浆电解槽用渗滤性隔膜将阴极区与阳极区分开,矿浆中加入电解质氯化物、载氯体浸出剂及过氧化剂。用酸调PH值保持在1～2,电解时调控槽电压10～15V电流密度30～120A/dm～2,搅拌浸出2～4h。在阳极区贵金属硫化矿物被氧化成金属离子,金属离子或络合离子透过隔膜进入阴极区并在阴极板上析出,收集阴极泥用酸分解分离精炼即得到贵金属产品。本方法对含有硫砷碳等有害杂质的的难浸贵金属矿物都能取得超高的浸出率。且流程短能耗低成本小,对环境有好。社会效益和经济效益显著。(The invention discloses a method for electrolyzing and extracting ore pulp of precious metal sulfide ore, and relates to the field of precious metal metallurgy. The invention aims at the precious metal sulphide ore, the ore is ground by a mill and then added into the anode area of an ore pulp electrolytic cell after size mixing, the cathode area and the anode area of the ore pulp electrolytic cell are separated by a percolation diaphragm, and the ore pulp is added with electrolyte chloride, a chlorine carrier leaching agent and a hyperoxidant. Adjusting the pH value to 1-2 with acid, and regulating the cell voltage to 10-15V and the current density to 30-120A/dm during electrolysis 2 And stirring and leaching for 2-4 h. And oxidizing the noble metal sulfide minerals into metal ions in the anode area, allowing the metal ions or complex ions to enter the cathode area through the diaphragm and be separated out on the cathode plate, collecting cathode mud, and decomposing, separating and refining the cathode mud by using acid to obtain the noble metal product. The method can obtain ultrahigh leaching rate for refractory precious metal minerals containing harmful impurities such as sulfur, arsenic, carbon and the like. And the process is short, the energy consumption is low, the cost is low, and the environment is good. The social benefit and the economic benefit are obvious.)

1. The invention discloses a method for electrolyzing and extracting ore pulp of precious metal sulfide ore, and relates to the field of precious metal metallurgy. The method is characterized in that: the method comprises the following steps:

(1) crushing the noble metal sulfide ore, and grinding the crushed noble metal sulfide ore into 200-400 meshes in a grinding machine;

(2) adding the ore pulp into an anode area of an ore pulp electrolytic cell after pulp mixing according to the solid-liquid ratio of 1: 2-6;

(3) the pulp electrolytic cell separates a cathode area from an anode area by using a percolating diaphragm, the anode is made of graphite or titanium alloy plates, and the cathode is made of a stainless steel plate;

(4) adding electrolyte chloride, chlorine carrier leaching agent and over-oxidant into the ore pulp. Adjusting the pH value to 1-2 by adding acid, adjusting the cell voltage to 10-15V during electrolysis, and adjusting the current density to 30-120A/dm²And stirring and leaching for 2-4 h.

(5) Under the combined action of current and leaching agent, the noble metal sulfide minerals in the anode region are oxidized into metal ions, the metal complex ions enter the cathode region through the diaphragm and are separated out on the cathode plate to obtain noble metal mud, and the noble metal mud is collected, decomposed, separated, refined and purified to obtain high-purity noble metals;

(6) after the electrolyzed ore pulp is subjected to liquid-solid separation, the electrolyte returns to the ore pulp electrolytic cell, and the leached residues enter a tailing pond for storage.

2. The process of claim 1 wherein the precious metal sulphide ore pulp is extracted electrolytically, wherein: in the step (4), the slurry is added with the electrolyte chloride NaCl, and the chlorine carrier leaching agent contains active chlorine atoms and can be at least one of trichloroisocyanuric acid, dichloroisocyanuric acid, sodium dichloroisocyanurate, chloramine B, chloramine T, dichloramine B and dichloramine T.

3. The process of claim 1 wherein the precious metal sulphide ore pulp is extracted electrolytically, wherein: the peroxide in the step (4) can be at least one of urea peroxide, boron peroxide, barium peroxide, potassium permanganate, sodium persulfate, ammonium persulfate, sodium percarbonate, ammonium percarbonate, calcium peroxide, sodium peroxide and hydrogen peroxide.

4. The process of claim 1 wherein the precious metal sulphide ore pulp is extracted electrolytically, wherein: and (4) adding an electrolyte chloride which is sodium chloride (NaCl) into the ore pulp in the step (4), wherein the concentration of the sodium chloride is 10-25% (W/W), the concentration of hydrochloric acid (HCI) is 0.1-0.2 mol/L, the concentration of a chlorine carrier oxidant is 0.05-0.3% (W/W), and the concentration of a peroxide is 0.05-0.4% (W/W).

5. The process of claim 1 wherein the precious metal sulphide ore pulp is extracted electrolytically, wherein: the current density of the regulating and controlling tank in the step (4) during electrolysis is 30-120A/dm under the voltage of 10-15V²。

6. The process of claim 1 wherein the precious metal sulphide ore pulp is extracted electrolytically, wherein: the method is characterized in that the leaching is carried out in the step (4) for 2-4 h under stirring at the speed of: 500 to 600 r/min.

Technical Field

The invention discloses a method for electrolyzing and extracting ore pulp of precious metal sulfide ore, and relates to the field of precious metal metallurgy.

Background

The pulp electrolysis is also a hydrometallurgical technology which is researched and developed by Beijing mining and metallurgy research institute for more than twenty years and has independent intellectual property rights in China, and from 1978, pulp electrolysis tests of chalcopyrite, galena, multi-metal sulfide ore, copper-aluminum ore containing gold and silver and waste copper ore are carried out domestically. A series of condition tests are carried out on the persimmon bamboo garden bismuth sulfide concentrate by an ore pulp electrolysis method, good industrial test indexes are obtained, and a 100 t-year bismuth ore pulp electrolysis test factory is built in a persimmon bamboo garden in 1997. The method adopts ore pulp electrolysis treatment on the Guangdong Lianjiang silver ore, develops a new process of ore pulp electrolysis-oxidation copper removal-sodium sulfite silver extraction, and is put into production in 1997. Meanwhile, the method has good effect on the pretreatment of the ore pulp for the Yuanyang gold mine by the electrolytic method. After the single-groove expansion test, the test is put into production at 12 months 1999 and passes acceptance and identification at 3 months 2000. While the pulp electrolysis is widely applied, the Qiuding Dynasty of the Beijing institute of mining and metallurgy and the Yang of the university of Kunming theory do a lot of work on the basic theory of pulp electrolysis, but there is no systematicness and depth, and some conclusions remain questionable.

The ore pulp electrolysis integrates three processes of leaching, solution purification and electrodeposition which are usually contained in hydrometallurgy, and the ore is leached by using the oxidation reaction of an anode in the electrodeposition process, so that the anode reaction which consumes a large amount of energy in the conventional electrodeposition process is converted into effective leaching of metal, and the metal is directly produced from the ore pulp, thereby greatly simplifying the flow, having high metal recovery rate, saving energy and having obvious economic benefit. Since most of the sulfur in the mineral and bound to the metal is produced as elemental sulfur, SO is essentially eliminated₂Thus being good for environmental protection. Due to flexible production scale, the method is very suitable for carrying out pithead smelting by building factories on site. Years of practical research shows that the pulp electrolysis technology is suitable for treating complex polymetallic ores and associated ores such as lead-zinc-silver mixed ores, complex antimony-lead ores, copper-bismuth mixed ores, lead-copper-containing complex gold concentrates, copper-nickel mixed ores, ocean bonded ores and the like, can realize selective extraction of certain metal, has high metal recovery rate and good comprehensive utilization of valuable elements, and is a novel environment-friendly metallurgy technology which conforms to the national strategy of sustainable development and utilization of mineral resources.

In the aspect of recovering valuable metals by electrolyzing ore pulp, although a plurality of valuable scientific researches are made by the technologists, the technologists only carry out the following steps on the more active metals in the sulfide ores such as: bismuth, antimony, copper, lead, zinc, vanadium, silver and the like are recovered by electrolysis, and sulfur and arsenic are dissociated by electrolytic oxidation. And less active noble metals such as: gold, platinum, palladium, ruthenium, rhodium, and the like are lacking in research for direct recovery by electrolysis. But the precious metals are retained in the electrolysis tailings and need to be leached and extracted further. This is not to say a disadvantage.

How to utilize the technical advantages of ore pulp electrolysis to directly electrolyze and recover the precious metals with lower activity inevitably brings better economic benefits to precious metal production enterprises and brings greater wealth to the society through the new statement of ore pulp electrolysis. Is the research direction of technical workers in the industry.

Disclosure of Invention

Aiming at the defects and problems in the prior art, the invention discloses a method for electrolyzing and extracting ore pulp of precious metal sulfide ore, relating to the field of metal metallurgy

The invention discloses a method for electrolyzing and extracting ore pulp of precious metal sulfide ore, and relates to the field of precious metal metallurgy. The method is characterized in that: and crushing the noble metal sulfide ore, and then grinding the crushed noble metal sulfide ore into 200-400 meshes in a grinding machine. The pulp electrolytic cell separates the cathode area from the anode area by a percolating diaphragm, the anode is made of graphite or titanium alloy plates, and the cathode is made of stainless steel plates. And adding the ore pulp into an anode area of the ore pulp electrolytic cell after the ore pulp is mixed according to the solid-liquid ratio of 1: 2-6. Adding electrolyte chloride, chlorine carrier leaching agent and over-oxidant into the ore pulp. Adding acid to adjust the pH value to be 1-2, adjusting and controlling the cell voltage to be 10-15V and the current density to be 30-120A/dm during electrolysis²And stirring and leaching for 2-4 h. Under the combined action of current and leaching agent, the noble metal element minerals in the anode region are oxidized into metal ions, the metal complex ions enter the cathode region through the diaphragm and are separated out on the cathode plate to obtain noble metal mud, and the noble metal mud is collected, decomposed, separated, refined and purified to obtain a high-purity noble metal product; after the electrolyzed ore pulp is subjected to liquid-solid separation, the electrolyte returns to the ore pulp electrolytic tank, and the leached residues enter a tailing pond for storage.

The invention relates to a method for electrolyzing and extracting precious metal sulfide ore pulp, wherein an electrolyte chloride is added into the ore pulp and a chlorine carrier leaching agent is a chemical product containing active chlorine atoms, and can be at least one of trichloroisocyanuric acid, dichloroisocyanuric acid, sodium dichloroisocyanurate, chloramine B, chloramine T, dichloramine B and dichloramine T, preferably trichlorisocyanuric acid.

The invention relates to a method for electrolyzing and extracting precious metal sulfide ore pulp, wherein a peroxide can be at least one of urea peroxide, boron peroxide, barium peroxide, potassium permanganate, sodium persulfate, ammonium persulfate, sodium percarbonate, ammonium percarbonate, calcium peroxide, sodium peroxide and hydrogen peroxide, and ammonium persulfate is preferred.

The invention relates to a method for electrolyzing and extracting precious metal sulfide ore pulp, wherein electrolyte chloride is added into the ore pulp and is sodium chloride (NaCl), the concentration of the NaCl is 10-25% (W/W), the concentration of hydrochloric acid (HCI) is 0.1-0.2 mol/L, the concentration of a chlorine carrier leaching agent is 0.05-0.3% (W/W), and the concentration of an over-leaching agent is 0.05-0.4% (W/W).

The invention relates to a precious metal sulfide ore pulp electrolysis extraction method, wherein the current density of a control tank during electrolysis is 30-120A/dm under the voltage of 10-15V^2，The current density is preferably 90-110A/dm²。

The invention relates to a precious metal sulfide ore pulp electrolytic extraction method, which comprises the following steps of stirring and leaching for 2-4 hours at the stirring speed: 400-500 r/min.

The chemical wet process for extracting noble metal, such as cyanide gold leaching, is aimed at ionizing gold in original state by redox reaction to obtain gold in ionic state, then combining it with ions of artificial leaching agent to form soluble complex, then making it be fed into solution, and making it be moved with the leaching solution to carry out ore leaching. The electrolytic reaction process comprises the following steps:

the anode region has the reaction formula: au → Au⁺+e^-

The reaction formula of the cathode region is as follows: o is₂+2H₂O+2e^-→H₂O₂+2OH^-

H₂O₂+2e^-→2OH^-

In the chemical gold extraction process, if an artificial electric field is applied, the electric field force can theoretically produce the following effects:

(1) the gold accelerating electrode in the original existence state is forced to be polarized to form gold in an ionic state, and the ionization formula is as follows: au → Au³⁺+3e^-。

(2) The gold in ionic state can be driven to accelerate migration along the direction of an electric field, rapidly diffuse, contact and react with leaching agent ions or complex ions as soon as possible to generate soluble complex compounds, enter the solution and then flow and are carried away along with the solution.

(3) While forming the gold complex, the ion concentration in the immersion liquid is reduced, and a space is left, so that the gold ionization can be continuously and thoroughly carried out towards the required direction due to the concentration effect.

(4) The artificial electric field force weakens or destroys the binding force of different gold-carrying minerals to various forms of gold to a certain extent, so that the gold in the original occurrence state can form more gold in an ionic state. The above-mentioned action can attain the goal of raising gold leaching rate and shortening leaching period.

The leaching agent of the invention only does not select sodium cyanide, because the sodium cyanide aqueous solution is quickly oxidized on the graphite anode to generate cyanate ions (CN) under the action of a direct current electric field^-+2OH^--2e^-→CNO^-+H₂O); cyanate is unstable in electric field, and a part of cyanate is hydrolyzed to generate ammonium and carbonate ionsA part of the oxygen is continuously electrolyzed and oxidized into carbon dioxide and nitrogen (2 CNO)^-+4H⁺-6e^-→2CO₂↑+N2↑+2H₂O). The preferred leachant is trichloroisocyanuric acid.

Trichloroisocyanuric acid is a very strong chlorinating agent of an oxidant, is one of chloroisocyanuric acid series products, is white crystalline powder or granular solid, has strong chlorine stimulation smell, and has the active chlorine content 2-3 times higher than that of bleaching powder. The content of available chlorine is more than 90 percent, and the chlorine-free chlorine release agent has the characteristics of high available chlorine content, stable storage. Therefore, its development and research are receiving attention from various countries. The trichloroisocyanuric acid has wide application, can be used as a bactericide for industrial water, swimming pool water, hospitals, tableware and the like, and has very wide development and utilization prospects. Trichloroisocyanuric acid has been widely used in industrial circulating water. Is a new generation product of bleaching powder and bleaching essence, the three wastes are greatly reduced compared with the bleaching essence, and advanced countries have a tendency of replacing the bleaching essence with the bleaching powder.

Chloride is inherently a good precious metal leaching agent and is used for gold leaching as early as sodium cyanide. After the invention is invented, the sodium cyanide is removed by diffusion. Trichloroisocyanuric acid is a gold leaching agent superior to other chloride gold leaching agents, and has better practicability, stronger oxidizability and stronger complexing ability on gold minerals.

Drawings

The attached figure 1 shows a flow chart of the precious metal sulphide ore pulp electrolytic extraction process.

Detailed Description

The invention will be further understood with reference to the following specific examples.

Example 1

Gold concentrate of some gold mine in the Hunan Water gap mountain. The sulfur content is 34%, the arsenic content is 2.9%, the gold content is 87g/T, and the concentrate powder is ground by a vertical mill to reach 85% in a superfine grinding mode with a mesh size of-350. The solid-liquid ratio of the ore pulp is mixed according to the ratio of 1: 5 and then added into the anode area of the ore pulp electrolytic cell. The pulp cell separates the cathode compartment from the anode compartment with a percolating membrane, the electrolyte in the cathode compartment being otherwise identical to the anode compartment except that there is no pulp. The anode is a graphite electrode, and the cathode is a stainless steel plate electrode. Adding 15% (W/W) electrolyte sodium chloride into the ore pulp, adding hydrochloric acid to adjust the pH value to be 1-2, adjusting the hydrochloric acid concentration to be 0.15mol/L, adding a leaching agent of 0.2% (W/W) trichloroisocyanuric acid, using a hyperoxidant and ammonium percarbonate, and adjusting the concentration to be 0.1% (W/W); the cell voltage is adjusted to be about 10V, and the current density is 110A/dm²Controlling the stirring speed as follows: 450 r/min. Stirring and electrolyzing to leach for 2 h. Obtaining gold mud in a cathode area, collecting, refining and purifying to obtain high-purity gold, wherein the leaching rate of gold reaches 99.3%.

Example 2

In a gold mine of Henan Lingbao, gold concentrate contains 32% of sulfur, 1.1% of arsenic and 61g/T of gold, and the mineral powder is ground by a vertical grinding machine until the granularity reaches 90% in a range of-350 meshes. The solid-liquid ratio of the ore pulp is mixed according to the ratio of 1: 5 and then added into the anode area of the ore pulp electrolytic cell. The pulp electrolyzer separates the cathode area from the anode area by a percolating membrane, the electrolyte of the cathode area except mineral powder does not containWhich is identical to the anode region. The anode is a graphite electrode, and the cathode is a stainless steel plate electrode. Adding electrolyte sodium chloride into the ore pulp, wherein the concentration of the electrolyte sodium chloride is 15% (W/W), adding hydrochloric acid to adjust the pH value to be 1-2, adjusting the concentration of the hydrochloric acid to be 0.2mol/L, adding a leaching agent trichloroisocyanuric acid, wherein the concentration of the leaching agent trichloroisocyanuric acid is 0.2% (W/W), and using ammonium carbonate as a peroxide agent, wherein the concentration of the ammonium carbonate is 0.1% (W/W); the cell voltage is adjusted to be about 12V, and the current density is 100A/dm²Controlling the stirring speed as follows: 400 r/min. Stirring and electrolyzing to leach for 2 h. Obtaining gold mud in a cathode area, collecting, refining and purifying to obtain high-purity gold, wherein the leaching rate of gold reaches 99.1%.

Example 3

The Burma gold concentrate contains 35% of sulfur, 1.8% of arsenic, 43g/T of gold and 160g/T of silver, and the ore powder is ground to 80% of minus 400 meshes by a vertical grinding machine. The solid-liquid ratio of the ore pulp is mixed according to the ratio of 1: 6 and then added into the anode area of the ore pulp electrolytic cell. The pulp cell uses a percolating diaphragm to separate the cathodic compartment from the anodic compartment, the cathodic compartment electrolyte being identical to the anodic compartment except for the absence of mineral fines. The anode is a graphite electrode, and the cathode is a stainless steel plate electrode. Adding 25% (W/W) of electrolyte sodium chloride into the ore pulp, adding hydrochloric acid to adjust the pH value to be 1-2, adjusting the hydrochloric acid concentration to be 0.2mol/L, adding 0.3% (W/W) of a leaching agent trichloroisocyanuric acid, using a peroxy oxidant and ammonium carbonate, and adjusting the concentration to be 0.15% (W/W); the cell voltage is adjusted to about 15V, and the current density is 120A/dm²Controlling the stirring speed as follows: 500 r/min. Stirring and electrolyzing to leach for 3 h. Gold and silver mud is obtained in the cathode area, and high-purity noble metal is obtained through collection, refining and purification. Through the analysis of tailings, the leaching rate of gold reaches 99.1 percent, and the leaching rate of silver reaches 98.3 percent.

Example 4

The concentrate powder of some noble metal ore in Yunnan province contains 35% of sulfur, 1.8% of arsenic, 43g/T of gold, 140g/T of silver, 15g/T of platinum, 23g/T of palladium and 11g/T of rhodium. The mineral powder is ground by a vertical grinder until the grain size reaches 90 percent in a range of-400 meshes. The solid-liquid ratio of the ore pulp is mixed according to the ratio of 1: 6 and then added into the anode area of the ore pulp electrolytic cell. The pulp electrolytic cell is characterized in that a cathode area and an anode area are separated by a percolation diaphragm, electrolyte in the cathode area is the same as that in the anode area except that no mineral powder exists, the anode is a graphite electrode, and the cathode is a stainless steel plate electrode. Adding electrolyte sodium chloride into the ore pulp with the concentration of 25% (W/W), and adding hydrochloric acid to adjust the pH value to be less than1, hydrochloric acid concentration is 0.2mol/L, a leaching agent trichloroisocyanuric acid concentration is added, 0.5% (W/W) of a peroxidation agent is used, ammonium carbonate is used, and the concentration is 0.2% (W/W); the cell voltage is adjusted to be about 15V, and the current density is 120A/dm²Controlling the stirring speed as follows: 500 r/min. Stirring and electroleaching for 4 hours. And (3) obtaining the noble metal mixed mud in the cathode region, collecting, separating, refining and purifying by acid decomposition to obtain a high-purity noble metal product. Through the analysis of tailings, the leaching rate of gold reaches 99.4 percent, the leaching rate of silver reaches 98.8 percent, the leaching rate of platinum reaches 93.3 percent, the leaching rate of palladium reaches 94.5 percent, and the leaching rate of rhodium reaches 97.1 percent

The above description is only for the preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art should be considered to be within the technical scope of the present invention, and the technical solutions and the inventive concepts thereof according to the present invention are equivalent to or changed within the technical scope of the present invention.