CN111154975B - Method for treating arsenic-antimony-containing gold-carrying material - Google Patents
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Abstract
The invention discloses a method for treating arsenic-antimony-containing gold-carrying materials. The method comprises the following steps: 1) crushing and grinding the arsenic-antimony-containing gold-carrying material; 2) mixing manganese oxidized minerals and arsenic-antimony-containing gold-carrying materials into acidic slurry in a strong acid sulfuric acid system; 3) heating the acidic slurry for oxidizing leaching, wherein the acidic slurry is oxidized leached slurry after the reaction is finished; 4) carrying out solid-liquid separation on the oxidation leaching slurry to obtain oxidation leaching slag and oxidation leaching liquid, and diluting the oxidation leaching slag with water or adjusting the oxidation leaching slag with dilute sulfuric acid or dilute hydrochloric acid to prepare slurry to obtain diluted slurry; 5) acidifying the chlorination gold extracting agent or directly adding the chlorination gold extracting agent into the diluted slurry prepared by size mixing in the step 4), and performing chlorination leaching of gold to obtain chlorination gold leaching slurry; 6) carrying out solid-liquid separation on the chloridized gold leaching slurry; and 7) respectively purifying, separating and purifying the chlorination leaching solution and the oxidation leaching solution. By applying the technical scheme of the invention, the effective comprehensive utilization of gold, arsenic, antimony and sulfur in the arsenic-containing and antimony-containing gold ore can be realized.
Description
Technical Field
The invention relates to the technical field of metallurgy, in particular to a method for treating a gold-loaded material containing arsenic and antimony.
Background
30 percent of gold reserves in China are refractory gold ores, arsenic-containing antimony-containing refractory gold ores or gold-containing materials are one of important carriers of gold, and are important resources for gold development and utilization in future in China. Gold in the refractory gold-bearing materials is mostly coated or impregnated in sulfide minerals in fine grains or sub-microgranules, and because gold is closely related to arsenopyrite and stibnite, direct gold leaching is difficult, and the crystal structure of the arsenopyrite and stibnite needs to be damaged to expose the gold and then the gold is leached.
At present, a pre-oxidation post-cyanidation leaching process is generally adopted for refractory gold ores containing arsenic and antimony, and the pre-oxidation is mainly oxygen-enriched roasting pre-oxidation, chlorination roasting pre-oxidation and biological pre-oxidation. The most common pre-oxidation method of gold ore difficult to treat is rich roasting pre-oxidation, which has wider applicability to ore, simple operation and maintenance and stable technology, but sulfur and arsenic in the roasting process of gold ore containing sulfide and reducing substances are removed by harmful gases such as sulfur dioxide, arsenic trioxide and the like, antimony is volatilized by antimony-containing flue gas, the roasting energy consumption is high at high temperature in the process, the utilization of arsenic, antimony and sulfur resources is difficult, and the environmental hazard is large. Although the biological treatment of the gold-containing materials is suitable for the gold-containing materials with low arsenic and low antimony contents, the biological treatment has poor adaptability to high-arsenic and high-antimony materials and long oxidation treatment period. The chloridizing roasting preoxidation is easy to generate harmful gases such as chlorine, hydrogen sulfide and the like, the atmosphere is difficult to seal and regulate, and the environmental pollution caused by the escape of the gases is also large. The material is pre-oxidized and then is leached by cyanidation, the toxicity of cyanide is high, cyanide leaching slag is difficult to treat, and the pollution to the surrounding environment is obvious.
The key point of wet oxidation as an important method for the oxidation of sulfide minerals is to find an economic and efficient oxidant. Oxides of high valence manganese often exhibit strong oxidizing properties in acidic systems, and numerous studies and practices have demonstrated that oxides of high valence manganese are effective oxidizing agents for sulfides. And the materials containing high-valence manganese oxides have wide sources and low prices, such as pyrolusite, manganese nodule and the like. The technology of wet oxidation of gold-bearing sulfide ore gold ore by manganese oxide ore has been reported, but almost all adopt acid to pre-oxidize sulfide in gold-bearing materials, add alkali to adjust the pH of leaching slag, and then cyanide and leach. In order to prevent the volatilization of cyanide under acidic conditions, the size mixing process needs to consume a large amount of alkali and repeatedly wash the leaching residue for control. The patent "a method for pretreating ocean polymetallic nodule and arsenic-containing gold ore by mixing" (CN104928468A) "utilizes high-valence manganese ore in manganese nodule to oxidize arsenic-containing gold ore, and then adopts cyanidation leaching to recover gold, besides the need of regulating acidity of acidic preoxidation slag, a fussy cyanide treatment process is set. The patent "a method for leaching arsenic-containing carbonaceous gold ore under high pressure-non-cyanidation by pyrolusite (CN 201810173568.1)" is to oxidize arsenic-containing sulfurized minerals and carbonaceous materials by an acid system under high temperature and high pressure with pyrolusite, and then to leach gold by using low-toxicity cyanurate after the oxidation slag is repeatedly washed, and the washing steps are complicated.
In conclusion, the prior pretreatment method for the arsenic-containing and antimony-containing gold ore has the problems of great technical difficulty, serious environmental pollution, high cost, high energy consumption, low resource utilization rate and the like. The method for reducing environmental pollution and realizing high resource utilization is of great significance.
Disclosure of Invention
The invention aims to provide a method for treating an arsenic-antimony-containing gold-loaded material, so as to provide an environment-friendly method for treating the gold-loaded material.
In order to achieve the above object, according to one aspect of the present invention, there is provided a method for treating an arsenic-antimony-containing gold-bearing material. The method comprises the following steps: 1) crushing and grinding the arsenic-antimony-containing gold-carrying material; 2) mixing manganese oxidized minerals and the arsenic-antimony-containing gold-carrying materials treated in the step 1) into acidic slurry in a strong acid sulfuric acid system; 3) heating and oxidizing the acidic slurry to leach sulfide minerals and other reducing substances in the arsenic-antimony-containing gold-carrying material, wherein the acidic slurry is an oxidized leached slurry after the reaction is finished; 4) carrying out solid-liquid separation on the oxidation leaching slurry to obtain oxidation leaching slag and oxidation leaching liquid, and diluting the oxidation leaching slag with water or adjusting the oxidation leaching slag with dilute sulfuric acid or dilute hydrochloric acid to prepare slurry to obtain diluted slurry; 5) acidifying the chlorination gold extracting agent or directly adding the chlorination gold extracting agent into the diluted slurry prepared by size mixing in the step 4), and performing chlorination leaching of gold to obtain chlorination gold leaching slurry; 6) carrying out solid-liquid separation on the chlorination gold leaching slurry to obtain chlorination leaching liquid and gold leaching tailing residues; and 7) respectively purifying, separating and purifying the chlorination leaching solution and the oxidation leaching solution.
Further, in the step 2), the mass ratio of the arsenic-antimony-containing gold-carrying material to the ore in the manganese oxide mineral is configured according to the mass-to-molar ratio of S to Mn of 1: 3-1: 6.
Further, in the step 3), the strong oxidation leaching of the sulfuric acid system adopts a liquid-solid ratio of 3: 1-10: 1, the concentration of sulfuric acid is 1-5 mol/L, the reaction temperature is 60-250 ℃, the reaction time is 1-4 hours, and the stirring speed is 100-600 r/min.
Further, in the step 4), the oxidation leaching residue is diluted by water or is adjusted by dilute sulfuric acid/dilute hydrochloric acid to be pulped, and the liquid-solid ratio is 3: 1-10: 1.
Further, in the step 4), the pH value of the diluted slurry is-0.5-6.
Furthermore, the arsenic content of the arsenic-antimony-containing gold-carrying material is 0.1-20%, the antimony content is 0.1-20%, the sulfur content is 5-40%, and the ore granularity of-200 meshes after ore grinding accounts for more than 80%.
Further, the manganese oxide minerals are one or more of pyrolusite, manganite and manganese nodule, and the content of Mn in the manganese oxide minerals is 10-63%.
Further, in the step 5), the chlorinating agent used for chlorinating the gold chloride extraction agent is one or more of hypochlorous acid and salts thereof, perchloric acid and salts thereof and chlorine gas; preferably, the dosage of the gold chloride leaching agent in the gold chloride leaching slurry is 0.01-0.2 mol/L; preferably, a regulator is also added in the chlorination leaching, and the regulator is sodium chloride or hydrochloric acid.
Further, in the step 5), in the chlorination leaching process, the liquid-solid ratio is 3: 1-10: 1, the stirring speed is 200-600 r/min, the leaching reaction temperature is room temperature-250 ℃, and the leaching time is 1-6 hours.
Further, recovering arsenic, antimony, manganese, sulfur and iron from the oxidation leachate obtained in the step 4) through an extraction-separation-fractional crystallization-separation process; preferably, in the step 7), gold and manganese are recovered from the chlorination leaching solution by an active metal replacement method.
By applying the technical scheme of the invention, the effective comprehensive utilization of gold, arsenic, antimony and sulfur in the arsenic-antimony-containing gold ore can be realized, the recovery rate of valuable metals such as gold, manganese, arsenic, antimony, iron, sulfur and the like reaches more than 95%, the resource utilization rate is high, and the defect that harmful gases such as arsenic oxide, sulfur dioxide and the like are generated in the conventional roasting pre-oxidation process is overcome; the non-cyanogen high-speed gold leaching agent is adopted, so that the pollution is small, and the gold leaching speed is high. The method has the advantages of simple process, stable performance and little environmental pollution.
Drawings
The accompanying drawings, which are incorporated in and constitute a part of this application, illustrate embodiments of the invention and, together with the description, serve to explain the invention and not to limit the invention. In the drawings:
FIG. 1 is a schematic flow chart of a method for treating an arsenic-antimony-containing gold-bearing material according to an embodiment of the invention.
Detailed Description
It should be noted that the embodiments and features of the embodiments in the present application may be combined with each other without conflict. The present invention will be described in detail below with reference to the embodiments with reference to the attached drawings.
Aiming at the problems of great technical difficulty, serious environmental pollution, high cost, high energy consumption, low resource utilization rate and the like in the effective utilization of the gold ore containing arsenic and antimony and difficult to treat. The invention provides a series of technical schemes.
According to an exemplary embodiment of the present invention, a method for treating an arsenic-antimony-containing gold-bearing material is provided. The processing method comprises the following steps: 1) crushing and grinding the arsenic-antimony-containing gold-carrying material; 2) mixing manganese oxidized minerals and the arsenic-antimony-containing gold-carrying materials treated in the step 1) into acidic slurry in a strong acid sulfuric acid system; 3) heating and oxidizing the acidic slurry to leach sulfide minerals and other reducing substances in the arsenic-antimony-containing gold-carrying material, wherein the acidic slurry is an oxidized leached slurry after the reaction is finished; 4) carrying out solid-liquid separation on the oxidation leaching slurry to obtain oxidation leaching slag and oxidation leaching liquid, and diluting the oxidation leaching slag with water or adjusting the oxidation leaching slag with dilute sulfuric acid or dilute hydrochloric acid to prepare slurry to obtain diluted slurry; 5) acidifying the chlorination gold extracting agent or directly adding the chlorination gold extracting agent into the diluted slurry prepared by size mixing in the step 4), and performing chlorination leaching of gold to obtain chlorination gold leaching slurry; 6) carrying out solid-liquid separation on the chlorination gold leaching slurry to obtain chlorination leaching liquid and gold leaching tailing residues; and 7) respectively purifying, separating and purifying the chlorination leaching solution and the oxidation leaching solution.
In the invention, the arsenic-antimony-containing gold-carrying material is antimony-containing and/or arsenic-containing gold-carrying sulfide ore, and antimony-containing and/or arsenic-containing reducing substance gold-carrying material, such as gold-arsenic-antimony sulfide concentrate, high-arsenic high-sulfur cyanide slag, stibnite silver gold ore and the like; the manganese oxide mineral is a material containing high-valence manganese oxide, such as pyrolusite, manganese nodule, manganosite, etc.
By applying the technical scheme of the invention, the method for oxidizing and strengthening chloridizing the arsenic-antimony-containing gold ore by utilizing the manganese oxide mineral in a recycling manner through strong acid oxidation, arsenic-antimony sulfide and other reducing substances in a gold-containing material are difficult to treat through the oxidation of the manganese oxide with high oxidation activity, leaching residues after the oxidation of the strong acid are directly prepared into slurry, and gold in the material is extracted through an acidic chloridizing gold leaching system, so that the effective comprehensive utilization of gold, arsenic, antimony and sulfur in the arsenic-antimony-containing gold ore can be realized, the recovery rate of valuable metals such as gold, manganese, arsenic, antimony, iron, sulfur and the like reaches more than 95 percent, the recycling utilization rate is high, and the defect that harmful gases such as arsenic oxide, sulfur dioxide and the like are generated by a conventional roasting pre-oxidation process is overcome; the non-cyanogen high-speed gold leaching agent is adopted, so that the pollution is small, and the gold leaching speed is high. The method has the advantages of simple process, stable performance and little environmental pollution. The method realizes the full-wet oxidation and gold leaching, is widely applicable to various arsenic-containing and antimony-containing gold-containing materials which are difficult to treat, has reliable technology and little environmental pollution, and can realize the simultaneous utilization of valuable metals in gold-carrying materials and manganese-carrying materials.
In the invention concept, sufficient manganese oxide can be used as an oxidant, reducing materials containing arsenic, antimony and sulfur in gold ore are fully oxidized in a heated sulfuric acid strong acid system to form soluble arsenic and antimony ionic phase, and gold remains in a slag phase; the strong acid oxidation leaching residue is diluted and size-mixed by water or dilute sulfuric acid or dilute hydrochloric acid, an acid chlorination gold extraction system is adopted to leach gold, and the excessive manganese oxide promotes the strengthening gold leaching process in the process. Preferably, in the step 2), the mass ratio of the arsenic-antimony-containing gold-carrying material to the ore in the manganese oxide ore is configured according to the mass molar ratio of S to Mn of 1: 3-1: 6, and the Mn ore is slightly excessive. Preferably, in the step 3), the strong oxidation leaching of the sulfuric acid system adopts a liquid-solid ratio of 3: 1-10: 1, the concentration of sulfuric acid is 1-5 mol/L, the reaction temperature is 60-220 ℃, the reaction time is 1-4 hours, and the stirring speed is 100-600 r/min.
In a typical embodiment of the invention, in the step 4), the oxidized leaching residue is diluted by water or is adjusted by dilute sulfuric acid or dilute hydrochloric acid to prepare slurry, and the specific dilution or slurry adjustment ratio can be determined according to the pH value of the slurry after solid-liquid separation, and the liquid-solid ratio is about 3:1 to 10: 1.
Preferably, in the step 4), the pH of the diluted slurry is-0.5-6, so that a proper acidic environment is provided for chlorination leaching.
According to a typical embodiment of the invention, the arsenic content in the arsenic-antimony-containing gold-carrying material is 0.1-20%, the antimony content is 0.1-20%, the sulfur content is 5-40%, and the ore granularity after ore grinding-200 meshes accounts for more than 80%. Preferably, the manganese oxide minerals are one or more of pyrolusite, manganite and manganese nodule, and the content of Mn in the manganese oxide minerals is 10-63%.
According to a typical embodiment of the invention, in the step 5), the chlorinating agent used for chlorination of the gold extraction agent is one or more of hypochlorous acid and salts thereof, perchloric acid and salts thereof, and chlorine gas; preferably, the dosage of the gold chloride leaching agent in the gold chloride leaching slurry is 0.01-0.2 mol/L; preferably, a regulator is also added in the chlorination leaching, and the regulator is sodium chloride or hydrochloric acid.
Preferably, in the step 5), in the chlorination leaching process, the liquid-solid ratio is 3: 1-10: 1, the stirring speed is 200-600 r/min, the leaching reaction temperature is room temperature-220 ℃, and the leaching time is 1-6 hours.
According to a typical embodiment of the invention, arsenic, antimony, manganese, sulfur and iron are recovered from the oxidation leachate obtained in step 4) by an extraction-separation-fractional crystallization-separation process; preferably, in the step 7), gold and manganese are recovered from the chlorination leaching solution by an active metal replacement method.
By using the method for oxidizing-chloridizing leaching of arsenic-antimony-containing gold-carrying materials by using the manganese oxidized minerals, valuable metal elements such as gold, manganese, arsenic, antimony, sulfur, iron and the like in the materials can be efficiently recovered. In a typical embodiment of the invention, after crushing and grinding arsenic-containing antimony-containing gold ore to a proper granularity, mixing the arsenic-containing antimony-containing gold ore with manganese oxidized ore with a proper granularity in a dilute sulfuric acid system, heating and stirring to oxidize and decompose sulfide or reducing substances in the gold ore, and performing solid-liquid separation on leached slurry to obtain an oxidation leaching solution and leached residues; oxidizing the leaching solution to recover valuable metals such as manganese, arsenic, antimony and the like; performing chlorination gold extraction on the oxidized leaching residue by adopting a chlorination leaching system, allowing gold to enter a leaching solution in a complex form and manganese to enter an ionic state, and performing solid-liquid separation to obtain a gold-containing pregnant solution and gold leaching tailings; in the acid chlorination gold leaching environment, the excessive manganese oxidized minerals oxidize hydrochloric acid or hypochlorous acid into chlorine gas, and the chlorination gold leaching is strengthened. The method can realize effective comprehensive utilization of gold, arsenic, antimony and sulfur in the arsenic-antimony-containing gold ore, the recovery rate of valuable metals such as gold, manganese, arsenic, antimony, iron, sulfur and the like reaches more than 95 percent, and the resource utilization rate is high. The defect that harmful gases such as arsenic oxide, sulfur dioxide and the like are generated in the conventional roasting and pre-oxidation process is overcome; the non-cyanogen high-speed gold leaching agent is adopted, so that the pollution is small, and the gold leaching speed is high. The method has the advantages of simple process, stable performance and little environmental pollution.
The following examples are provided to further illustrate the advantageous effects of the present invention.
Example 1
Referring to fig. 1, a method for enhanced chlorination leaching of arsenic-antimony-containing gold-carrying materials by utilizing manganese oxidized minerals is disclosed, wherein the arsenic-antimony-containing gold ore is taken from a certain high-arsenic high-antimony refractory gold concentrate in Hunan, the arsenic content is 3.72%, the antimony content is 7.56%, the sulfur content is 17.2%, the gold content is 60.2g/t, the gold leaching rate is lower than 20% when the gold ore is directly leached in cyanidation, the used manganese oxides are certain high-grade pyrolusite in Liaoning, and the Mn grade is 53.3%. Grinding the two types of ores until the ore is 90% of minus 200 meshes, preparing the materials according to the mass ratio of Mn to S in the materials of 4:1, adding the materials into 100mL of sulfuric acid solution with the concentration of 3mol/L, uniformly mixing slurry according to the liquid-solid ratio of 5:1, placing the mixed slurry in a sealed reaction kettle, heating, stirring, oxidizing and leaching at the leaching speed of 300r/min, the oxidizing and leaching reaction temperature of 180 ℃, the oxidizing and reaction time of 2h, cooling after the reaction is finished, concentrating and filtering, returning the filtrate to the process or separating valuable metals such as manganese, arsenic, antimony and the like, calculating the dissolution rates of arsenic and antimony by the filtrate to be higher than 96%, leaving the gold in an oxidizing slag phase, and keeping the residual amount of manganese in the slag to be about 5%; mixing the filter residue with water to obtain a slurry with a liquid-solid ratio of 5:1, wherein the pH of the slurry is 0.5, adding 0.2mol/L sodium hypochlorite and 1mol/L sodium chloride into the slurry, and leaching for 2 hours at a stirring speed of 400r/min and a temperature of 60 ℃ to obtain a gold-containing pregnant solution subjected to chlorination leaching and a chlorination leaching residue; the gold leaching rate is calculated by using gold-containing pregnant solution to reach 97.0 percent.
In another preoxidation leaching treatment mode of the arsenic-antimony-containing ore, two materials are ground until the content of Mn in the materials is 85 percent in a-200 mesh manner, the materials are prepared according to the quantity ratio of Mn to S in the materials being 6:1, the materials are added into 300mL of 3.0mol/L sulfuric acid solution according to the liquid-solid ratio being 6:1 to prepare mixed slurry, the mixed slurry is placed in a heating reaction kettle, the oxidation-reduction leaching is carried out at the constant temperature of 90 ℃, the leaching rotation speed is 300r/min, the oxidation reaction time is 2 hours, the filtrate is returned to the process or is subjected to valuable metal separation such as manganese, arsenic, antimony and the like, the dissolution rates of the arsenic and the antimony calculated by the filtrate are respectively 96.5 percent and 94.3 percent, the gold is left in an oxidation slag phase, and the residual amount of the manganese in the slag is about 9 percent; adjusting the oxidation slag slurry according to the liquid-solid ratio of 3:1, wherein the pH of the slurry is-0.5, adding 0.3mol/L sodium perchlorate into the slag phase, and leaching for 2h at 60 ℃ under stirring to obtain gold-containing pregnant solution and chlorination leaching slag; the gold leaching rate is calculated by gold-containing pregnant solution to reach 98.2 percent.
In another preoxidation leaching treatment mode of the arsenic-antimony-containing ore, two materials are ground to be 90% of-200 meshes, the materials are prepared according to the quantity ratio of Mn to S in the materials being 3:1, the materials are added into 300mL of 1.5mol/L sulfuric acid solution according to the liquid-solid ratio being 3:1 to prepare mixed slurry, the mixed slurry is placed in a heating reaction kettle, oxidation-reduction leaching is carried out at the constant temperature of 250 ℃, the leaching rotation speed is 300r/min, the oxidation reaction time is 2 hours, filtrate is returned to the process or is subjected to valuable metal separation such as manganese, arsenic, antimony and the like, the dissolution rates of arsenic and antimony calculated by the filtrate are respectively 92.5% and 91.3%, gold is left in an oxidation slag phase, and the residual amount of manganese in the slag is about 9%; adjusting the oxidation slag slurry according to the liquid-solid ratio of 5:1, adjusting the pH of the slurry to 5.5, adding 0.2mol/L sodium hypochlorite and 0.5mol/L sodium chloride into the slag phase, and stirring and leaching at 90 ℃ for 2h to obtain chloridized leached gold-containing pregnant solution and chloridized leaching slag; the leaching rate of gold calculated by using gold-containing pregnant solution reaches 84.3 percent, which is 63.5 percent higher than that of gold not subjected to manganese-carrying material oxidation treatment.
Example 2
Referring to fig. 1, a method for enhanced chlorination leaching of arsenic-antimony-containing gold-bearing material by using manganese oxidized ore is provided, wherein cyanidation tailings containing arsenic and antimony are taken from a certain cyanidation smelting plant of Fujian, the ore contains 2.13% of arsenic, 0.56% of antimony and 29.2% of sulfur, the gold content is 4.2g/t, the recovery rate of gold recyaniation leaching after roasting of the leaching residue is 43%, and manganese oxide used is ocean manganese nodule, the manganese content is 20.7%, the nickel content is 1.7%, the cobalt content is 0.2% and the copper content is 1.3%. Grinding the two materials until the two materials account for 85 percent in a-200 mesh state, preparing the materials according to the quantity ratio of Mn to S in the materials of 3.5:1, adding the materials into 1000mL of 2.5mol/L sulfuric acid solution according to the liquid-solid ratio of 6:1 to prepare mixed slurry, placing the mixed slurry into a heating reaction kettle, carrying out constant-temperature stirring oxidation-reduction leaching at the leaching rotation speed of 300r/min, the leaching reaction temperature of 90 ℃, the oxidation reaction time of 4 hours, cooling after the reaction is finished, filtering, calculating the leaching rates of arsenic, antimony, manganese, nickel, cobalt and copper by using the oxidation leaching filtrate as 94.5 percent, 90.2 percent, 90.5 percent, 90.7 percent, 91.7 percent and 88.6 percent, and keeping gold in an oxidation-reduction leaching slag phase; and (3) mixing the filter residue with water to obtain a slurry with a liquid-solid ratio of 4:1, wherein the pH of the slurry is 0.5, adding 0.2mol/L of sodium hypochlorite and 1mol/L of hydrochloric acid into the slurry, leaching for 0.5h at the temperature of 120 ℃ at the stirring speed of 400r/min, wherein the gold leaching rate is 95.3%, and the recovery rates of nickel, manganese, copper and cobalt are more than 99% calculated according to the metal content in the chlorination leaching residue.
Example 3
Referring to fig. 1, a method for enhanced chlorination leaching of arsenic-antimony-containing gold-carrying materials by using manganese oxidized minerals is disclosed, wherein refractory gold sulfide concentrate containing arsenic and antimony is obtained from Yunnan, the ore contains 6.6% of arsenic, 2.6% of antimony and 20.2% of sulfur, the gold content is 48.2g/t, gold is leached by strong oxidation under the condition of excessive gold chloride leaching agent, and the gold extraction rate reaches 96.3%; the manganese oxide used is a low-grade manganese oxide ore in Hunan, and the manganese grade is 22.5%. Grinding the two materials to-200 meshes which account for 93%, preparing the materials by combining the Mn and S materials according to the amount ratio of 5:1, adding the materials into 300mL of 3.5mol/L sulfuric acid solution according to the liquid-solid ratio of 10:1 to prepare mixed slurry, placing the mixed slurry into a heating reaction kettle, carrying out constant-temperature stirring oxidation leaching at the leaching speed of 600r/min, the oxidation leaching reaction temperature of 160 ℃, the reaction time of 2 hours, cooling after the reaction is finished, concentrating and filtering, separating valuable metals such as manganese, arsenic, antimony and the like in oxidation leaching filtrate, and calculating the leaching rates of arsenic and antimony by the filtrate to be 96% and 94.5% respectively; and (3) mixing the filter residue with dilute hydrochloric acid to obtain a slurry with a liquid-solid ratio of 10:1, wherein the pH of the slurry is 1.2, adding 0.03mol/L of sodium perchlorate and 0.1mol/L of hydrochloric acid into the slurry, leaching for 0.5h at the temperature of 40 ℃ at the stirring speed of 400r/min, and filtering to obtain gold-containing pregnant solution, wherein the gold leaching rate is 96.8%.
From the above description, it can be seen that the above-described embodiments of the present invention achieve the following technical effects:
1. the method utilizes the oxidation activity of manganese oxidized minerals, oxidizes reductive components in gold ores in an acidic system, and simultaneously utilizes harmful substances such as arsenic, antimony, sulfur and the like in the gold ores to fully expose gold in the gold ores; the gold is leached by the oxidized leaching slag directly in an acid environment by adopting a chlorination leaching system, so that the washing and size mixing process is omitted, the process is simple, and the comprehensive utilization rate of valuable metals is high.
2. The invention treats refractory metallurgical ore by a full wet process, harmful components such as arsenic, antimony, sulfur and the like in the gold ore enter the solution in an ionic state, thereby being beneficial to subsequent separation and recovery and having little process environmental pollution.
3. The invention can recover valuable elements in gold ores and manganese oxide ores simultaneously, has wider adaptability to materials, simple operation and maintenance and reliable technology, and can realize the simultaneous utilization of valuable metals in gold-carrying materials and manganese-carrying materials.
The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention, and various modifications and changes may be made by those skilled in the art. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (9)
1. A method for treating arsenic-antimony-containing gold-loaded material is characterized by comprising the following steps:
1) crushing and grinding the arsenic-antimony-containing gold-carrying material;
2) mixing manganese oxidized minerals and the arsenic-antimony-containing gold-loaded material treated in the step 1) into acidic slurry in a strong acid sulfuric acid system;
3) heating and oxidizing the acidic slurry to leach sulfide minerals and other reducing substances in the arsenic-antimony-containing gold-carrying material, wherein the acidic slurry is an oxidized leached slurry after the reaction is finished;
4) carrying out solid-liquid separation on the oxidation leaching slurry to obtain oxidation leaching slag and oxidation leaching liquid, wherein the oxidation leaching slag is diluted by water or is adjusted by dilute sulfuric acid or dilute hydrochloric acid to be pulped to obtain diluted slurry;
5) acidifying a chlorination gold extracting agent or directly adding the chlorination gold extracting agent into the diluted slurry prepared by size mixing in the step 4), and performing chlorination leaching of gold to obtain chlorination gold leaching slurry;
6) carrying out solid-liquid separation on the chlorination gold leaching slurry to obtain chlorination leaching liquid and gold leaching tailing residues; and
7) respectively purifying, separating and purifying the chlorination leaching solution and the oxidation leaching solution;
in the step 2), the mass ratio of the arsenic-antimony-containing gold-loaded material to the ore in the manganese oxide mineral is configured according to the mass molar ratio of S to Mn of 1: 3-1: 6;
in the step 3), the strong oxidation leaching of the sulfuric acid system adopts a liquid-solid ratio of 3: 1-10: 1, the concentration of sulfuric acid is 1-5 mol/L, the reaction temperature is 60-250 ℃, the reaction time is 1-4 hours, and the stirring speed is 100-600 r/min;
in the step 4), the oxidation leaching residue is diluted by water or is adjusted by dilute sulfuric acid/dilute hydrochloric acid to be pulped, and the liquid-solid ratio is 3: 1-10: 1; in the step 4), the pH value of the diluted slurry is-0.5-6.
2. The treatment method according to claim 1, wherein the arsenic content, the antimony content and the sulfur content in the arsenic-containing antimony-containing gold-carrying material are respectively 0.1-20% and 0.1-20%, and the ore granularity after ore grinding is-200 meshes and accounts for more than 80%.
3. The treatment method according to claim 1, wherein the manganese oxide minerals are one or more of pyrolusite, manganite and manganese nodules, and the content of Mn in the manganese oxide minerals is 10-63%.
4. The treatment method according to claim 1, wherein in the step 5), the chlorinating agent used for the chlorination of the gold extraction agent is one or more of hypochlorous acid and salts thereof, perchloric acid and salts thereof, and chlorine gas.
5. The treatment method according to claim 4, wherein the amount of the chlorination gold leaching agent in the chlorination gold leaching slurry is 0.01-0.2 mol/L.
6. The treatment method as claimed in claim 4, wherein a conditioning agent is further added to the chlorination leaching, and the conditioning agent is sodium chloride or hydrochloric acid.
7. The treatment method according to claim 1, wherein in the step 5), the liquid-solid ratio in the chlorination leaching process is 3: 1-10: 1, the stirring speed is 200-600 r/min, the leaching reaction temperature is room temperature-250 ℃, and the leaching time is 1-6 hours.
8. The treatment process according to claim 1, wherein the oxidation leachate in step 4) is subjected to an extraction-separation-fractional crystallization-separation process for recovering arsenic, antimony, manganese, sulphur and iron.
9. The treatment method according to claim 1, wherein in the step 7), gold and manganese are recovered from the chlorination leachate by using an active metal replacement method.
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| CN115572835B (en) * | 2022-09-28 | 2024-04-09 | 中国恩菲工程技术有限公司 | Water chlorination gold extraction method for micro-fine particle gold-containing material |
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