CN114182097A - Method for cooperative recycling of copper-zinc-containing oxide and zinc sulfide - Google Patents

Method for cooperative recycling of copper-zinc-containing oxide and zinc sulfide Download PDF

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CN114182097A
CN114182097A CN202111496173.3A CN202111496173A CN114182097A CN 114182097 A CN114182097 A CN 114182097A CN 202111496173 A CN202111496173 A CN 202111496173A CN 114182097 A CN114182097 A CN 114182097A
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zinc
copper
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CN114182097B (en
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王耀宁
马红周
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Xian University of Architecture and Technology
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    • C—CHEMISTRY; METALLURGY
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    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
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    • C22B1/24—Binding; Briquetting ; Granulating
    • C22B1/2406—Binding; Briquetting ; Granulating pelletizing
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    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
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    • C22B19/04—Obtaining zinc by distilling
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    • C22B9/00—General processes of refining or remelting of metals; Apparatus for electroslag or arc remelting of metals
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Abstract

The invention provides a method for synergistically recycling copper-containing zinc oxide and zinc sulfide, which comprises the following steps: mixing and briquetting a carbon reducing agent, a waste catalyst containing copper and zinc oxide and a material containing zinc sulfide to obtain pellets; and (3) carrying out vacuum distillation on the pellets, wherein the distillate obtained by the vacuum distillation is metal zinc, and the distillation residue obtained by the vacuum distillation is a copper sulfide material containing copper and sulfur. The method of the invention uses carbon to reduce copper oxide into metal, then uses metal copper to reduce zinc sulfide into metal zinc, and simultaneously uses the characteristic of easy volatilization of zinc to realize the separation of copper and zinc. The method has the advantages of convenient operation, simple process, high energy utilization rate, safety, sanitation and no pollution.

Description

Method for cooperative recycling of copper-zinc-containing oxide and zinc sulfide
Technical Field
The invention belongs to the field of resource utilization of copper-zinc-containing waste catalysts, and particularly relates to a method for synergistically recycling copper-zinc-containing oxide and zinc sulfide.
Background
The catalyst containing copper and zinc oxide is widely applied to the chemical production and petroleum refining industries, after the catalyst is used for a period of time, the catalytic activity of the catalyst is reduced or loses efficacy due to the change of the catalyst structure, chemical components, specific surface area and the like, the lost catalyst needs to be replaced by a new catalyst, and the replaced lost catalyst is called as a waste catalyst. The waste catalyst is listed as a hazardous waste because of the potential risk to the environment due to the heavy metals contained therein.
The metal-containing spent catalyst is utilized mainly by extracting metals therefrom, and the main components of the spent catalyst containing copper-zinc oxide are zinc oxide, copper oxide and framework materials. The method for extracting copper and zinc from copper-zinc-containing oxide is mainly wet extraction, the commonly adopted process is to leach zinc and copper in the catalyst by using an acid solution, the copper and the zinc are both oxides and enter the solution at the same time, and the framework material of the waste catalyst is separated from the copper and the zinc in a solid form because the framework material is difficult to dissolve in the acid solution. The copper and the zinc in the leaching solution are further separated and extracted into single zinc and copper, the residual framework materials after the zinc and the copper are leached still belong to dangerous wastes because the framework materials also carry metal ions such as copper, zinc and the like, and acidic wastewater generated after the copper and the zinc are extracted needs to be treated. Therefore, the wet method for recycling the waste catalyst containing the copper and zinc oxide is long in process and high in energy consumption, and meanwhile, the skeleton material still belonging to dangerous waste and the acidic wastewater needing to be treated can be generated, so that the sustainable development of waste catalyst recycling enterprises is not facilitated.
The zinc sulfide is typically zinc sulfide mineral, and can also be used as a waste zinc sulfide catalyst produced in a chemical catalysis process or a zinc sulfide precipitate produced in a heavy metal treatment process. The mainstream process for extracting zinc from the zinc sulfide material comprises the following steps: firstly, zinc sulfide is oxidized into zinc oxide, the zinc oxide is leached by sulfuric acid to produce a zinc sulfate solution, and the zinc sulfate solution is purified and then produced into metal zinc by electrodeposition. The zinc sulfide generates SO during oxidation2The flue gas treatment needs a huge dust collecting system and flue gas purifying equipment,result in SO2The treatment cost of the flue gas is higher, and simultaneously, the low-concentration SO is prevented2And (4) discharging.
Disclosure of Invention
In order to solve the problems in the prior art, the invention provides a method for synergistically recycling copper-zinc-containing oxide and zinc sulfide.
The technical scheme adopted by the invention is as follows:
a method for synergistically recycling copper-containing zinc oxide and zinc sulfide comprises the following steps:
preparing a carbon reducing agent, a waste catalyst containing copper and zinc oxide and a material containing zinc sulfide, and then mixing and briquetting to obtain pellets;
and (3) carrying out vacuum distillation on the pellets, wherein the distillate obtained by the vacuum distillation is metal zinc, and the distillation residue obtained by the vacuum distillation is a copper sulfide material containing copper and sulfur.
Preferably: the mixture requirements of the three materials of the carbon reducing agent, the waste catalyst containing copper and zinc oxide and the zinc sulfide material are as follows: mZnS∶MCuO1: 0.5-1; (M)ZnO+MCuO)∶MC1: 1-1.2;
wherein: mZnSThe mole number of zinc in the form of ZnS in the mixture;
MCuOthe mole number of copper existing in the form of CuO in the mixture;
MZnOthe mole number of zinc existing in the form of ZnO in the mixture;
MCis the mole number of fixed carbon in the reducing agent carbon in the mixture.
Preferably, the particle size of the carbonaceous reducing agent is below 80 mesh, the particle size of the waste catalyst containing copper-zinc oxide is below 80 mesh, and the particle size of the material containing zinc sulfide is below 80 mesh when preparing the pellets.
Preferably, when preparing the pellets, the carbon reducing agent, the waste catalyst containing copper and zinc oxide and the water in the material containing zinc sulfide are dried, mixed and pelletized.
Preferably, when preparing the pellets, the pellets are pressed under the pressure of 24MPa-50MPa to prepare the pellets
Figure BDA0003400133930000021
The pellets of (4).
Preferably, the carbon reducing agent is one or a mixture of more of raw coal, coke powder and blue carbon powder.
Preferably, the material containing zinc sulfide comprises one or a mixture of several of waste catalyst containing zinc sulfide and minerals containing zinc sulfide.
Preferably, the temperature of the vacuum distillation is 1100 ℃ to 1200 ℃.
Preferably, the temperature time of the vacuum distillation is 1-10 hours.
Preferably, the pressure during vacuum distillation is 200Pa or less.
The invention has the following beneficial effects:
the invention can realize the cooperative recycling of the copper-containing zinc oxide and the zinc sulfide, and the principle is as follows: when the carbon reducing agent, the waste catalyst containing the copper-zinc oxide and the pellets obtained by processing the material containing the zinc sulfide are subjected to vacuum distillation, the copper oxide in the waste catalyst containing the copper-zinc oxide is reduced into the metal copper by the carbon in the carbon reducing agent, and then the zinc in the material containing the zinc sulfide is reduced into the metal zinc by taking the generated metal copper as the reducing agent. The reaction principle is expressed by chemical reaction as follows: ZnS + CuO + C ═ zn (g) + CuS + co (g). From the above, the invention can realize the cooperative resource utilization of the copper-containing zinc oxide and the zinc sulfide. As can be seen from the implementation process of the process, the process has the following characteristics: 1. the method of the invention realizes the reduction of zinc sulfide and obtains the metal zinc by utilizing the replacement reaction of the metal generated by the reduction of copper oxide by carbon and the zinc sulfide under the vacuum condition. 2. The zinc concentrate obtained by the method mainly exists in a metal state, the subsequent separation process is simple, and the method has the characteristics of high enrichment speed and high production efficiency. 3. When the method of the invention is used for extracting the zinc sulfide, the sulfur in the zinc sulfide is converted into copper sulfide, so that the fixation of the sulfur is realized, and the pollution of the sulfur to the environment in the conventional zinc extraction process is avoided. The cost increase caused by sulfur dioxide treatment in the zinc extraction process and the potential risk to the environment in the sulfur dioxide treatment process are reduced. 4. The method provided by the invention can be used for volatilizing zinc in the zinc sulfide, has the characteristics of short flow, high efficiency and high comprehensive utilization rate of resources, and can be used for greatly improving the separation and extraction efficiency of metal in slag. 5. The method not only realizes the extraction of zinc in the zinc sulfide, but also converts the reducing slag into copper sulfide, can use the copper sulfide in a copper smelting plant, realizes the waste slag problem in the resource utilization process of the zinc sulfide and the copper-containing zinc oxide waste catalyst, and realizes the clean and efficient utilization of the zinc sulfide and the waste catalyst. 6. The carbon added by the method only needs to reduce copper oxide, and the zinc is extracted by the replacement reaction of the metal copper and the zinc sulfide, so that the consumption of the carbon is reduced.
Drawings
FIG. 1 is a diagram showing the main phases of zinc and sulfur in a zinc sulfide spent catalyst according to an embodiment of the present invention;
FIG. 2 is a diagram showing the main phases of copper and zinc in a copper-zinc oxide-containing catalyst according to an embodiment of the present invention;
FIG. 3 is a diagram showing the analysis of the main phase of the reduced slag obtained by reduction in example 7 of the present invention.
Detailed Description
The present invention is not limited to the following embodiments, and all equivalent changes based on the technical solutions of the present invention fall within the protection scope of the present invention. The present invention will be described in further detail with reference to examples.
Because the prior waste catalyst containing copper-zinc oxide has long resource process, and generates the problems of dangerous waste and SO existing in the production process of zinc sulfide2Tackling the problem ofThe invention provides a method for synergistically recycling copper-zinc-containing oxide and zinc sulfide, which can be used for efficiently extracting zinc in a copper-zinc oxide catalyst and zinc in zinc sulfide, converting copper oxide into copper sulfide to prepare a copper sulfide raw material required by copper smelting, and avoiding the problem of waste water and waste residue generated in the treatment process of a waste catalyst. The invention solves the problems of multiple extraction processes, long process and complex pollutant treatment process of the existing waste catalyst containing copper and zinc oxide, and enables the copper to be converted into a form which is easier to be utilized in copper smelting, realizes the extraction of zinc in the catalyst and zinc in zinc sulfide in the process, and has simple process and environmental protection.
The invention adopts the following specific scheme:
the process of the method for the cooperative recycling of the copper-zinc-containing oxide and the zinc sulfide comprises the following steps:
the method comprises the steps of fully mixing zinc sulfide powder, waste catalyst powder containing copper-zinc oxide and a carbon reducing agent (such as carbon powder), pressing into balls, adding the balls into a vacuum distillation furnace, vacuumizing until the pressure in the vacuum distillation furnace is below 200Pa, starting heating, preserving heat when the temperature in the vacuum distillation furnace reaches 1100-1200 ℃, preserving heat for 1-10 hours, collecting distillate obtained by distillation, namely metal zinc, and distillation residue which is a copper and sulfur-rich copper sulfide material, realizing primary extraction of zinc sulfide and zinc in the waste catalyst by carbothermic reduction distillation, obtaining metallic zinc, converting the copper oxide into copper sulfide which is easy to melt at high temperature, further refining zinc obtained by primary distillation separation, obtaining high-purity zinc, and using distillation residues as a raw material for pyrometallurgical copper smelting. The invention realizes the resource utilization of the waste catalyst containing the copper-zinc oxide and the zinc in the zinc sulfide, and creates conditions for the utilization of the copper. The formula is characterized in that the formula comprises the following components in percentage by weight when three materials, namely a carbon reducing agent, a waste catalyst containing copper and zinc oxide and a zinc sulfide material are mixed: mZnS∶MCuO1: 0.5-1; (M)ZnO+MCuO)∶M C1 to (1-1.2).
The invention can convert the copper oxide in the copper-zinc-containing catalyst into sulfur while extracting the zinc in the two materialsThe copper is melted and supplied to the copper smelter in the form of copper concentrate. Through the synergistic effect of the two types of materials, the extraction of zinc in the copper-zinc-containing catalyst and the extraction of zinc in zinc sulfide are realized, the zinc sulfide is enabled to generate copper sulfide in the synergistic treatment process and enters a copper smelting system in the form of copper concentrate, the waste catalyst containing the copper-zinc oxide is not produced with waste residues in the resource recycling process, and SO is not produced in the zinc extraction process in the extraction of the zinc sulfide2A gas. In particular to a method for reducing zinc oxide and copper oxide in a copper-zinc-containing spent catalyst into metal zinc and metal copper respectively by using carbon, and then the reduced metal copper and zinc sulfide generate a displacement reaction to convert zinc in the zinc sulfide into metal zinc and convert copper into copper sulfide.
In the technical scheme of the invention, zinc sulfide and copper-containing zinc oxide are produced from waste catalysts produced in a chemical process. The zinc sulfide material can also be zinc sulfide ore or other materials containing zinc sulfide (such as waste catalyst containing zinc sulfide), and the material containing copper zinc oxide can be used as waste catalyst containing copper zinc oxide, or other types of materials containing copper zinc oxide or materials containing only copper oxide. The carbonaceous reducing agent can be raw coal, and can also be carbonaceous materials such as coke powder or blue carbon powder.
The components of the zinc sulfide spent catalyst referred to in the following examples are shown in table 1, wherein sulfur and zinc are present in the form of zinc sulfide, and the components of the copper-zinc oxide spent catalyst are shown in table 2, wherein copper and zinc are present in the form of oxides, and the mass percentages in tables 1 and 2 are shown.
TABLE 1
Zn/％ S/％ Impurities
62.24 30.6 Balance of
TABLE 2
Cu/％ Zn/％ Impurities
37.28 25.38 Balance of
Example 1:
the embodiment provides a method for cooperative recycling of copper-containing zinc oxide and zinc sulfide, which comprises the following specific processes: respectively taking waste catalyst containing zinc sulfide, waste catalyst containing copper zinc oxide and reducing agent carbon (semi coke with carbon content of 75%) powder, the grain size of all three powders is below 80 meshes, drying the three materials at 100 deg.C, uniformly mixing the dried zinc sulfide catalyst, copper zinc catalyst and semi coke powder according to the following proportion requirement, MZnS∶MCuOIs 1: 0.5; (M)ZnO+MCuO)∶MCThe ratio of the ingredients is 1: 1, the ingredients are uniformly mixed and then pressed into balls by a ball press machine under the pressure of 24MPa, and the product is prepared
Figure BDA0003400133930000061
Placing the mixture pellets in a corundum crucible, placing the mixture pellets in a vacuum distillation furnace, and starting a vacuum pump to ensure that the pressure in the vacuum furnace reaches 200PaHeating, keeping the temperature at 1100 ℃ for 5 hours, cooling to normal temperature after keeping the temperature, breaking vacuum, and collecting distillate obtained by distillation, namely the separated metal zinc.
And weighing the distillation residues, analyzing the zinc content in the distillation residues, and calculating the volatilization rate of zinc, wherein the volatilization rate of zinc after distillation reaches 96.2%.
Example 2:
the embodiment provides a method for cooperative recycling of copper-containing zinc oxide and zinc sulfide, which comprises the following specific processes: respectively taking waste catalyst containing zinc sulfide, waste catalyst containing copper-zinc oxide and reducing agent carbon (semi-coke with carbon content of 75%) powder, drying at 100 deg.C, uniformly mixing the dried zinc sulfide catalyst, copper-zinc catalyst and semi-coke powder according to the following proportion requirementsZnS∶MCuOIs 1: 0.5; (M)ZnO+MCuO)∶MCThe ratio of the ingredients to the raw materials is 1: 1.1, and the ingredients are uniformly mixed and then pressed into balls by a ball press machine under the pressure of 24MPa to prepare the product
Figure BDA0003400133930000062
Placing the mixture pellets in a corundum crucible, placing the mixture pellets in a vacuum distillation furnace, starting a vacuum pump to enable the pressure in the vacuum furnace to reach below 200Pa, starting heating, keeping the temperature for 5 hours when the temperature is 1200 ℃, breaking the vacuum after the temperature is reduced to the normal temperature after the temperature is kept, and collecting distillate obtained by distillation, namely the separated metal zinc.
And weighing the distillation residues, analyzing the zinc content in the distillation residues, and calculating the volatilization rate of zinc, wherein the volatilization rate of zinc after distillation reaches 96.6%.
Example 3:
the embodiment provides a method for cooperative recycling of copper-containing zinc oxide and zinc sulfide, which comprises the following specific processes: respectively taking waste catalyst containing zinc sulfide, waste catalyst containing copper-zinc oxide and reducing agent carbon (semi coke with carbon content of 75%) powder, the grain size of all three powders is below 80 meshes, drying the three materials at 100 deg.C, and pressing the dried zinc sulfide catalyst, copper-zinc catalyst and semi coke powderThe proportion requires uniform mixing, MZnS∶MCuOIs 1: 0.5; (M)ZnO+MCuO)∶MCThe ratio of the ingredients to the raw materials is 1: 1.2, the ingredients are uniformly mixed and then pressed into balls by a ball press machine under the pressure of 24MPa, and the product is prepared
Figure BDA0003400133930000071
Placing the mixture pellets in a corundum crucible, placing the mixture pellets in a vacuum distillation furnace, starting a vacuum pump to enable the pressure in the vacuum furnace to reach below 200Pa, starting heating, keeping the temperature for 5 hours when the temperature is 1200 ℃, breaking the vacuum after the temperature is reduced to the normal temperature after the temperature is kept, and collecting distillate obtained by distillation, namely the separated metal zinc.
And weighing the distillation residues, analyzing the zinc content in the distillation residues, and calculating the volatilization rate of zinc, wherein the volatilization rate of zinc after distillation reaches 99.4%.
Example 4:
the embodiment provides a method for cooperative recycling of copper-containing zinc oxide and zinc sulfide, which comprises the following specific processes: respectively taking waste catalyst containing zinc sulfide, waste catalyst containing copper-zinc oxide and reducing agent carbon (semi-coke with carbon content of 75%) powder, drying at 100 deg.C, uniformly mixing the dried zinc sulfide catalyst, copper-zinc catalyst and semi-coke powder according to the following proportion requirementsZnS∶MCuOThe ratio is 1: 1; (M)ZnO+MCuO)∶MCThe ratio of the ingredients to the raw materials is 1: 1.2, the ingredients are uniformly mixed and then pressed into balls by a ball press machine under the pressure of 24MPa, and the product is prepared
Figure BDA0003400133930000072
Placing the mixture pellets in a corundum crucible, placing the mixture pellets in a vacuum distillation furnace, starting a vacuum pump to enable the pressure in the vacuum furnace to reach below 200Pa, starting heating, keeping the temperature for 5 hours when the temperature is 1200 ℃, breaking the vacuum after the temperature is reduced to the normal temperature after the temperature is kept, and collecting distillate obtained by distillation, namely the separated metal zinc.
And weighing the distillation residues, analyzing the zinc content in the distillation residues, and calculating the volatilization rate of zinc, wherein the volatilization rate of zinc after distillation reaches 89.7%.
Example 5:
the embodiment provides a method for cooperative recycling of copper-containing zinc oxide and zinc sulfide, which comprises the following specific processes: respectively taking waste catalyst containing zinc sulfide, waste catalyst containing copper-zinc oxide and reducing agent carbon (semi-coke with carbon content of 75%) powder, drying at 100 deg.C, uniformly mixing the dried zinc sulfide catalyst, copper-zinc catalyst and semi-coke powder according to the following proportion requirementsZnS∶MCuOIs 1: 0.8; (M)ZnO+MCuO)∶MCThe ratio of the ingredients to the raw materials is 1: 1.2, the ingredients are uniformly mixed and then pressed into balls by a ball press machine under the pressure of 24MPa, and the product is prepared
Figure BDA0003400133930000081
Placing the mixture pellets in a corundum crucible, placing the mixture pellets in a vacuum distillation furnace, starting a vacuum pump to enable the pressure in the vacuum furnace to reach below 200Pa, starting heating, keeping the temperature for 5 hours when the temperature is 1200 ℃, breaking the vacuum after the temperature is reduced to the normal temperature after the temperature is kept, and collecting distillate obtained by distillation, namely the separated metal zinc.
And weighing the distillation residues, analyzing the zinc content in the distillation residues, and calculating the volatilization rate of zinc, wherein the volatilization rate of zinc after distillation reaches 90.9%.
Example 6:
the embodiment provides a method for cooperative recycling of copper-containing zinc oxide and zinc sulfide, which comprises the following specific processes: respectively taking waste catalyst containing zinc sulfide, waste catalyst containing copper-zinc oxide and reducing agent carbon (semi-coke with carbon content of 75%) powder, drying at 100 deg.C, uniformly mixing the dried zinc sulfide catalyst, copper-zinc catalyst and semi-coke powder according to the following proportion requirementsZnS∶MCuOIs 1: 0.5; (M)ZnO+MCuO)∶MCThe ratio of the ingredients to the raw materials is 1: 1.2, the ingredients are uniformly mixed and then pressed into balls by a ball press machine under the pressure of 24MPa, and the product is prepared
Figure BDA0003400133930000082
Placing the mixture pellets in a corundum crucible, putting the mixture pellets in a vacuum distillation furnace, starting a vacuum pump to enable the pressure in the vacuum furnace to reach below 200Pa, starting heating, keeping the temperature for 1 hour when the temperature is 1100 ℃, breaking the vacuum after cooling to the normal temperature after the temperature is kept, and collecting distillate obtained by distillation, namely the separated metal zinc.
And weighing the distillation residues, analyzing the zinc content in the distillation residues, and calculating the volatilization rate of zinc, wherein the volatilization rate of zinc after distillation reaches 90.2%.
Example 7:
the embodiment provides a method for cooperative recycling of copper-containing zinc oxide and zinc sulfide, which comprises the following specific processes: respectively taking waste catalyst containing zinc sulfide, waste catalyst containing copper-zinc oxide and reducing agent carbon (semi-coke with carbon content of 75%) powder, drying at 100 deg.C, uniformly mixing the dried zinc sulfide catalyst, copper-zinc catalyst and semi-coke powder according to the following proportion requirementsZnS∶MCuOIs 1: 0.5; (M)ZnO+MCuO)∶MCThe ratio of the ingredients to the raw materials is 1: 1.2, the ingredients are uniformly mixed and then pressed into balls by a ball press machine under the pressure of 24MPa, and the product is prepared
Figure BDA0003400133930000091
Placing the mixture pellets in a corundum crucible, placing the mixture pellets in a vacuum distillation furnace, starting a vacuum pump to enable the pressure in the vacuum furnace to reach below 200Pa, starting heating, keeping the temperature for 5 hours when the temperature is 1100 ℃, breaking the vacuum after cooling to the normal temperature after the temperature is kept, and collecting distillate obtained by distillation, namely the separated metal zinc.
Weighing the distillation residue, analyzing the zinc content in the distillation residue, calculating the volatilization rate of zinc, and analyzing the phase of the distillation residue, wherein the volatilization rate of zinc after distillation reaches 96.6%, and the result of phase analysis is shown in figure 3, and the main phase in the reduction residue is Cu1.96S, and a zinc sulfide phase and a zinc oxide phase are not detected, which shows that the technical scheme of the invention can realize that sulfur in zinc sulfide is changed into Cu by copper1.96S form is fixed in distillation residue, SO SO is avoided2And (4) generating gas. It can also be said that the reaction process is roughly: the carbon reduces copper oxide to metallic copper, the generated metallic copper is used as a reducing agent to reduce zinc in the material containing zinc sulfide to metallic zinc, the metallic zinc is volatilized from the solid material in the form of steam at high temperature, and Cu is converted into Cu1.96And S. The technical proposal of the invention realizes the separation of copper and zinc and leads sulfur to be solidified into Cu1.96And S, the high-efficiency, environment-friendly and low-carbon resource utilization of various materials is realized.
Example 8:
the embodiment provides a method for cooperative recycling of copper-containing zinc oxide and zinc sulfide, which comprises the following specific processes: respectively taking waste catalyst containing zinc sulfide, waste catalyst containing copper-zinc oxide and reducing agent carbon (semi-coke with carbon content of 75%) powder, drying at 100 deg.C, uniformly mixing the dried zinc sulfide catalyst, copper-zinc catalyst and semi-coke powder according to the following proportion requirementsZnS∶MCuOIs 1: 0.5; (M)ZnO+MCuO)∶MCThe ratio of the ingredients to the raw materials is 1: 1.2, the ingredients are uniformly mixed and then pressed into balls by a ball press machine under the pressure of 50MPa, and the product is prepared
Figure BDA0003400133930000101
Placing the mixture pellets in a corundum crucible, placing the mixture pellets in a vacuum distillation furnace, starting a vacuum pump to enable the pressure in the vacuum furnace to reach below 200Pa, starting heating, keeping the temperature for 10 hours when the temperature is 1100 ℃, breaking the vacuum after cooling to normal temperature after the temperature is kept, and collecting distillate obtained by distillation, namely the separated metal zinc.
And weighing the distillation residues, analyzing the zinc content in the distillation residues, and calculating the volatilization rate of zinc, wherein the volatilization rate of zinc after distillation reaches 98.6%.
Example 9:
the embodiment provides a method for cooperative recycling of copper-containing zinc oxide and zinc sulfide, which comprises the following specific processes: respectively taking the waste catalyst containing zinc sulfide, the waste catalyst containing copper-zinc oxide and reducing agent carbon (semi coke with carbon content of 75%) powder and three kinds of powderThe granularity is below 80 meshes, the three materials are dried at 100 ℃, the dried zinc sulfide catalyst, the copper-containing zinc catalyst and the semi-coke powder are uniformly mixed according to the following proportion requirement, MZnS∶MCuOIs 1: 0.5; (M)ZnO+MCuO)∶MCThe ratio of the ingredients to the raw materials is 1: 1.2, the ingredients are uniformly mixed and then pressed into balls by a ball press machine under the pressure of 50MPa, and the product is prepared
Figure BDA0003400133930000102
Placing the mixture pellets in a corundum crucible, putting the mixture pellets in a vacuum distillation furnace, starting a vacuum pump to enable the pressure in the vacuum furnace to reach below 200Pa, starting heating, keeping the temperature for 1 hour when the temperature is 1200 ℃, breaking the vacuum after the temperature is reduced to the normal temperature after the temperature is kept, and collecting distillate obtained by distillation, namely the separated metal zinc.
And weighing the distillation residues, analyzing the zinc content in the distillation residues, and calculating the volatilization rate of zinc, wherein the volatilization rate of zinc after distillation reaches 95.1%.
Example 10:
the embodiment provides a method for cooperative recycling of copper-containing zinc oxide and zinc sulfide, which comprises the following specific processes: respectively taking waste catalyst containing zinc sulfide, waste catalyst containing copper-zinc oxide and reducing agent carbon (semi-coke with carbon content of 75%) powder, drying at 100 deg.C, uniformly mixing the dried zinc sulfide catalyst, copper-zinc catalyst and semi-coke powder according to the following proportion requirementsZnS∶MCuOIs 1: 0.5; (M)ZnO+MCuO)∶MCThe ratio of the ingredients to the raw materials is 1: 1.2, the ingredients are uniformly mixed and then pressed into balls by a ball press machine under the pressure of 50MPa, and the product is prepared
Figure BDA0003400133930000111
Placing the mixture pellets in a corundum crucible, placing the mixture pellets in a vacuum distillation furnace, starting a vacuum pump to enable the pressure in the vacuum furnace to reach below 200Pa, starting heating, keeping the temperature for 5 hours when the temperature is 1200 ℃, breaking the vacuum after the temperature is reduced to the normal temperature after the temperature is kept, and collecting distillate obtained by distillation, namely the separated metal zinc.
And weighing the distillation residues, analyzing the zinc content in the distillation residues, and calculating the volatilization rate of zinc, wherein the volatilization rate of zinc after distillation reaches 97.6%.
Example 10:
the embodiment provides a method for cooperative recycling of copper-containing zinc oxide and zinc sulfide, which comprises the following specific processes: respectively taking waste catalyst containing zinc sulfide, waste catalyst containing copper-zinc oxide and reducing agent carbon (semi-coke with carbon content of 75%) powder, drying at 100 deg.C, uniformly mixing the dried zinc sulfide catalyst, copper-zinc catalyst and semi-coke powder according to the following proportion requirementsZnS∶MCuOIs 1: 0.5; (M)ZnO+MCuO)∶MCThe ratio of the ingredients to the raw materials is 1: 1.2, the ingredients are uniformly mixed and then pressed into balls by a ball press machine under the pressure of 50MPa, and the product is prepared
Figure BDA0003400133930000112
Placing the mixture pellets in a corundum crucible, placing the mixture pellets in a vacuum distillation furnace, starting a vacuum pump to enable the pressure in the vacuum furnace to reach below 200Pa, starting heating, keeping the temperature for 5 hours when the temperature is 1200 ℃, breaking the vacuum after the temperature is reduced to the normal temperature after the temperature is kept, and collecting distillate obtained by distillation, namely the separated metal zinc.
And weighing the distillation residues, analyzing the zinc content in the distillation residues, and calculating the volatilization rate of zinc, wherein the volatilization rate of zinc after distillation reaches 98.6%.
Example 11:
the embodiment provides a method for cooperative recycling of copper-containing zinc oxide and zinc sulfide, which comprises the following specific processes: respectively taking waste catalyst containing zinc sulfide, waste catalyst containing copper-zinc oxide and reducing agent carbon (semi-coke with carbon content of 75%) powder, drying at 100 deg.C, uniformly mixing the dried zinc sulfide catalyst, copper-zinc catalyst and semi-coke powder according to the following proportion requirementsZnS∶MCuOIs 1: 0.5; (M)ZnO+MCuO)∶MCThe ratio of the ingredients to the raw materials is 1: 1.2, and the ingredients are uniformly mixed and then are pressed by a ball press machine under the pressure of 40MPaPressing the ball to obtain
Figure BDA0003400133930000121
Placing the mixture pellets in a corundum crucible, placing the mixture pellets in a vacuum distillation furnace, starting a vacuum pump to enable the pressure in the vacuum furnace to reach below 200Pa, starting heating, keeping the temperature for 5 hours when the temperature is 1200 ℃, breaking the vacuum after the temperature is reduced to the normal temperature after the temperature is kept, and collecting distillate obtained by distillation, namely the separated metal zinc.
And weighing the distillation residues, analyzing the zinc content in the distillation residues, and calculating the volatilization rate of zinc, wherein the volatilization rate of zinc after distillation reaches 99.7%.
Example 12:
the embodiment provides a method for cooperative recycling of copper-containing zinc oxide and zinc sulfide, which comprises the following specific processes: respectively taking waste catalyst containing zinc sulfide, waste catalyst containing copper-zinc oxide and reducing agent carbon (semi-coke with carbon content of 75%) powder, drying at 100 deg.C, uniformly mixing the dried zinc sulfide catalyst, copper-zinc catalyst and semi-coke powder according to the following proportion requirementsZnS∶MCuOIs 1: 0.5; (M)ZnO+MCuO)∶MCThe ratio of the ingredients to the raw materials is 1: 1.2, the ingredients are uniformly mixed and then pressed into balls by a ball press machine under the pressure of 40MPa, and the product is prepared
Figure BDA0003400133930000122
Placing the mixture pellets in a corundum crucible, placing the mixture pellets in a vacuum distillation furnace, starting a vacuum pump to enable the pressure in the vacuum furnace to reach below 200Pa, starting heating, keeping the temperature for 10 hours when the temperature is 1200 ℃, breaking the vacuum after the temperature is reduced to the normal temperature after the temperature is kept, and collecting distillate obtained by distillation, namely the separated metal zinc.
And weighing the distillation residues, analyzing the zinc content in the distillation residues, and calculating the volatilization rate of zinc, wherein the volatilization rate of zinc after distillation reaches 99.9%.
It can be seen from the above that the method of the present invention can realize the reduction of zinc oxide and zinc sulfide and convert sulfur in zinc sulfide into copper sulfide, and the method not only realizes the extraction and resource utilization of zinc in copper zinc oxide and zinc sulfide, but also converts sulfur into copper sulfide, and creates conditions for transferring copper sulfide into a pyrometallurgical process.

Claims (10)

1. A method for cooperative recycling of copper-containing zinc oxide and zinc sulfide is characterized by comprising the following steps:
mixing and briquetting a carbon reducing agent, a waste catalyst containing copper and zinc oxide and a material containing zinc sulfide to obtain pellets;
and (3) carrying out vacuum distillation on the pellets, wherein the distillate obtained by the vacuum distillation is metal zinc, and the distillation residue obtained by the vacuum distillation is a copper sulfide material containing copper and sulfur.
2. The method for the cooperative recycling of copper-containing zinc oxide and zinc sulfide as claimed in claim 1, wherein:
the mixing requirements of the carbon reducing agent, the waste catalyst containing copper and zinc oxide and the zinc sulfide material are as follows: mZnS：MCuO1: 0.5-1; (M)ZnO+MCuO)∶MC1: 1-1.2;
wherein: mZnSThe mole number of zinc in the form of ZnS in the mixture;
MCuOthe mole number of copper existing in the form of CuO in the mixture;
MZnOthe mole number of zinc existing in the form of ZnO in the mixture;
MCis the mole number of fixed carbon in the reducing agent carbon in the mixture.
3. The method as claimed in claim 1, wherein the pellet is prepared by using the waste catalyst containing copper zinc oxide and zinc sulfide, and the material containing zinc sulfide has a particle size of 80 mesh or less, and the particle size of the waste catalyst containing copper zinc oxide is 80 mesh or less.
4. The method as claimed in claim 1, wherein the carbon reducing agent, the waste catalyst containing copper and zinc oxide and the water in the material containing zinc sulfide are dried, mixed and pelletized.
5. The method as claimed in claim 1, wherein the pellets are pressed under a pressure of 24MPa-50MPa to obtain the final product
Figure FDA0003400133920000011
The pellets of (4).
6. The method for cooperative recycling of copper-containing zinc oxide and zinc sulfide as claimed in claim 1, wherein the carbonaceous reducing agent is one or more of raw coal, coke powder and blue carbon powder.
7. The method for cooperative recycling of copper-zinc-containing oxide and zinc sulfide as claimed in claim 1, wherein the zinc sulfide-containing material comprises a mixture of one or more of a zinc sulfide-containing spent catalyst and a zinc sulfide-containing mineral.
8. The method as claimed in claim 1, wherein the vacuum distillation temperature is 1100-1200 ℃.
9. The method as claimed in claim 1 or 8, wherein the temperature of vacuum distillation is 1-10 hours.
10. The method as claimed in claim 1, wherein the pressure during vacuum distillation is below 200 Pa.
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GB189807904A (en) * 1898-04-02 1898-09-10 Amedee Mathurin Gabri Sebillot Improvements in Method and Apparatus for Reducing Zinc Ores and other Volatile Metals in Blast Furnaces.
GB2048309B (en) * 1979-03-09 1983-01-12 Univ Birmingham Method of recovering non-ferrous metals from their sulphide ores
GB2173820B (en) * 1985-04-03 1989-06-28 Cra Services Smelting process
FI93659C (en) * 1992-05-20 1995-05-10 Outokumpu Research Oy Process for the production of volatile metals such as zinc, lead and cadmium from sulphide raw materials
US5443614A (en) * 1994-07-28 1995-08-22 Noranda, Inc. Direct smelting or zinc concentrates and residues
PE74299A1 (en) * 1997-02-17 1999-08-11 Buka Tech Pty Ltd IMPROVED PROCESSING OF A MATERIAL CONTAINING ZINC SULFIDE
CN1303235C (en) * 2004-10-29 2007-03-07 云南云铜锌业股份有限公司 Dressing and smelting united technology for processing refractory copper zinc ore mixtures
CN108251651B (en) * 2018-02-10 2019-12-13 西安建筑科技大学 method for separating zinc-cadmium-lead alloy materials from copper-cadmium slag and nickel-cobalt slag generated in zinc smelting process

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