CN114182097B - Method for cooperatively recycling copper-zinc-containing oxide and zinc sulfide - Google Patents

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

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CN114182097B
CN114182097B CN202111496173.3A CN202111496173A CN114182097B CN 114182097 B CN114182097 B CN 114182097B CN 202111496173 A CN202111496173 A CN 202111496173A CN 114182097 B CN114182097 B CN 114182097B
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zinc
copper
zinc sulfide
sulfide
zinc oxide
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CN114182097A (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
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • 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
    • C22B7/001—Dry processes
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B1/00—Preliminary treatment of ores or scrap
    • C22B1/14—Agglomerating; Briquetting; Binding; Granulating
    • C22B1/24—Binding; Briquetting ; Granulating
    • C22B1/2406—Binding; Briquetting ; Granulating pelletizing
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B15/00—Obtaining copper
    • C22B15/0002—Preliminary treatment
    • C22B15/0004—Preliminary treatment without modification of the copper constituent
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B15/00—Obtaining copper
    • C22B15/0026—Pyrometallurgy
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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
    • C22B19/00—Obtaining zinc or zinc oxide
    • C22B19/04—Obtaining zinc by distilling
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B19/00—Obtaining zinc or zinc oxide
    • C22B19/30—Obtaining zinc or zinc oxide from metallic residues or scraps
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B5/00—General methods of reducing to metals
    • C22B5/02—Dry methods smelting of sulfides or formation of mattes
    • C22B5/10—Dry methods smelting of sulfides or formation of mattes by solid carbonaceous reducing agents
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B9/00—General processes of refining or remelting of metals; Apparatus for electroslag or arc remelting of metals
    • C22B9/02—Refining by liquating, filtering, centrifuging, distilling, or supersonic wave action including acoustic waves
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B9/00—General processes of refining or remelting of metals; Apparatus for electroslag or arc remelting of metals
    • C22B9/04—Refining by applying a vacuum
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    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
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    • Y02P10/20—Recycling

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Abstract

The invention provides a method for cooperatively recycling copper-containing zinc oxide and zinc sulfide, which comprises the following steps: mixing a carbon reducing agent, a waste catalyst containing copper and zinc oxide and a material containing zinc sulfide, and agglomerating to obtain pellets; and carrying out vacuum distillation on the pellets, wherein a distillate obtained by the vacuum distillation is metallic zinc, and a distillation residue obtained by the vacuum distillation is a copper sulfide material containing copper and sulfur. The method of the invention uses carbon reduction copper oxide as metal, then uses metal copper to reduce zinc sulfide as metal zinc, and simultaneously uses the characteristic of easy volatilization of zinc to realize 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 cooperatively recycling copper-zinc-containing oxide and zinc sulfide
Technical Field
The invention belongs to the field of recycling of copper-zinc-containing waste catalysts, and particularly relates to a method for synergetic recycling of copper-zinc-containing oxide and zinc sulfide.
Background
The catalyst containing copper zinc oxide is widely applied to 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 the catalyst is invalid due to the changes of the catalyst structure, chemical components, specific surface area and the like, the invalid catalyst needs to be replaced by a new catalyst, and the replaced inactivated catalyst is called as a spent catalyst. Since the spent catalyst contains heavy metals, it is a potential hazard to the environment, and thus the spent catalyst is classified as dangerous waste.
The metal-containing spent catalyst is mainly used for extracting metal from the metal-containing spent catalyst, 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 in the copper-zinc-containing oxide mainly adopts a wet extraction method, and the commonly adopted process is to leach the zinc and copper in the catalyst by using an acid solution, wherein the copper and 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 zinc in the leaching solution are further separated and extracted into single zinc and copper, and the residual framework materials after leaching the zinc and the copper still belong to dangerous wastes because the framework materials also carry metal ions such as copper, zinc and the like, and acid wastewater is generated after extracting the copper and the zinc and needs to be treated. Therefore, the wet method for recycling the waste catalyst containing the copper-zinc oxide has longer process and higher energy consumption, and simultaneously, the framework material still belonging to dangerous waste and the acid wastewater to be treated can be produced, thus being unfavorable for the sustainable development of waste catalyst recycling enterprises.
Zinc sulfide is typically zinc sulfide minerals, and also can be used as a waste zinc sulfide catalyst produced in a chemical catalytic process, or as zinc sulfide sediment produced in a heavy metal treatment process, and the like. The main flow process for extracting zinc from zinc sulfide materials comprises the following steps: firstly, zinc sulfide is oxidized into zinc oxide, zinc sulfate solution is produced by leaching the zinc oxide through sulfuric acid, and metal zinc is produced by electro-deposition after the zinc sulfate solution is purified. Zinc sulfide generates SO when oxidized 2 Flue gas, flue gas treatment requires a huge dust collection system and flue gas purification equipment, resulting in SO 2 The treatment cost of the flue gas is higher, and meanwhile, the low-concentration SO is prevented 2 Is arranged in the air.
Disclosure of Invention
In order to solve the problems in the prior art, the invention provides a method for synergetic recycling of copper-containing zinc oxide and zinc sulfide, and the method has the characteristics of simple process and environmental friendliness.
The technical scheme adopted by the invention is as follows:
a method for cooperatively recycling copper-containing zinc oxide and zinc sulfide, which 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 carrying out vacuum distillation on the pellets, wherein a distillate obtained by the vacuum distillation is metallic zinc, and a distillation residue obtained by the vacuum distillation is a copper sulfide material containing copper and sulfur.
Preferably: the three materials of the carbon reducing agent, the dead catalyst containing copper zinc oxide and the zinc sulfide material are mixed according to the following material mixing requirements: m is M ZnS ∶M CuO 1:0.5-1; (M) ZnO +M CuO )∶M C 1:1-1.2;
wherein: m is M ZnS Is the mole number of zinc in ZnS form in the mixture;
M CuO the mole number of copper in the mixture in the form of CuO;
M ZnO the mole number of zinc in the mixture in the form of ZnO;
M C is the mole number of fixed carbon in the reducing agent carbon in the mixture.
Preferably, when preparing pellets, the granularity of the carbon reducing agent is below 80 meshes, the granularity of the waste catalyst containing copper and zinc oxide is below 80 meshes, and the granularity of the material containing zinc sulfide is below 80 meshes.
Preferably, when preparing pellets, the carbon reducing agent, the waste catalyst containing copper and zinc oxide and the moisture in the material containing zinc sulfide are dried, mixed and agglomerated.
Preferably, when preparing the pellets, the pellets are pressed under the pressure of 24MPa to 50MPa to prepareIs not limited to the pellet.
Preferably, the carbon reducing agent adopts one or a mixture of more of raw coal, coke powder and semi-coke powder.
Preferably, the zinc sulfide-containing material comprises one or a mixture of a waste catalyst containing zinc sulfide and a mineral containing zinc sulfide.
Preferably, the temperature of the vacuum distillation is 1100-1200 ℃.
Preferably, the temperature of the vacuum distillation is 1 to 10 hours.
Preferably, the pressure during vacuum distillation is 200Pa or less.
The invention has the following beneficial effects:
the invention can cooperatively recycle the copper-zinc oxide and the zinc sulfide, and specifically adopts the following principle: when the carbon reducing agent, the waste catalyst containing copper and zinc oxide and pellets obtained by processing materials containing zinc sulfide are subjected to vacuum distillation, carbon in the carbon reducing agent reduces copper oxide in the waste catalyst containing copper and zinc oxide into metallic copper, and then generated metallic copper is used as a reducing agent to reduce zinc in the materials containing zinc sulfide into metallic zinc. The reaction principle is expressed as chemical reaction: 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 above technical implementation process of the invention, the invention has the following characteristics: 1. the method of the invention realizes the reduction of zinc sulfide and obtains metallic zinc by utilizing the displacement reaction of the metal generated by the reduction of copper oxide by carbon and zinc sulfide under the vacuum condition, and the method has convenient operation, safety, sanitation and no pollution. 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 is used for extracting zinc sulfide, sulfur in the zinc sulfide is converted into copper sulfide, so that the sulfur is fixed, and the pollution of 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 caused by the sulfur dioxide treatment process are reduced. 4. The method of the invention realizes volatilization of zinc in zinc sulfide, has the characteristics of short flow, high efficiency and high comprehensive utilization rate of resources, and can greatly improve the separation and extraction efficiency of metals in slag. 5. The method not only realizes the extraction of zinc in zinc sulfide, but also converts reducing slag into copper sulfide, and can use the copper sulfide in copper smelting plants, thereby realizing the waste residue problem in the recycling process of zinc sulfide and copper-containing zinc oxide waste catalyst and realizing the clean and efficient utilization of zinc sulfide and waste catalyst. 6. The method only needs to reduce copper oxide, and realizes extraction of zinc by displacement reaction of metallic copper and zinc sulfide, thereby reducing the consumption of carbon.
Drawings
FIG. 1 is a diagram of the major phases of zinc and sulfur in a zinc sulfide spent catalyst according to an embodiment of the invention;
FIG. 2 is a diagram of the major phases of copper and zinc in a catalyst comprising copper and zinc oxide according to an embodiment of the present invention;
FIG. 3 is a diagram showing the analysis of the main phases in the reduced slag obtained in example 7 of the present invention.
Detailed Description
The following specific embodiments of the present invention are given according to the above technical solutions, and it should be noted that the present invention is not limited to the following specific embodiments, and all equivalent changes made on the basis of the technical solutions of the present application fall within the protection scope of the present invention. The present invention will be described in further detail with reference to examples.
Because the existing dead catalyst containing copper-zinc oxide is tedious in resource technology, and generates dangerous waste and SO existing in the zinc sulfide production process 2 In order to solve the problems, the invention provides a method for synergetic recycling of copper-zinc oxide and zinc sulfide, which is used for efficiently extracting zinc in a copper-zinc oxide catalyst and zinc in zinc sulfide, converting copper oxide into copper sulfide and preparing copper sulfide raw materials required by copper smelting, and avoiding the problems of waste water and waste residues generated in the treatment process of a waste catalyst. The invention solves the problems of more extraction procedures, lengthy process and complex pollutant treatment procedures of the existing dead catalyst containing copper and zinc oxide, and converts copper into a form which is easier to be utilized in copper smelting, and realizes the extraction of zinc in the catalyst and zinc in zinc sulfide in the process, and the invention has simple process and environmental protection.
The invention adopts the following specific scheme:
the process of the method for synergetic recycling of the copper-containing zinc oxide and the zinc sulfide comprises the following steps:
the method comprises the steps of fully mixing zinc sulfide powder, copper-zinc oxide-containing waste catalyst powder and a carbon reducing agent (such as carbon powder), pressing balls, then adding the mixture 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 ℃ for 1-10 hours, collecting distillates obtained by distillation to obtain metallic zinc, distilling residual residues to obtain copper sulfide materials rich in copper and sulfur, performing carbothermic reduction distillation to realize primary extraction of zinc in the zinc sulfide and the waste catalyst, obtaining metallic zinc, converting the copper oxide into copper sulfide which is easy to smelt at high temperature, and refining the zinc obtained by primary distillation separation to obtain high-purity zinc, wherein the distilled residues are used as a raw material for pyrometallurgical copper smelting. The invention realizes the utilization of zinc resources in the zinc sulfide and the dead catalyst containing copper-zinc oxide, and creates conditions for the utilization of copper. Wherein, the material mixing 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: m is M ZnS ∶M CuO 1:0.5-1; (M) ZnO +M CuO )∶M C 1 to 1-1.2.
The method disclosed by the invention can be used for extracting zinc from two materials, simultaneously converting copper oxide in the copper-zinc-containing catalyst into copper sulfide, and providing the copper sulfide to a copper smelting plant in the form of copper concentrate. Through the synergistic effect of the two materials, not only realizes the extraction of zinc in the copper-containing zinc catalyst, but also realizes the extraction of zinc in zinc sulfide, and in the synergistic treatment process, zinc sulfide is made to generate copper sulfide and enter a copper smelting system in the form of copper concentrate, thereby realizing the no waste residue output of the copper-containing zinc oxide waste catalyst in the recycling process, and realizing no SO (sulfur dioxide) in the zinc extraction process in the zinc sulfide extraction process 2 And (3) gas. In particular to a method for converting zinc in zinc sulfide into metallic zinc and converting copper into copper sulfide by utilizing carbon to reduce zinc oxide and copper oxide in a copper-zinc-containing dead catalyst into metallic zinc and metallic copper respectively and then carrying out displacement reaction on the reduced metallic copper and the zinc sulfide.
In the technical scheme of the invention, both zinc sulfide and copper-zinc oxide are produced from waste catalysts produced in the 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 waste catalyst containing copper-zinc oxide, or other types of materials containing copper-zinc oxide or materials containing copper oxide only. The carbonaceous reducing agent may be raw coal, or may be carbonaceous materials such as coke powder or semi-coke powder.
The zinc sulfide spent catalyst components referred to in the following examples are shown in table 1, wherein sulfur and zinc are present as zinc sulfide, and the copper-zinc oxide spent catalyst components are shown in table 2, wherein copper and zinc are both present as oxides, and the mass percentages in table 1 and table 2 are shown.
TABLE 1
Zn/％ S/％ Impurity(s)
62.24 30.6 Allowance of
TABLE 2
Cu/％ Zn/％ Impurity(s)
37.28 25.38 Allowance of
Example 1:
the embodiment provides a method for cooperatively recycling 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 reducer carbon (semi-coke with carbon content of 75%) powder, wherein the granularity of the three powders is below 80 meshes, drying the three materials at 100 ℃, and uniformly mixing the dried zinc sulfide catalyst, copper zinc catalyst and semi-coke powder according to the following proportion requirement, wherein M ZnS ∶M CuO 1:0.5; (M) ZnO +M CuO )∶M C 1:1, and pressing the mixture into balls under 24MPa by a ball pressing machinePlacing the mixture pellets into a corundum crucible, placing the mixture pellets into a vacuum distillation furnace, starting a vacuum pump to enable the pressure in the vacuum furnace to be lower than 200Pa, starting heating, preserving heat for 5 hours when the temperature is 1100 ℃, cooling to normal temperature after the heat preservation is finished, breaking vacuum, and collecting distillate obtained by distillation, namely the separated metallic zinc.
And weighing the distillation residues, analyzing the zinc content in the distillation residues, and calculating the volatilization rate of the zinc, wherein the volatilization rate of the zinc reaches 96.2% after distillation.
Example 2:
the embodiment provides a method for cooperatively recycling 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, wherein the granularity of the three powders is below 80 meshes, and the granularity of the three materials is 100Drying at the temperature, uniformly mixing the dried zinc sulfide catalyst, copper-zinc-containing catalyst and semi-coke powder according to the following proportion requirement, and M ZnS ∶M CuO 1:0.5; (M) ZnO +M CuO )∶M C 1:1.1, and pressing the mixture into balls under 24MPa by a ball pressing machinePlacing the mixture pellets into a corundum crucible, placing the mixture pellets into a vacuum distillation furnace, starting a vacuum pump to enable the pressure in the vacuum furnace to be lower than 200Pa, starting heating, preserving heat for 5 hours when the temperature is 1200 ℃, cooling to normal temperature after the heat preservation is finished, breaking vacuum, and collecting distillate obtained by distillation, namely the separated metallic zinc.
And weighing the distillation residues, analyzing the zinc content in the distillation residues, and calculating the volatilization rate of the zinc, wherein the volatilization rate of the zinc reaches 96.6% after distillation.
Example 3:
the embodiment provides a method for cooperatively recycling copper-containing zinc oxide and zinc sulfide, which comprises the following specific processes: respectively taking waste catalyst containing zinc sulfide, waste catalyst containing copper and zinc oxide and reducing agent carbon (semi-coke with carbon content of 75%) powder, wherein the granularity of the three powders is below 80 meshes, drying the three materials at 100 ℃, and uniformly mixing the dried zinc sulfide catalyst, the dried copper-zinc catalyst and the semi-coke powder according to the following proportion requirement, wherein M ZnS ∶M CuO 1:0.5; (M) ZnO +M CuO )∶M C Is 1:1.2, and the mixture is uniformly mixed and then is pressed into balls under the pressure of 24MPa by a ball pressing machine to prepare the ball-pressing machinePlacing the mixture pellets into a corundum crucible, placing the mixture pellets into a vacuum distillation furnace, starting a vacuum pump to enable the pressure in the vacuum furnace to be lower than 200Pa, starting heating, preserving heat for 5 hours when the temperature is 1200 ℃, cooling to normal temperature after the heat preservation is finished, breaking vacuum, and collecting distillate obtained by distillation, namely the separated metallic 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 reaches 99.4% after distillation.
Example 4:
the embodiment provides a method for cooperatively recycling copper-containing zinc oxide and zinc sulfide, which comprises the following specific processes: respectively taking waste catalyst containing zinc sulfide, waste catalyst containing copper and zinc oxide and reducing agent carbon (semi-coke with carbon content of 75%) powder, wherein the granularity of the three powders is below 80 meshes, drying the three materials at 100 ℃, and uniformly mixing the dried zinc sulfide catalyst, the dried copper-zinc catalyst and the semi-coke powder according to the following proportion requirement, wherein M ZnS ∶M CuO Is 1:1; (M) ZnO +M CuO )∶M C Is 1:1.2, and the mixture is uniformly mixed and then is pressed into balls under the pressure of 24MPa by a ball pressing machine to prepare the ball-pressing machinePlacing the mixture pellets into a corundum crucible, placing the mixture pellets into a vacuum distillation furnace, starting a vacuum pump to enable the pressure in the vacuum furnace to be lower than 200Pa, starting heating, preserving heat for 5 hours when the temperature is 1200 ℃, cooling to normal temperature after the heat preservation is finished, breaking vacuum, and collecting distillate obtained by distillation, namely the separated metallic zinc.
And weighing the distillation residues, analyzing the zinc content in the distillation residues, and calculating the volatilization rate of the zinc, wherein the volatilization rate of the zinc reaches 89.7% after distillation.
Example 5:
the embodiment provides a method for cooperatively recycling copper-containing zinc oxide and zinc sulfide, which comprises the following specific processes: respectively taking waste catalyst containing zinc sulfide, waste catalyst containing copper and zinc oxide and reducing agent carbon (semi-coke with carbon content of 75%) powder, wherein the granularity of the three powders is below 80 meshes, drying the three materials at 100 ℃, and uniformly mixing the dried zinc sulfide catalyst, the dried copper-zinc catalyst and the semi-coke powder according to the following proportion requirement, wherein M ZnS ∶M CuO 1:0.8; (M) ZnO +M CuO )∶M C Is 1:1.2, and the mixture is uniformly mixed and then is pressed into balls under the pressure of 24MPa by a ball pressing machine to prepare the ball-pressing machinePlacing the mixture pellets into a corundum crucible, placing the mixture pellets into a vacuum distillation furnace, starting a vacuum pump to enable the pressure in the vacuum furnace to be lower than 200Pa, starting heating, preserving heat for 5 hours when the temperature is 1200 ℃, cooling to normal temperature after the heat preservation is finished, breaking vacuum, and collecting distillate obtained by distillation, namely the separated metallic zinc.
And weighing the distillation residues, analyzing the zinc content in the distillation residues, and calculating the volatilization rate of the zinc, wherein the volatilization rate of the zinc reaches 90.9% after distillation.
Example 6:
the embodiment provides a method for cooperatively recycling copper-containing zinc oxide and zinc sulfide, which comprises the following specific processes: respectively taking waste catalyst containing zinc sulfide, waste catalyst containing copper and zinc oxide and reducing agent carbon (semi-coke with carbon content of 75%) powder, wherein the granularity of the three powders is below 80 meshes, drying the three materials at 100 ℃, and uniformly mixing the dried zinc sulfide catalyst, the dried copper-zinc catalyst and the semi-coke powder according to the following proportion requirement, wherein M ZnS ∶M CuO 1:0.5; (M) ZnO +M CuO )∶M C Is 1:1.2, and the mixture is uniformly mixed and then is pressed into balls under the pressure of 24MPa by a ball pressing machine to prepare the ball-pressing machinePlacing the mixture pellets into a corundum crucible, placing the mixture pellets into a vacuum distillation furnace, starting a vacuum pump to enable the pressure in the vacuum furnace to be lower than 200Pa, starting heating, preserving heat for 1 hour when the temperature is 1100 ℃, cooling to normal temperature after the heat preservation is finished, breaking vacuum, and collecting distillate obtained by distillation, namely the separated metallic zinc.
And weighing the distillation residues, analyzing the zinc content in the distillation residues, and calculating the volatilization rate of the zinc, wherein the volatilization rate of the zinc reaches 90.2% after distillation.
Example 7:
the embodiment provides a method for cooperatively recycling copper-containing zinc oxide and zinc sulfide, which comprises the following specific processes: waste catalyst containing zinc sulfide is respectively takenThe catalyst, the waste catalyst containing copper and zinc oxide and the reducing agent carbon (semi-coke with carbon content of 75%) powder are all of granularity below 80 meshes, the three materials are dried at 100 ℃, and the dried zinc sulfide catalyst, the copper-zinc catalyst and the semi-coke powder are uniformly mixed according to the following proportion requirement, M ZnS ∶M CuO 1:0.5; (M) ZnO +M CuO )∶M C Is 1:1.2, and the mixture is uniformly mixed and then is pressed into balls under the pressure of 24MPa by a ball pressing machine to prepare the ball-pressing machinePlacing the mixture pellets into a corundum crucible, placing the mixture pellets into a vacuum distillation furnace, starting a vacuum pump to enable the pressure in the vacuum furnace to be lower than 200Pa, starting heating, preserving heat for 5 hours when the temperature is 1100 ℃, cooling to normal temperature after the heat preservation is finished, breaking vacuum, and collecting distillate obtained by distillation, namely the separated metallic zinc.
Weighing the distillation residues, analyzing zinc content, calculating zinc volatilization rate, distilling to obtain zinc volatilization rate of 96.6%, and phase analyzing the distillation residues to obtain the main phase Cu in the reducing slag as shown in figure 3 1.96 S, zinc sulfide phase and zinc oxide phase are not detected, and the technical scheme of the invention can realize that sulfur in zinc sulfide is replaced by Cu 1.96 S form is fixed in distillation residue, SO is avoided 2 And (3) generating gas. It can thus also be stated that the reaction process is approximately: the carbon reduces the copper oxide into metallic copper, the generated metallic copper is used as a reducing agent to reduce zinc in the material containing zinc sulfide into metallic zinc, the metallic zinc volatilizes from the solid material in a vapor form at high temperature, and Cu is converted into Cu 1.96 S, S. The technical proposal of the invention not only realizes the separation of copper and zinc, but also ensures that sulfur is solidified to form Cu 1.96 S, the recycling utilization of various materials with high efficiency, environmental protection and low carbon is realized.
Example 8:
the embodiment provides a method for cooperatively recycling copper-containing zinc oxide and zinc sulfide, which comprises the following specific processes: respectively taking the waste catalyst containing zinc sulfide and the oxide containing copper and zincWaste catalyst and reducer carbon (semi-coke with carbon content of 75%) powder, the granularity of the three powders is below 80 meshes, the three materials are dried at 100 ℃, and the dried zinc sulfide catalyst, copper-zinc-containing catalyst and semi-coke powder are uniformly mixed according to the following proportion requirement, M ZnS ∶M CuO 1:0.5; (M) ZnO +M CuO )∶M C Is 1:1.2, and the mixture is uniformly mixed and then is pressed into balls under the pressure of 50MPa by a ball pressing machine to prepare the ball-pressing machinePlacing the mixture pellets into a corundum crucible, placing the mixture pellets into a vacuum distillation furnace, starting a vacuum pump to enable the pressure in the vacuum furnace to be lower than 200Pa, starting heating, preserving heat for 10 hours when the temperature is 1100 ℃, cooling to normal temperature after the heat preservation is finished, breaking vacuum, and collecting distillate obtained by distillation, namely the separated metallic 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 reaches 98.6% after distillation.
Example 9:
the embodiment provides a method for cooperatively recycling copper-containing zinc oxide and zinc sulfide, which comprises the following specific processes: respectively taking waste catalyst containing zinc sulfide, waste catalyst containing copper and zinc oxide and reducing agent carbon (semi-coke with carbon content of 75%) powder, wherein the granularity of the three powders is below 80 meshes, drying the three materials at 100 ℃, and uniformly mixing the dried zinc sulfide catalyst, the dried copper-zinc catalyst and the semi-coke powder according to the following proportion requirement, wherein M ZnS ∶M CuO 1:0.5; (M) ZnO +M CuO )∶M C Is 1:1.2, and the mixture is uniformly mixed and then is pressed into balls under the pressure of 50MPa by a ball pressing machine to prepare the ball-pressing machinePlacing the mixture pellets into a corundum crucible, placing the corundum crucible into a vacuum distillation furnace, starting a vacuum pump to enable the pressure in the vacuum furnace to be lower than 200Pa, starting heating, preserving heat for 1 hour when the temperature is 1200 ℃, cooling to normal temperature after the heat preservation is finished, breaking vacuum, and collecting steamThe distillate obtained by distillation is the separated zinc metal.
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 reaches 95.1% after distillation.
Example 10:
the embodiment provides a method for cooperatively recycling copper-containing zinc oxide and zinc sulfide, which comprises the following specific processes: respectively taking waste catalyst containing zinc sulfide, waste catalyst containing copper and zinc oxide and reducing agent carbon (semi-coke with carbon content of 75%) powder, wherein the granularity of the three powders is below 80 meshes, drying the three materials at 100 ℃, and uniformly mixing the dried zinc sulfide catalyst, the dried copper-zinc catalyst and the semi-coke powder according to the following proportion requirement, wherein M ZnS ∶M CuO 1:0.5; (M) ZnO +M CuO )∶M C Is 1:1.2, and the mixture is uniformly mixed and then is pressed into balls under the pressure of 50MPa by a ball pressing machine to prepare the ball-pressing machinePlacing the mixture pellets into a corundum crucible, placing the mixture pellets into a vacuum distillation furnace, starting a vacuum pump to enable the pressure in the vacuum furnace to be lower than 200Pa, starting heating, preserving heat for 5 hours when the temperature is 1200 ℃, cooling to normal temperature after the heat preservation is finished, breaking vacuum, and collecting distillate obtained by distillation, namely the separated metallic 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 reaches 97.6% after distillation.
Example 10:
the embodiment provides a method for cooperatively recycling copper-containing zinc oxide and zinc sulfide, which comprises the following specific processes: respectively taking waste catalyst containing zinc sulfide, waste catalyst containing copper and zinc oxide and reducing agent carbon (semi-coke with carbon content of 75%) powder, wherein the granularity of the three powders is below 80 meshes, drying the three materials at 100 ℃, and uniformly mixing the dried zinc sulfide catalyst, the dried copper-zinc catalyst and the semi-coke powder according to the following proportion requirement, wherein M ZnS ∶M CuO 1:0.5; (M) ZnO +M CuO )∶M C Is 1:1.2, and the mixture is uniformly mixed and then is pressed into balls under the pressure of 50MPa by a ball pressing machine to prepare the ball-pressing machinePlacing the mixture pellets into a corundum crucible, placing the mixture pellets into a vacuum distillation furnace, starting a vacuum pump to enable the pressure in the vacuum furnace to be lower than 200Pa, starting heating, preserving heat for 5 hours when the temperature is 1200 ℃, cooling to normal temperature after the heat preservation is finished, breaking vacuum, and collecting distillate obtained by distillation, namely the separated metallic 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 reaches 98.6% after distillation.
Example 11:
the embodiment provides a method for cooperatively recycling copper-containing zinc oxide and zinc sulfide, which comprises the following specific processes: respectively taking waste catalyst containing zinc sulfide, waste catalyst containing copper and zinc oxide and reducing agent carbon (semi-coke with carbon content of 75%) powder, wherein the granularity of the three powders is below 80 meshes, drying the three materials at 100 ℃, and uniformly mixing the dried zinc sulfide catalyst, the dried copper-zinc catalyst and the semi-coke powder according to the following proportion requirement, wherein M ZnS ∶M CuO 1:0.5; (M) ZnO +M CuO )∶M C Is 1:1.2, and the mixture is uniformly mixed and then is pressed into balls under the pressure of 40MPa by a ball pressing machine to prepare the ball-pressing machinePlacing the mixture pellets into a corundum crucible, placing the mixture pellets into a vacuum distillation furnace, starting a vacuum pump to enable the pressure in the vacuum furnace to be lower than 200Pa, starting heating, preserving heat for 5 hours when the temperature is 1200 ℃, cooling to normal temperature after the heat preservation is finished, breaking vacuum, and collecting distillate obtained by distillation, namely the separated metallic 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 reaches 99.7% after distillation.
Example 12:
the present embodiment givesThe method for cooperatively recycling the copper-containing zinc oxide and the zinc sulfide comprises the following specific processes: respectively taking waste catalyst containing zinc sulfide, waste catalyst containing copper and zinc oxide and reducing agent carbon (semi-coke with carbon content of 75%) powder, wherein the granularity of the three powders is below 80 meshes, drying the three materials at 100 ℃, and uniformly mixing the dried zinc sulfide catalyst, the dried copper-zinc catalyst and the semi-coke powder according to the following proportion requirement, wherein M ZnS ∶M CuO 1:0.5; (M) ZnO +M CuO )∶M C Is 1:1.2, and the mixture is uniformly mixed and then is pressed into balls under the pressure of 40MPa by a ball pressing machine to prepare the ball-pressing machinePlacing the mixture pellets into a corundum crucible, placing the mixture pellets into a vacuum distillation furnace, starting a vacuum pump to enable the pressure in the vacuum furnace to be lower than 200Pa, starting heating, preserving heat for 10 hours when the temperature is 1200 ℃, cooling to normal temperature after the heat preservation is finished, breaking vacuum, and collecting distillate obtained by distillation, namely the separated metallic zinc.
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 reaches 99.9% after distillation.
From the above, the method 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 recycling of zinc in copper zinc oxide and zinc sulfide, but also converts sulfur into copper sulfide, thereby creating conditions for transferring copper sulfide into a pyrometallurgy process.

Claims (6)

1. A method for cooperatively recycling copper-containing zinc oxide and zinc sulfide, which is characterized by comprising the following steps:
mixing a carbon reducing agent, a waste catalyst containing copper and zinc oxide and a material containing zinc sulfide, and agglomerating to obtain pellets;
carrying out vacuum distillation on the pellets, wherein distillate obtained by the vacuum distillation is metallic zinc, and distillation residues obtained by the vacuum distillation are copper sulfide materials containing copper and sulfur;
the material mixing requirements of the carbon reducing agent, the waste catalyst containing copper and zinc oxide and the zinc sulfide material are as follows: m is M ZnS ：M CuO 1:0.5-1; (M) ZnO +M CuO ）∶M C 1:1-1.2;
wherein: m is M ZnS Is the mole number of zinc in ZnS form in the mixture;
M CuO the mole number of copper in the mixture in the form of CuO;
M ZnO the mole number of zinc in the mixture in the form of ZnO;
M C the mole number of fixed carbon in the reducing agent carbon in the mixture;
the temperature of vacuum distillation is 1100-1200 ℃;
the heat preservation time of vacuum distillation is 1-10 hours;
the pressure during vacuum distillation was 200Pa or less.
2. The method for the synergistic recycling of copper-zinc oxide and zinc sulfide according to claim 1, wherein the particle size of the carbon reducing agent is below 80 meshes, the particle size of the waste catalyst of the copper-zinc oxide is below 80 meshes, and the particle size of the material containing zinc sulfide is below 80 meshes when preparing pellets.
3. The method for synergic recycling of copper-zinc oxide and zinc sulfide according to claim 1, wherein the carbon reducing agent, the waste catalyst containing copper-zinc oxide and the water in the material containing zinc sulfide are dried before mixing and briquetting.
4. The method for the synergistic recycling of copper-zinc oxide and zinc sulfide according to claim 1, wherein the pellets are prepared by pressing the pellets under the pressure of 24MPa to 50MPa to prepare the pellets with the diameter of 10 mm to 50 mm.
5. The method for the synergistic recycling of copper-zinc oxide and zinc sulfide according to claim 1, wherein the carbon reducing agent is one or a mixture of more of raw coal, coke powder and semi-coke powder.
6. A method for the co-recycling of copper-zinc oxide and zinc sulfide according to 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.
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