CN115627367A - Method for lead and antimony co-smelting - Google Patents
Method for lead and antimony co-smelting Download PDFInfo
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- CN115627367A CN115627367A CN202211261190.3A CN202211261190A CN115627367A CN 115627367 A CN115627367 A CN 115627367A CN 202211261190 A CN202211261190 A CN 202211261190A CN 115627367 A CN115627367 A CN 115627367A
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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
- C22B13/00—Obtaining lead
- C22B13/02—Obtaining lead by dry processes
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B17/00—Sulfur; Compounds thereof
- C01B17/69—Sulfur trioxide; Sulfuric acid
- C01B17/74—Preparation
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B7/00—Hydraulic cements
- C04B7/14—Cements containing slag
- C04B7/147—Metallurgical slag
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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
- C22B30/00—Obtaining antimony, arsenic or bismuth
- C22B30/02—Obtaining antimony
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
Abstract
The invention discloses a method for lead and antimony collaborative smelting, which comprises the following steps: lead concentrate, antimony concentrate and lime are uniformly mixed and then placed in a smelting furnace for oxygen-enriched enhanced smelting, antimony-enriched lead bullion is produced after smelting, refined lead and antimony-containing anode mud are obtained after the antimony-enriched lead bullion is subjected to electrolytic refining, antimony-containing anode mud is blown in a converter and leached by nitric acid to obtain lead nitrate leachate and antimony oxide powder, the antimony oxide powder is granulated and then placed in a reduction furnace, and hydrogen is introduced for reduction smelting to prepare metal antimony. In the process, the lead concentrate and the antimony concentrate are subjected to synergistic smelting, the similar interaction reaction between lead and antimony is fully utilized, the smelting temperature of the lead concentrate is reduced, and the problems that the heat utilization rate is low and the concentration of sulfur dioxide in flue gas cannot be used for preparing acid in the volatilization smelting process of the antimony concentrate are solved. And in the process of preparing crude antimony by reducing antimony oxide powder, the carbon reducing agent is replaced by hydrogen, so that the reduction temperature is reduced, the defects of high energy consumption, large carbon dioxide generation, low direct recovery rate caused by secondary volatilization of antimony and the like in the traditional reduction smelting process are overcome, and the method has a wide industrial application prospect.
Description
Technical Field
The invention belongs to the technical field of nonferrous metallurgy, and particularly relates to a method for lead and antimony collaborative smelting.
Background
Metallic antimony is a silvery white, lustrous, hard and brittle metal, and antimony has been widely used for producing various flame retardants, alloys, ceramics, glass, semiconductor elements, and the like. Modern metallurgical production methods of antimony can be divided into pyrometallurgy and hydrometallurgy, the industry mainly adopts pyrometallurgy and mainly adopts a volatilization smelting-reduction smelting method, namely, antimony concentrate is firstly subjected to volatilization smelting to generate antimony oxide powder (antimony trioxide), and the antimony oxide powder is subjected to reduction smelting to generate crude antimony. The volatilization equipment commonly used at present comprises a shaft furnace, a blast furnace and the like. However, the current volatilization smelting has more outstanding problems: (1) SO produced in the process 2 The flue gas concentration is low, and acid can not be prepared; (2) The smelting process has low thermal efficiency and needs to consume more expensive metallurgical coke; (3) The charging hole of the blast furnace has large area and cannot be sealed, which causes the escape of smoke dust and smoke gas and pollutes the environment. In addition, in the reduction smelting process, anthracite, charcoal, carbon powder and the like are used as reducing agents to perform reduction reaction with antimony oxide powder at the temperature of 1000-1200 ℃ to prepare the metal antimony, wherein the using amount of the reducing agents is about 10-30% of the mass of the antimony oxide powder. The use of carbonaceous reducing agents not only has high reduction temperature and serious antimony volatilization, but also can generate a large amount of carbon dioxide, which is not beneficial to realizing the strategic goal of 'double carbon'.
Chinese patent document CN 103173636B discloses a method for smelting antimony sulfide concentrate in an oxygen-rich molten pool. The method comprises the steps of carrying out oxygen-enriched molten pool smelting on antimony concentrate, limestone, quartz sand and iron ore ingredients to obtain precious antimony, smelting slag and flue gas after smelting, wherein the smelting slag is subjected to smelting reduction to generate crude antimony. Although the method realizes the self-heating smelting of the antimony sulfide concentrate and reduces the energy consumption, the content of sulfur in the raw material is required to be more than 16 percent, and the concentration of sulfur dioxide in the generated flue gas meets the requirement of acid preparation.
Chinese patent document CN 104278162A discloses a method for selectively smelting a complex material containing antimony and lead in a molten pool. The method comprises the steps of mixing materials containing antimony and lead with pyrite, quartz and limestone, uniformly mixing, granulating, adding the mixture into oxidation smelting slag containing antimony oxide, smelting, controlling the content of antimony in the oxidation smelting slag to enable most of lead, bismuth and silver to be reduced and enter crude lead, and carrying out reduction smelting on high-antimony oxidation slag through a molten pool to obtain crude antimony. Although the method realizes the comprehensive smelting of lead and antimony and the primary separation of lead and antimony, the smelting temperature in the process is high, and waste gas is generated in the reduction smelting process of antimony oxide slag in a molten pool and the reduction smelting slag needs to be further treated.
Chinese patent document CN 101157994A discloses a method for oxygen molten pool smelting of lead-antimony ore, which comprises the steps of carrying out oxidation smelting on lead concentrate or mixed ore of lead-antimony ore and lead concentrate, flux, smoke dust, solid fuel and other materials, and then adding the materials into molten oxidation bottom slag to produce lead-antimony alloy and oxidation smelting slag for fuming treatment. Although the process has the advantages of short flow and capability of preparing acid by using flue gas, the method has the problems of high smelting temperature, strict requirements on the granularity and the moisture of raw materials and the like in the smelting process of a molten pool. In addition, the invention only provides the idea of a molten pool smelting process, and does not further separate the produced lead-antimony alloy and effectively enrich the precious metals in the lead-antimony ore.
At present, the oxygen-enriched smelting technology of lead concentrate has relatively perfect theoretical and practical experience, and the problems of low concentration of sulfur dioxide in flue gas, high reduction smelting temperature and the like exist in the volatilization smelting-reduction smelting process of antimony. If smelting of antimony concentrate can be integrated into a lead smelting system to realize the synergistic smelting of lead and antimony, the lead smelting temperature can be reduced, the problems of low sulfur dioxide concentration, low heat utilization rate and the like in flue gas in the antimony concentrate volatilization smelting process can be effectively avoided, and the method has important significance for sustainable development of lead and antimony smelting in China.
Disclosure of Invention
The invention provides a method for lead and antimony collaborative smelting aiming at the series problems of low concentration of flue gas sulfur dioxide, low heat utilization rate, high energy consumption, large amount of carbon dioxide generation and the like in the antimony concentrate volatilization smelting process, and the method has the advantages of low energy consumption, high heat utilization rate, capability of making acid by flue gas, low antimony oxide powder reduction temperature and the like.
The above purpose of the invention is realized by the following technical scheme:
a method for lead and antimony co-smelting comprises the following steps:
(1) And uniformly mixing the lead concentrate, the antimony concentrate and the lime, placing the mixture into a smelting furnace, and introducing oxygen to perform oxygen-enriched intensified smelting. Smelting to produce antimony-rich crude lead, high-temperature smoke dust and smelting slag. The oxidation reaction and the lead-antimony type interaction reaction which occur in the smelting process mainly comprise the following steps:
2PbS+3O 2 ＝2PbO+2SO 2
2Sb 2 S 3 +9O 2 ＝2Sb 2 O 3 +6SO 2
2Sb 2 S 3 +11O 2 ＝2Sb 2 O 5 +6SO 2
2Sb 2 O 5 +5PbS＝5Sb+4Pb+5SO 2
Sb 2 S 3 +2Sb 2 O 3 ＝6Sb+3SO 2
PbS+2PbO＝3Pb+SO 2
(2) And (2) carrying out electrolytic refining on the antimony-rich crude lead in the step (1) to obtain refined lead and antimony-rich anode mud, and carrying out converter blowing and nitric acid leaching on the antimony-rich anode mud to obtain lead nitrate leachate and antimony oxide powder.
(3) And (3) granulating the antimony oxide powder in the step (2), putting the granulated antimony oxide powder into a reduction furnace, and introducing hydrogen to carry out reduction smelting to prepare the metal antimony. The chemical equation for the main occurrence of the reduction smelting process is as follows:
Sb 2 O 3 +3H 2 ＝2Sb+3H 2 O
2Sb 2 O 3 +3C＝4Sb+3CO 2
wherein the mass ratio of the lead concentrate to the antimony concentrate to the lime in the step (1) is 100: (20 to 100): (3-10); in the oxygen-enriched intensified smelting process, the oxygen-enriched concentration is 40-90%, the smelting temperature is 700-1050 ℃, and the smelting time is 1-3 h;
in the step (3), the hydrogen consumption is 105-130% of the chemical reaction equivalent required by completely converting the antimony compound in the antimony oxide powder into the metallic antimony, and the reduction smelting temperature is 650-850 ℃.
Preferably, the antimony concentrate in the step (1) is stibnite or stibnite concentrate.
The high-temperature smoke dust generated in the oxygen-enriched intensified smelting in the step (1) is used for preparing sulfuric acid after waste heat utilization and flue gas purification; and volatilizing the smelting slag generated by the oxygen-enriched intensified smelting in a fuming furnace, and then using the smelting slag to produce cement.
In the step (2), the blowing temperature of the converter is 800-950 ℃.
The nitric acid leaching temperature in the step (2) is 20-90 ℃, the leaching time is 25-85 min, the liquid-solid ratio is 1 mL/g-8.
And (3) reacting the lead nitrate leaching solution in the step (2) with sulfuric acid to realize regeneration of nitric acid, and returning the byproduct lead sulfate to the oxygen-enriched intensified smelting process. The regeneration temperature of the nitric acid is room temperature, the stirring speed is 200-220 rmp, the dosage of the sulfuric acid is 0.95-1.2 times of the reaction equivalent, and the mass fraction of the sulfuric acid in the sulfuric acid solution is 70-98%.
In the step (3), the antimony oxide powder is uniformly mixed with a small amount of carbonaceous reducing agent and then granulated; the carbonaceous reducing agent is one or more of coke, anthracite and charcoal, and the dosage of the carbonaceous reducing agent is 0 to 5 percent of the mass of the antimony oxide powder.
Compared with the prior art, the technical scheme of the invention has the following positive effects:
in the invention, antimony concentrate and lead concentrate are subjected to synergistic smelting, antimony-rich crude lead is produced by utilizing the interaction between lead and antimony, refined lead and antimony-rich anode mud are obtained by electrolytic refining, the antimony-rich anode mud is subjected to converter blowing and nitric acid leaching to separate lead and antimony to obtain lead nitrate solution and antimony oxide powder, the antimony oxide powder is subjected to reduction smelting to obtain metal antimony, and precious metals are enriched in the precious lead. The similar interaction reaction between lead and antimony is fully utilized in the smelting process, the smelting temperature is reduced, the concentration of sulfur dioxide in the generated flue gas is high, the flue gas can be used for preparing sulfuric acid, and the smelting slag can be used for producing cement after being treated. In the process of preparing the metal antimony by reducing and smelting the antimony oxide powder, hydrogen is adopted to replace most of carbonaceous reducing agents, and the method has the advantages of low reduction temperature, high reaction speed and no generation of carbon dioxide. The process overcomes the problems that the heat utilization rate is low, the concentration of sulfur dioxide in flue gas is low, acid can not be prepared, the reduction temperature is high, a large amount of carbon dioxide is generated and the like in the reduction smelting process of antimony oxide powder in the traditional antimony concentrate volatilization smelting process, and has wide industrial application prospect.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings used in the description of the embodiments will be briefly introduced below, and it is obvious that the drawings in the description of the following drawings are only some embodiments of the present invention, and it is obvious for those skilled in the art to obtain other drawings based on the drawings without creative efforts.
FIG. 1 is a flow chart of the lead and antimony co-smelting method provided by the invention.
Detailed Description
In order to make the technical problems, technical solutions and advantages of the present invention more apparent, the following detailed description is given with reference to the accompanying drawings and specific embodiments.
Example 1
100g of lead concentrate, 20g of stibnite and 3g of lime are uniformly mixed and then placed in a smelting furnace, the temperature in the furnace is maintained at 700 ℃, 40% oxygen-enriched air is introduced for smelting, 108.4g of antimony-enriched crude lead is obtained after reaction for 3 hours, and the concentration of sulfur dioxide in flue gas is 20%. Carrying out electrolytic refining on the antimony-rich crude lead to obtain refined lead and antimony-containing anode mud, and converting the antimony-containing anode mud at 800 ℃ in a converter to obtain the lead-rich antimony oxide. Then, nitric acid (in the embodiment of the invention, industrial nitric acid with the concentration of about 65%) is used as a leaching agent, lead-rich antimony oxide is leached under the conditions that the temperature is 20 ℃, the liquid-solid ratio is 3:1mL/g, the use amount of the nitric acid is 1 time of the reaction equivalent, and the leaching time is 25min, the lead leaching rate reaches 95.54%, and antimony oxide powder and lead nitrate leaching liquid are obtained after leaching. And then adding sulfuric acid into the lead nitrate leaching solution, wherein the regeneration of nitric acid can be realized under the conditions of room temperature, the stirring speed of 200rmp, the use amount of the sulfuric acid being 0.95 time of the reaction equivalent and the mass fraction of the sulfuric acid in the sulfuric acid solution being 98%, and the by-product lead sulfate is returned to the oxygen-enriched intensified smelting process. And finally, uniformly mixing the antimony oxide powder and the coke according to a mass ratio of 100 to 3, granulating, placing the mixture into a magnetic boat, placing the magnetic boat into a tube furnace, and maintaining the temperature in the furnace at 650 ℃. Introducing hydrogen to carry out reduction reaction to prepare the metallic antimony, wherein the hydrogen consumption is 105% of the chemical reaction equivalent required by completely converting the antimony compound in the antimony oxide powder into the metallic antimony.
Example 2
The lead-rich antimony oxide in example 1 is leached by nitric acid under the conditions of 70 ℃, liquid-solid ratio of 8 [ 1mL/g ], nitric acid dosage of 1.5 times of reaction equivalent and leaching time of 85min, lead leaching rate reaches 97.06%, and antimony oxide powder and lead nitrate leaching solution are obtained after leaching. And then adding sulfuric acid into the lead nitrate leaching solution, wherein the regeneration of nitric acid can be realized under the conditions of room temperature, the stirring speed of 220rmp, the use amount of the sulfuric acid being 1.2 times of the reaction equivalent and the mass fraction of the sulfuric acid in the sulfuric acid solution being 70%, and the by-product lead sulfate can be returned to the oxygen-enriched intensified smelting process. And finally, uniformly mixing the antimony oxide powder and the anthracite coal according to a mass ratio of 100. Introducing hydrogen to carry out reduction reaction to prepare the metallic antimony, wherein the hydrogen consumption is 110% of the chemical reaction equivalent required by completely converting the antimony compound in the antimony oxide powder into the metallic antimony.
Example 3
100g of lead concentrate, 50g of stibnite and 5g of lime are uniformly mixed and then placed in a smelting furnace, the temperature in the furnace is maintained at 1050 ℃, 80% of oxygen-enriched air is introduced for smelting, and after reaction for 1 hour, 136.3g of antimony-enriched lead bullion is obtained, wherein the concentration of sulfur dioxide in flue gas is 23%. Carrying out electrolytic refining on the antimony-rich crude lead to obtain refined lead and antimony-containing anode mud, and blowing the antimony-containing anode mud at 950 ℃ by a converter to obtain the lead-rich antimony oxide. Then, nitric acid is used as a leaching agent, lead-rich antimony oxide is leached under the conditions that the temperature is 90 ℃, the liquid-solid ratio is 5 [ 1mL/g ], the using amount of the nitric acid is 1.2 times of the reaction equivalent, and the leaching time is 45min, the leaching rate of lead reaches 97.11%, and antimony oxide powder and lead nitrate leaching liquid are obtained after leaching. And then adding sulfuric acid into the lead nitrate leaching solution, wherein the regeneration of nitric acid can be realized under the conditions of room temperature, stirring speed of 200rmp, the use amount of the sulfuric acid being 1 time of the reaction equivalent and the mass fraction of the sulfuric acid in the sulfuric acid solution being 80%, and the by-product lead sulfate can be returned to the oxygen-enriched strengthening smelting process. And finally, directly taking the appropriate amount of antimony oxide powder, granulating, placing the obtained product in a magnetic boat, placing the magnetic boat in a tube furnace, and maintaining the temperature in the furnace at 800 ℃. Introducing hydrogen to carry out reduction reaction to prepare the metallic antimony, wherein the hydrogen consumption is 130% of the chemical reaction equivalent required by completely converting the antimony compound in the antimony oxide powder into the metallic antimony.
Example 4
The antimony oxide powder and the charcoal leached by the nitric acid in example 3 were uniformly mixed and granulated at a mass ratio of 100. Introducing hydrogen to carry out reduction reaction to prepare metallic antimony, wherein the dosage of the metallic antimony is 115% of the chemical reaction equivalent required by completely converting the antimony compound in the antimony oxide powder into the metallic antimony.
Example 5
100g of lead concentrate, 100g of antimony gold concentrate and 10g of lime are uniformly mixed and then placed in a smelting furnace, the temperature in the smelting furnace is maintained at 900 ℃, 90% of oxygen-enriched air is introduced for smelting, 182.1g of antimony-enriched crude lead is obtained after reaction for 2 hours, and the concentration of sulfur dioxide in flue gas is 25%. Carrying out electrolytic refining on the antimony-rich crude lead to obtain refined lead and antimony-containing anode mud, and blowing the antimony-containing anode mud at 950 ℃ by a converter to obtain the lead-rich antimony-oxygen. Leaching lead-rich antimony oxide by using nitric acid under the conditions of 80 ℃, liquid-solid ratio of 8 [ 1mL/g ], use amount of the nitric acid being 1.5 times of reaction equivalent and leaching time being 85min, wherein the leaching rate of lead reaches 97.49%, and leaching to obtain antimony oxide powder and lead nitrate leaching liquid. And then adding sulfuric acid into the lead nitrate leaching solution, wherein the regeneration of nitric acid can be realized under the conditions of room temperature, the stirring speed of 210rmp, the use amount of the sulfuric acid being 1.2 times of the reaction equivalent and the mass fraction of the sulfuric acid in the sulfuric acid solution being 90%, and the by-product lead sulfate can be returned to the oxygen-enriched intensified smelting process. And finally, uniformly mixing the antimony oxide powder and the anthracite coal according to a mass ratio of 100. And introducing hydrogen to carry out reduction reaction to prepare the metallic antimony, wherein the hydrogen consumption is 130% of the chemical reaction equivalent required by completely converting the antimony compound in the antimony oxide powder into the metallic antimony.
The above description is only for the preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any changes or substitutions that can be easily conceived by those skilled in the art within the technical scope of the present invention are also included in the scope of the present invention. Therefore, the protection scope of the present invention should be subject to the protection scope of the claims.
Claims (9)
1. The method for lead and antimony collaborative smelting is characterized by comprising the following steps:
(1) Lead concentrate, antimony concentrate and lime are uniformly mixed and then placed in a smelting furnace, oxygen is introduced for oxygen-enriched intensified smelting, and antimony-enriched crude lead, high-temperature smoke dust and smelting slag are produced through smelting;
(2) Carrying out electrolytic refining on the antimony-rich crude lead in the step (1) to obtain refined lead and antimony-rich anode mud, and carrying out converter blowing and nitric acid leaching on the antimony-rich anode mud to obtain lead nitrate leachate and antimony oxide powder;
(3) Granulating the antimony oxide powder in the step (2), putting the granulated antimony oxide powder into a reduction furnace, and introducing hydrogen to carry out reduction smelting to prepare metal antimony;
wherein the mass ratio of the lead concentrate to the antimony concentrate to the lime in the step (1) is 100: (20 to 100): (3-10); in the oxygen-enriched intensified smelting process, the oxygen-enriched concentration is 40-90%, the smelting temperature is 700-1050 ℃, and the smelting time is 1-3 h;
in the step (3), the hydrogen consumption is 105-130% of the equivalent of chemical reaction required by completely converting the antimony compound in the antimony oxide powder into the metal antimony, and the reduction smelting temperature is 650-850 ℃.
2. The method for lead and antimony co-smelting according to claim 1, wherein the antimony concentrate in step (1) is stibnite or antimony gold concentrate.
3. The method for lead and antimony co-smelting according to claim 1 or 2, characterized in that the high temperature flue dust generated by oxygen-enriched enhanced smelting in step (1) is used for preparing sulfuric acid after waste heat utilization and flue gas purification; and/or the smelting slag generated by the oxygen-enriched intensified smelting is volatilized by a fuming furnace and then is used for producing cement.
4. The method for lead and antimony co-smelting according to claim 1, wherein the converter blowing temperature in the step (2) is 800-950 ℃.
5. The method for lead and antimony co-smelting according to claim 1, wherein in the step (2), the nitric acid leaching temperature is 20-90 ℃, the leaching time is 25-85 min, the liquid-solid ratio is 3-1mL/g-8.
6. The method for lead and antimony co-smelting according to claim 1, wherein the lead nitrate leaching solution in the step (2) is reacted with sulfuric acid to realize regeneration of nitric acid, and the by-produced lead sulfate is returned to the oxygen-enriched intensified smelting process.
7. The method for lead and antimony co-smelting according to claim 6, wherein the regeneration temperature of the nitric acid is room temperature, the stirring speed is 200 to 220rmp, the amount of the sulfuric acid is 0.95 to 1.2 times of the reaction equivalent, and the mass fraction of the sulfuric acid in the sulfuric acid solution is 70 to 98 percent.
8. The method for lead and antimony co-smelting according to claim 1, wherein in step (3), the antimony oxide powder is uniformly mixed with a small amount of carbonaceous reducing agent and then granulated.
9. The method for lead and antimony co-smelting according to claim 8, wherein the carbonaceous reducing agent is one or more of coke, anthracite and charcoal, and the amount of the carbonaceous reducing agent is 0-5% of the mass of antimony oxide powder.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN117210706A (en) * | 2023-08-07 | 2023-12-12 | 昆明理工大学 | Method for reducing antimony oxide by hydrogen |
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| CN112662894A (en) * | 2020-11-17 | 2021-04-16 | 中国恩菲工程技术有限公司 | Method for producing antimony from antimony oxide powder |
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| CN117210706A (en) * | 2023-08-07 | 2023-12-12 | 昆明理工大学 | Method for reducing antimony oxide by hydrogen |
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