CN115181855A - Method for producing alloy by enriching germanium from germanium-containing smelting slag - Google Patents
Method for producing alloy by enriching germanium from germanium-containing smelting slag Download PDFInfo
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- 229910052732 germanium Inorganic materials 0.000 title claims abstract description 178
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 title claims abstract description 178
- 238000003723 Smelting Methods 0.000 title claims abstract description 161
- 239000002893 slag Substances 0.000 title claims abstract description 123
- 229910045601 alloy Inorganic materials 0.000 title claims abstract description 25
- 239000000956 alloy Substances 0.000 title claims abstract description 25
- 238000004519 manufacturing process Methods 0.000 title abstract description 6
- 238000000034 method Methods 0.000 claims abstract description 44
- 239000000779 smoke Substances 0.000 claims abstract description 33
- 239000000428 dust Substances 0.000 claims abstract description 29
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 27
- 239000011701 zinc Substances 0.000 claims abstract description 26
- 239000010949 copper Substances 0.000 claims abstract description 24
- 229910052802 copper Inorganic materials 0.000 claims abstract description 23
- 239000003638 chemical reducing agent Substances 0.000 claims abstract description 21
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 20
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 17
- 230000009467 reduction Effects 0.000 claims abstract description 16
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims abstract description 14
- 230000004907 flux Effects 0.000 claims abstract description 14
- 229910052742 iron Inorganic materials 0.000 claims abstract description 13
- 239000000463 material Substances 0.000 claims abstract description 11
- 238000002156 mixing Methods 0.000 claims abstract description 10
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 10
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 7
- 239000000292 calcium oxide Substances 0.000 claims description 7
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 claims description 7
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Chemical compound [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 claims description 4
- 238000005275 alloying Methods 0.000 claims description 2
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 claims description 2
- 239000000377 silicon dioxide Substances 0.000 claims description 2
- 229910052814 silicon oxide Inorganic materials 0.000 claims description 2
- 229910052751 metal Inorganic materials 0.000 abstract description 20
- 239000002184 metal Substances 0.000 abstract description 14
- 230000008901 benefit Effects 0.000 abstract description 9
- 239000002699 waste material Substances 0.000 abstract description 8
- 150000002739 metals Chemical class 0.000 abstract description 7
- 239000002253 acid Substances 0.000 abstract description 6
- 238000000605 extraction Methods 0.000 abstract description 5
- 238000003912 environmental pollution Methods 0.000 abstract description 4
- 239000002351 wastewater Substances 0.000 abstract description 3
- 229910001021 Ferroalloy Inorganic materials 0.000 abstract 1
- 238000002386 leaching Methods 0.000 description 19
- 239000011133 lead Substances 0.000 description 17
- 238000011084 recovery Methods 0.000 description 17
- 230000008569 process Effects 0.000 description 11
- 239000012141 concentrate Substances 0.000 description 9
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 8
- 239000000203 mixture Substances 0.000 description 8
- 239000002994 raw material Substances 0.000 description 8
- 238000004064 recycling Methods 0.000 description 8
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 6
- 239000007788 liquid Substances 0.000 description 5
- 239000006004 Quartz sand Substances 0.000 description 4
- 238000001514 detection method Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 3
- 239000003546 flue gas Substances 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 2
- 238000006477 desulfuration reaction Methods 0.000 description 2
- 230000023556 desulfurization Effects 0.000 description 2
- 239000003077 lignite Substances 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 1
- 229910000640 Fe alloy Inorganic materials 0.000 description 1
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 1
- 229910005793 GeO 2 Inorganic materials 0.000 description 1
- RHZUVFJBSILHOK-UHFFFAOYSA-N anthracen-1-ylmethanolate Chemical compound C1=CC=C2C=C3C(C[O-])=CC=CC3=CC2=C1 RHZUVFJBSILHOK-UHFFFAOYSA-N 0.000 description 1
- 239000003830 anthracite Substances 0.000 description 1
- 239000002802 bituminous coal Substances 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 239000003610 charcoal Substances 0.000 description 1
- 239000000571 coke Substances 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- -1 copper and iron Chemical class 0.000 description 1
- 238000009854 hydrometallurgy Methods 0.000 description 1
- JQJCSZOEVBFDKO-UHFFFAOYSA-N lead zinc Chemical compound [Zn].[Pb] JQJCSZOEVBFDKO-UHFFFAOYSA-N 0.000 description 1
- 229910001092 metal group alloy Inorganic materials 0.000 description 1
- 239000002006 petroleum coke Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 229920001864 tannin Polymers 0.000 description 1
- 239000001648 tannin Substances 0.000 description 1
- 239000002918 waste heat Substances 0.000 description 1
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Classifications
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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
- C22B15/00—Obtaining copper
- C22B15/0026—Pyrometallurgy
- C22B15/0054—Slag, slime, speiss, or dross treating
-
- 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
- C22B19/04—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
- C22B41/00—Obtaining germanium
-
- 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
- C22B7/006—Wet 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
- 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
- C22B7/02—Working-up flue dust
-
- 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 producing alloy by enriching germanium from germanium-containing smelting slag. The method comprises the following steps: mixing the germanium-containing smelting slag, the flux and the carbonaceous reducing agent to obtain a mixed material; adding the mixed material into a vacuum smelting furnace for reduction volatilization smelting to produce an alloy containing copper and iron, and obtaining smoke containing germanium, zinc and lead; wherein the smelting temperature is 1100-1450 ℃, and the pressure in the vacuum smelting furnace is less than or equal to 10Pa. According to the invention, germanium-containing smelting slag is subjected to reduction volatilization smelting in the vacuum smelting furnace, so that germanium element is enriched in smoke dust and copper-containing ferroalloy is obtained, thereby facilitating the subsequent wet germanium extraction, reducing the use amount of acid liquor, reducing the discharge of waste water and waste residue, avoiding environmental pollution, efficiently recovering valuable metals in the germanium-containing smelting slag into the alloy, avoiding resource waste and improving economic benefit.
Description
Technical Field
The invention relates to the technical field of recovery and utilization of germanium-containing smelting slag, in particular to a method for enriching germanium and producing alloy from the germanium-containing smelting slag, which improves the comprehensive utilization value of the germanium-containing smelting slag.
Background
Germanium concentrate, according to the non-ferrous metal industry standard, the germanium concentrate is divided into two main categories according to the sources, wherein the two main categories comprise 9 grades, one category is the germanium concentrate produced by germanium-containing lignite, and the grade and the chemical composition of the germanium concentrate meet the regulations in a table 1; the other is germanium concentrate produced by other raw materials (such as lead-zinc, copper and iron smelting, secondary germanium recovery and the like), and the grade and chemical composition of the germanium concentrate meet the specification of the table 2.
TABLE 1 germanium concentrate grade and chemical composition from germanium-containing lignite
TABLE 2 germanium concentrate grade and chemical composition from other raw materials
In the prior art, the commonly adopted wet process for leaching germanium in germanium concentrate comprises hydrochloric acid (reduction) leaching, sulfuric acid (oxidation) leaching, sulfuric acid direct leaching, hydrochloric acid direct leaching and the like. As shown in the table above, these wet leaching processes often require a Ge content in the leach feed of greater than 1%. For example, the document "experimental study of germanium-enriched smelting slag containing germanium" (2013, lixiao and the like) is that germanium in the slag is enriched by adopting a process of sulfuric acid oxidation leaching-pre-neutralization-tannin germanium precipitation on the germanium-containing smelting slag containing germanium with the Ge content of 1.43%, and the germanium leaching efficiency is improved to a certain extent.
However, the inventor of the present application finds that for smelting slag with low germanium content, especially with Ge content lower than 1%, a great amount of acid liquor is consumed if the metal germanium is directly extracted by hydrometallurgy, and a great amount of leaching slag and leaching liquid are generated at the same time, so that environmental pollution and resource waste are caused; in addition, some valuable metal elements in the smelting slag are not paid attention and are not effectively recovered, so that the economic recovery benefit is reduced. Therefore, it is necessary to develop a new and efficient recycling process for the low-germanium-content smelting slag with high treatment difficulty in the wet process.
Disclosure of Invention
According to one embodiment of the present invention, it is an object to provide a method for producing an alloy enriched in germanium from a germanium-containing slag. The method can efficiently enrich the germanium element in the smoke dust, thereby facilitating the subsequent wet-process germanium extraction, effectively recycling valuable metals to the alloy, avoiding resource waste and improving the comprehensive recycling value of the germanium-containing smelting slag.
The purpose can be realized by the implementation mode of the following technical scheme:
the invention provides a method for enriching germanium and producing alloy by using germanium-containing smelting slag, which comprises the following steps: mixing the germanium-containing smelting slag, a flux and a carbonaceous reducing agent to obtain a mixed material; adding the mixed material into a vacuum smelting furnace, and carrying out reduction volatilization smelting to produce an alloy containing copper and iron so as to obtain smoke containing germanium, zinc and lead; wherein the smelting temperature is 1100-1450 ℃, and the pressure in the vacuum smelting furnace is less than or equal to 10Pa.
Optionally, the germanium-containing smelting slag has a germanium content of less than 1%.
Optionally, the method further comprises: and (3) taking the smoke dust containing germanium, zinc and lead as a raw material, and extracting germanium by a wet method.
Optionally, the content of Ge element in the smelting slag produced after smelting is not higher than 60ppm.
Optionally, the content of Ge element in the smelting slag produced after smelting is 10ppm to 50ppm.
Optionally, during batching, the ratio of the germanium-containing smelting slag to the flux to the carbonaceous reducing agent is 100: (5-7): (0.5-5).
Optionally, the flux comprises calcium oxide and/or silicon oxide. Optionally, the smelting slag is CaO/SiO 2 ＝0.5～0.8。
Optionally, the germanium-containing smelting slag component is FeO-CaO-SiO 2 Ternary is dominant and the silica content therein is not higher than 40%.
Optionally, the germanium content in the smoke containing germanium, zinc and lead is enriched to be not less than 7000ppm.
Optionally, in the copper-containing iron alloy, the iron content is 30.5% -70.4%, and the copper content is 18.8% -58.7%.
Optionally, the produced smelting slag has a zinc content and a lead content of not higher than 0.5%.
According to the embodiment of the invention, the germanium-containing smelting slag after being proportioned is sent into the vacuum smelting furnace for reduction volatilization smelting, germanium element is efficiently enriched into smoke dust, and valuable metal elements copper and iron are efficiently recycled into alloy, so that the comprehensive recycling value of the germanium-containing smelting slag is improved, and the economic benefit is improved.
The above-described embodiments of the present invention also have the following advantages and advantageous effects, compared to the prior art.
1) The germanium-containing smelting slag is fed into a vacuum smelting furnace for reduction smelting after being mixed with molten slag and a reducing agent, the smelting temperature and the smelting pressure are controlled, the volatilization rate of germanium elements in the germanium-containing smelting slag is improved, the germanium elements are efficiently enriched into smoke dust, and the germanium content in the smelting slag produced after smelting can be reduced to about 10 ppm.
2) Compared with the prior art that the smelting slag containing less than 1 percent of germanium is directly subjected to the wet germanium extraction process, the germanium element of the smelting slag containing less than 1 percent of germanium is efficiently enriched into smoke dust, and the smoke dust is used as a raw material, so that the wet germanium extraction is more favorably carried out, the acid liquor usage amount can be greatly reduced, the discharge of waste water and waste residues is reduced, the wet leaching process cost is reduced, and the environmental pollution is avoided.
3) The germanium-containing smelting slag is fed into a vacuum smelting furnace for reduction smelting after being mixed with molten slag and a reducing agent, and the smelting temperature and pressure are controlled, so that valuable metals, namely copper and iron, in the germanium-containing smelting slag are efficiently recycled into the alloy, the waste of valuable metal resources is avoided, and the economic benefit is improved.
4) The addition amount of the flux and the reducing agent and the slag form are improved and optimized aiming at the germanium-containing smelting slag, so that the recovery rate of valuable metals is further improved, and the economic benefit is improved.
5) Compare and collect germanium with solid-state calcination mode of volatilizing, the enrichment of volatilizing is carried out to this application in the vacuum melting furnace with germanium-containing smelting slag based on under molten bath (liquid) state, has further improved germanium element's in the germanium-containing smelting slag volatility to the problem of the difficult collection of volatilizing of solid-state material center department germanium has been overcome.
Drawings
FIG. 1 is a schematic flow chart of the method for producing alloy by enriching germanium from the germanium-containing smelting slag.
FIG. 2 is a graph comparing the effect of different pressures involved in the present invention on the Gibbs free energy of the reaction formula.
Detailed Description
The technical solutions of the present invention will be described clearly and completely below with reference to embodiments of the present invention, and it should be apparent that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. The following description of at least one exemplary embodiment is merely illustrative in nature and is in no way intended to limit the invention, its application, or uses. All other embodiments, which can be obtained by a person skilled in the art without inventive step based on the embodiments of the present invention, are within the scope of protection of the present invention.
As described in the background art, the present inventors have found that there is no effective process for recycling germanium-containing slag with low content, such as germanium content lower than 1%, so that a large amount of resources in the germanium-containing slag are wasted, and the economic benefit is low. At the end of 2021 years, the price fluctuation range of the germanium ingots is about 8950-9250 yuan/kg, taking the Ge content in the smelting slag as 0.05 percent as an example, the value of only the Ge content in one ton of smelting slag can reach 4475-4625 yuan, and if the value of other valuable metal elements such as lead, zinc, copper and the like in the smelting slag is added, the recycling value of the germanium-containing smelting slag can be further improved. Based on the above, the application provides a method for efficiently recycling germanium-containing smelting slag, in particular to a method for enriching germanium to produce alloy, which is especially used for treating germanium-containing smelting slag with the germanium content lower than 1%, and germanium element enrichment (in smoke dust) is realized by mixing the germanium-containing smelting slag, a flux and a carbonaceous reducing agent, and then adding the mixture into a vacuum smelting furnace for reduction volatilization smelting, so that the usage amount of acid liquor is effectively reduced in the subsequent wet smelting purification process, the generation of leaching slag and leaching liquid is reduced, and the method is more environment-friendly compared with the direct wet leaching process of the germanium-containing smelting slag; and meanwhile, valuable metal elements in the germanium-containing smelting slag are efficiently recovered, so that the comprehensive recovery and utilization value of the germanium-containing smelting slag is improved, and the economic benefit is improved.
FIG. 1 schematically illustrates a germanium-enriched alloying method of germanium-containing slag according to an embodiment of the present invention.
As shown in figure 1, the germanium-containing smelting slag germanium-enriched alloy production method comprises the following steps:
and S10, mixing the germanium-containing smelting slag, the flux and the carbonaceous reducing agent to obtain a mixed material.
The invention relates to treatment of germanium-containing smelting slag, which mainly aims at the germanium-containing smelting slag with the germanium content of less than 1 percent, such as the germanium content of less than 1 percent, 0.5 percent, 0.1 percent, 0.05 percent, 0.01 percent, 0.001 percent and the like, so as to overcome a series of problems of the low-content germanium-containing smelting slag in the prior art. According to the embodiment, the germanium-containing smelting slag is subjected to reduction volatilization smelting, germanium elements are efficiently enriched in the dust, and the germanium-enriched dust is used as a raw material for extracting germanium by a wet method, so that the germanium is extracted, the using amount of acid liquor is reduced, the leaching slag and the leaching solution are reduced, the environmental pollution is avoided, and the economic benefit is improved.
The germanium-containing smelting slag comprises the components of FeO-CaO-SiO 2 Mainly comprises three elements, also has valuable metal elements such as Zn, pb, cu and the like, and the invention adopts CaO and/or SiO to the composition of the germanium-containing smelting slag 2 Adjusting the smelting slag type of the germanium-containing smelting slag as a flux, and adjusting the CaO/SiO content of the smelting slag 2 And (5) = 0.5-0.8. In addition, the reducing agent is a carbonaceous reducing agent, and the carbonaceous reducing agent can be one or more of coke, bituminous coal, anthracite, petroleum coke, charcoal and the like. Furthermore, based on the germanium-containing smelting slag, the mass ratio of the germanium-containing smelting slag to the flux to the reducing agent is 100: (5-7): (0.5 to 5); the specific adding amount of the reducing agent is adjusted according to the content of the valuable metals Zn, pb, ge and Cu in the smelting slag, for example, the using amount range of the reducing agent can be adjusted to be 1-2 kg based on 100kg of the germanium-containing smelting slag, the reduction volatilization smelting efficiency is further improved, and the recovery rate of the valuable metals is improved. By improving and optimizing the proportion of the germanium-containing smelting slag, the flux and the carbonaceous reducing agent aiming at the smelting slag with low germanium content and controlling the type and the slag type of the flux, the recovery rate of valuable metals such as iron, copper and the like is improved, and the efficient enrichment of germanium elements is realized.
In addition, the germanium-containing smelting slag comprises FeO-CaO-SiO 2 Ternary-based, and SiO 2 The content is not higher than 40 percent, and FeO-CaO-SiO is formed in the smelting process 2 The ternary slag system molten pool is used for volatilizing and enriching the germanium-containing smelting slag in a molten pool (liquid state) state, so that the volatilization rate of germanium elements in the germanium-containing smelting slag is improved, and the recovery rate of germanium can reach more than 95%; when SiO is contained in the germanium-containing smelting slag 2 When the content is too high, particularly higher than 60%, the solid-solid reaction is carried out in the smelting process, a molten pool cannot be formed, and the volatilization rate of the germanium element is low.
And S20, adding the mixed material into a vacuum smelting furnace for reduction and volatilization smelting to produce an alloy containing copper and iron, and obtaining smoke containing germanium, zinc and lead.
The vacuum smelting furnace comprises a furnace body, wherein a smelting chamber is arranged in the furnace body and is connected with a vacuumizing device, a material inlet, a slag discharge port, an alloy discharge port and a smoke outlet are formed in the furnace body, and the smoke outlet is connected with a smoke collecting device to collect germanium-enriched smoke after smelting. The mixed material enters the smelting chamber from the material inlet, reduction volatilization smelting is carried out in a vacuum state, the alloy and the smelting slag are discharged from the alloy discharge port and the slag discharge port respectively, and the smoke dust is discharged from the smoke dust outlet and collected. Optionally, the flue gas outlet of the furnace body can be connected with a flue gas treatment device, and the flue gas produced by smelting is subjected to secondary combustion, waste heat recovery and desulfurization treatment after dust collection, and is discharged after the desulfurization treatment is qualified, so that the pollution problem is avoided. Meanwhile, the smoke dust obtained after dust collection can be sent into a vacuum smelting furnace for further reduction, volatilization and smelting, so that the comprehensive recovery efficiency of the germanium-containing smelting slag is improved, and the resource waste is avoided.
And controlling the pressure in the vacuum smelting furnace to be less than or equal to 10Pa during reduction and volatilization smelting. The inventor of the application finds that: with the increase of the vacuum degree, geO 2 + C = GeO + CO, the gibbs free energy is significantly reduced, as shown in fig. 2: under the condition of 101325Pa, when the smelting temperature is higher than 900 ℃, the reaction formula can happen; when the pressure is less than 10Pa, the reaction formula can be generated when the smelting temperature is higher than 500 ℃; with the increase of the vacuum degree, the reaction formula GeO 2 The greater the driving force for the rightward reaction of + C = GeO + CO. By reducing the pressure to 10Pa or below, the volatilization rate of the germanium element in the germanium-containing smelting slag is improved, the slag element is efficiently enriched in dust, and the recovery rate of the germanium can reach more than 95%.
In addition, the smelting temperature is 1100-1450 ℃ during reduction volatilization smelting. Although the vacuum degree is improved, the volatilization temperature of the germanium element can be properly reduced, the temperature in the vacuum melting furnace is controlled to be 1100-1450 ℃, the recovery of the by-product metal alloy is facilitated under the range, the volatilization rate of the germanium element is improved, and the high-efficiency enrichment rate is further improved. Therefore, the high-efficiency comprehensive recycling value of the germanium-containing smelting slag is realized by controlling the pressure in the vacuum smelting furnace to be less than or equal to 10Pa and controlling the smelting temperature to be 1100-1450 ℃ aiming at the germanium-containing smelting slag with low germanium content, and the content of Ge element in the produced smelting slag is not higher than 60ppm.
In one embodiment, when the germanium content in the germanium-containing smelting slag is 0.1%, based on the method, the smelting slag is produced, wherein the content of Ge element is in the range of 10ppm to 50ppm, and the content of zinc and lead is not higher than 0.5%; the smoke dust mainly contains germanium, zinc and lead elements, and the content of germanium is enriched to be not less than 7000ppm; the content of iron in the alloy is within the range of 30.5-70.4%, and the content of copper is within the range of 18.8-58.7%. In the preferred embodiment, when the smelting temperature is controlled to be 1200-1350 ℃ and the pressure is controlled to be 0.1-0.5 Pa, the content of Ge element in the produced smelting slag can be reduced to be below 13ppm, and the content of Ge element in the smoke dust can be enriched to be above 8000 ppm.
And step S30, taking smoke dust containing germanium, zinc and lead as a raw material, and carrying out wet germanium extraction.
Through the steps S10 and S20, the germanium element in the germanium-containing smelting slag is efficiently enriched into the smoke dust, and then the smoke dust enriched with germanium is used as a raw material for extracting germanium by a wet method, so that the wet purification treatment is facilitated. The specific method for extracting germanium by wet method is not limited, and can be common wet method processes, such as hydrochloric acid leaching, sulfuric acid leaching and the like. According to calculation, compared with the method that germanium is directly extracted from the germanium-containing smelting slag with the content of less than 1% by a wet method, germanium is efficiently enriched and recovered into smoke dust, the germanium-enriched smoke dust is used as a raw material for extracting germanium by the wet method, the using amount of acid liquor is greatly reduced, and the generation of leaching slag and leaching liquid, namely waste residue and waste water is reduced.
The technical solution of the present application will be described in more detail below with reference to specific embodiments and corresponding germanium enrichment effects and metal recovery effects. In the germanium-containing smelting slag used in examples 1 to 3 and comparative example 1, the composition of the main component was as shown in table 3, the Ge content was 870ppm, and the smelting slag contained valuable metal elements such as Zn, pb, ge, and Cu.
TABLE 3
| Element(s) | Zn | Pb | Fe | SiO 2 | CaO | MgO | Al 2 O 3 |
| Content/%) | 6.829 | 3.249 | 16.964 | 26.5 | 19.7 | 5.6 | 3.40 |
| Element(s) | Na 2 O | K 2 O | Cu | S | As | Ge(ppm) | |
| Content/% | 2.85 | 0.49 | 0.5 | 0.34 | 0.41 | 870 |
Example 1
The Ge content in the smelting slag containing Ge is 870ppm. The method comprises the following steps of (1) mixing germanium-containing smelting slag, quartz sand and a carbonaceous reducing agent according to a mass ratio of 100:6:1.14 adding the mixture into a vacuum smelting furnace after uniform mixing, and smelting for 2 hours at 1100 ℃ under the condition of 10Pa.
Through detection, in the produced smelting slag, the content of Ge element is reduced to 50ppm, the content of Zn is reduced to 0.5%, the content of lead is reduced to 0.4%, and the content of copper is reduced to 0.018%. In the smoke dust, the content of Ge is enriched to 7660ppm, the content of Zn is enriched to 62.358 percent, and the content of Pb is enriched to 28.286 percent. 1.253kg of a metal phase was produced in which the Fe content was 50.5% and the copper content was 38.7%. Under the smelting condition, the recovery rate of germanium is 95.12%.
Example 2
The Ge content in the smelting slag containing Ge is 870ppm. Uniformly mixing the germanium-containing smelting slag, quartz sand and a carbonaceous reducing agent according to a mass ratio of 100.5.
Through detection, in the produced smelting slag, the content of Ge element is reduced to 33ppm, the content of Zn is reduced to 0.4%, the content of lead is reduced to 0.3%, and the content of copper is reduced to 0.012%. In the smoke dust, the content of Ge is enriched to 8120ppm, the content of Zn is enriched to 62.618 percent, and the content of Pb is enriched to 28.802 percent. 2.60kg of metal phase was produced, in which the Fe content was 70.4% and the Cu content was 18.8%. Under the smelting condition, the recovery rate of germanium is 96.78%.
Example 3
The content of Ge in the smelting slag containing Ge is 870ppm. Uniformly mixing germanium-containing smelting slag, quartz sand and a carbonaceous reducing agent according to a mass ratio of 100.5.
Through detection, the content of Ge element in the produced smelting slag is reduced to 12ppm, the content of Zn is reduced to 0.3%, the content of lead is reduced to 0.2%, and the content of copper is reduced to 0.012%. In the smoke dust, the content of Ge is enriched to 80808080ppm, the content of Zn is enriched to 61.8 percent, and the content of Pb is enriched to 28.9 percent. 0.835kg of metal phase with 30.5% Fe and 58.7% Cu was produced. Under the smelting condition, the recovery rate of germanium is 97.88 percent.
Comparative example 1
The content of Ge in the smelting slag containing Ge is 870ppm. Uniformly mixing the germanium-containing smelting slag, quartz sand and a carbonaceous reducing agent according to a mass ratio of 100.5.
Through detection, the content of Ge element in the produced smelting slag is reduced to 67ppm, the content of Zn is reduced to 1%, the content of lead is reduced to 0.8%, and the content of copper is 0.581%. In the smoke dust, the Ge content is enriched to 7158ppm, the Zn content is enriched to 53.23 percent, and the Pb content is enriched to 22.84 percent. Under the smelting condition, the recovery rate of germanium is 93.17 percent.
The description of the present invention has been presented for purposes of illustration and description, and is not intended to be exhaustive or limited to the invention in the form disclosed. Many modifications and variations will be apparent to practitioners skilled in this art. The embodiment was chosen and described in order to best explain the principles of the invention and the practical application, and to enable others of ordinary skill in the art to understand the invention for various embodiments with various modifications as are suited to the particular use contemplated.
Claims (10)
1. A method for enriching germanium and producing alloy from germanium-containing smelting slag is characterized by comprising the following steps:
the method comprises the following steps of (1) mixing germanium-containing smelting slag, a flux and a carbonaceous reducing agent to obtain a mixed material;
adding the mixed material into a vacuum smelting furnace, and carrying out reduction volatilization smelting to produce an alloy containing copper and iron so as to obtain smoke containing germanium, zinc and lead; wherein the smelting temperature is 1100-1450 ℃, and the pressure in the vacuum smelting furnace is less than or equal to 10Pa.
2. The germanium-containing smelting slag germanium-enriched alloy producing method according to claim 1, further comprising: and (3) extracting germanium from the smoke dust containing germanium, zinc and lead by a wet method.
3. The method of any one of claims 1-2, wherein the germanium-containing slag has a germanium content of less than 1%.
4. The method of claim 3, wherein the content of Ge element in the metallurgical slag produced after smelting is not higher than 60ppm.
5. The method of claim 4, wherein the smelting slag produced after smelting has a Ge content of 10ppm to 50ppm.
6. The method of claim 1, wherein the ratio of germanium-containing slag, flux and carbonaceous reducing agent is 100: (5-7): (0.5-5).
7. The germanium-containing slag enriched germanium alloying method of claim 6, wherein the flux comprises calcium oxide and/or silicon oxide.
8. The method of claim 7 wherein the slag is CaO/SiO in the form of molten slag 2 ＝0.5～0.8。
9. The germanium-containing smelting slag germanium-enriched alloy producing method according to claim 4, wherein the germanium-containing smelting slag component is FeO-CaO-SiO 2 Ternary, and wherein the silica content is not higher than 40%; the germanium content in the smoke dust containing germanium, zinc and lead is enriched to be not less than 7000ppm.
10. The method of claim 9, wherein the copper-containing and iron-containing alloy contains 30.5% -70.4% iron and 18.8% -58.7% copper; in the produced smelting slag, the zinc content and the lead content are not higher than 0.5%.
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Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| RU2458997C1 (en) * | 2011-06-02 | 2012-08-20 | Сергей Иванович Ивандаев | Method for extracting metals from solid slag when it is being discharged from coal-fired boiler, and device for its implementation |
| CN106801151A (en) * | 2017-01-22 | 2017-06-06 | 中国恩菲工程技术有限公司 | The method of flyash reduction melting enriched germanium |
| CN107604171A (en) * | 2017-08-25 | 2018-01-19 | 金川集团股份有限公司 | A kind of method of the melting enriching noble metals from complicated high content of nickel copper anode mud leached mud |
| CN111575488A (en) * | 2020-05-29 | 2020-08-25 | 上海交通大学 | Method for separating, enriching and extracting arsenic, tungsten and germanium-containing waste in sections |
| CN113337725A (en) * | 2021-06-29 | 2021-09-03 | 红河学院 | Method for enriching germanium from smelting slag |
| CN114032397A (en) * | 2021-11-18 | 2022-02-11 | 昆明理工大学 | Method for reducing and leaching germanium-containing smoke dust in lead-zinc smelting through ultrasonic enhancement |
-
2022
- 2022-07-06 CN CN202210788019.1A patent/CN115181855A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| RU2458997C1 (en) * | 2011-06-02 | 2012-08-20 | Сергей Иванович Ивандаев | Method for extracting metals from solid slag when it is being discharged from coal-fired boiler, and device for its implementation |
| CN106801151A (en) * | 2017-01-22 | 2017-06-06 | 中国恩菲工程技术有限公司 | The method of flyash reduction melting enriched germanium |
| CN107604171A (en) * | 2017-08-25 | 2018-01-19 | 金川集团股份有限公司 | A kind of method of the melting enriching noble metals from complicated high content of nickel copper anode mud leached mud |
| CN111575488A (en) * | 2020-05-29 | 2020-08-25 | 上海交通大学 | Method for separating, enriching and extracting arsenic, tungsten and germanium-containing waste in sections |
| CN113337725A (en) * | 2021-06-29 | 2021-09-03 | 红河学院 | Method for enriching germanium from smelting slag |
| CN114032397A (en) * | 2021-11-18 | 2022-02-11 | 昆明理工大学 | Method for reducing and leaching germanium-containing smoke dust in lead-zinc smelting through ultrasonic enhancement |
Non-Patent Citations (1)
| Title |
|---|
| 普世坤;兰尧中;: "碱氧化预处理蒸馏分离回收还原精矿中的锗", 有色金属(冶炼部分), no. 12, pages 43 - 46 * |
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