CN111378845A - Method for recovering valuable metals from white smoke - Google Patents
Method for recovering valuable metals from white smoke Download PDFInfo
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- CN111378845A CN111378845A CN202010306692.8A CN202010306692A CN111378845A CN 111378845 A CN111378845 A CN 111378845A CN 202010306692 A CN202010306692 A CN 202010306692A CN 111378845 A CN111378845 A CN 111378845A
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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
- C22B7/02—Working-up flue dust
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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
- C22B1/00—Preliminary treatment of ores or scrap
- C22B1/02—Roasting processes
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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
- C22B13/04—Obtaining lead by wet processes
- C22B13/045—Recovery from waste materials
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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
- C22B15/00—Obtaining copper
- C22B15/0063—Hydrometallurgy
- C22B15/0065—Leaching or slurrying
- C22B15/0067—Leaching or slurrying with acids or salts thereof
- C22B15/0071—Leaching or slurrying with acids or salts thereof containing sulfur
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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
- C22B15/00—Obtaining copper
- C22B15/0063—Hydrometallurgy
- C22B15/0084—Treating solutions
- C22B15/0089—Treating solutions by chemical methods
- C22B15/0091—Treating solutions by chemical methods by cementation
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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
- C22B19/00—Obtaining zinc or zinc oxide
- C22B19/20—Obtaining zinc otherwise than by distilling
- C22B19/22—Obtaining zinc otherwise than by distilling with leaching with acids
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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
- C22B25/00—Obtaining tin
- C22B25/04—Obtaining tin by wet processes
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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
- C22B25/00—Obtaining tin
- C22B25/06—Obtaining tin from scrap, especially tin scrap
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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
- C22B30/04—Obtaining arsenic
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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
- C22B58/00—Obtaining gallium or indium
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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
- C22B7/006—Wet processes
- C22B7/007—Wet processes by acid leaching
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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
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Abstract
The invention discloses a method for recovering valuable metals in white smoke, which comprises the following steps: white smoke is selected, and the white smoke and concentrated sulfuric acid are fully pulped and roasted to obtain smoke; carrying out sulfuric acid leaching treatment on the roasting slag by using a dilute sulfuric acid solution to obtain a primary leaching solution and primary leaching slag; performing zinc powder replacement reaction on the primary leaching solution to form copper sponge and a primary replaced solution; carrying out pressure acid leaching treatment on the primary leaching residue to obtain secondary leaching residue and secondary leaching liquid, and carrying out zinc powder replacement reaction on the secondary leaching liquid to obtain sponge indium and secondary replaced liquid; mixing the first-stage displaced liquid and the second-stage displaced liquid, and concentrating by adopting an evaporation concentration method to obtain zinc sulfate heptahydrate; and the secondary leaching slag is used as a lead-tin smelting raw material, namely the recovery of valuable metals in the white smoke is finished. The invention can realize the high-efficiency recycling of metals in the white smoke dust, can avoid the pollution to the environment and is beneficial to popularization and application.
Description
Technical Field
The invention relates to the technical field of white smoke, in particular to a method for recovering valuable metals in white smoke.
Background
The white smoke is generated in the copper smelting process, the white smoke has complex components, contains valuable metals such as copper, lead, zinc, tin, indium and the like on one hand, and has high recycling value; on the other hand, the arsenic content is high, the environmental potential hazard is large, and the harmless and resource utilization process is complicated. The processing of white smoke arsenic and the comprehensive utilization of valuable metals are key points and difficulties in the processing of high-arsenic copper smoke.
At present, the methods for treating valuable metals in white smoke mainly comprise a pyrogenic method and a wet method. The pyrogenic process treatment method is characterized in that white smoke dust is added into lead ore at high temperature to be reduced and smelted in a blast furnace, volatile elements such as arsenic, zinc and the like enter the smoke dust to be collected, most of lead is recovered in a crude lead form, and copper is recovered in a matte form. And roasting the smoke dust by using a static reverberatory furnace to remove arsenic, recovering the arsenic in the smoke dust in the form of an arsenic trioxide product, and recovering zinc and indium in the roasting slag by using a wet leaching method. The wet leaching method is to use sulfuric acid to immerse soluble elements such as arsenic, copper, zinc, indium and the like in the white smoke dust into solution, lead, tin, bismuth and the like are left in leaching slag, and the leaching slag is used as a lead and tin smelting raw material. The leachate adopts a neutralization method to remove arsenic in the form of arsenic slag, a replacement method is adopted to recover copper and indium in the form of sponge copper and sponge indium respectively, and zinc in the leachate is recovered in the form of zinc sulfate heptahydrate. The problems of the pyrogenic process are: the elements are dispersed, and the process flow is long. The wet treatment has problems that: arsenic slag cannot be utilized, and the risk of environmental pollution exists. In view of the above problems, the present invention provides a method for recovering valuable metals from white smoke.
Disclosure of Invention
The invention aims to solve the defects in the prior art and provides a method for recovering valuable metals from white smoke.
In order to achieve the purpose, the invention adopts the following technical scheme:
a method for recovering valuable metals from white smoke dust comprises the following steps:
s1: selecting white smoke dust, fully slurrying the white smoke dust and concentrated sulfuric acid for 2-3h, roasting the slurried white smoke dust for 2-4h at the temperature of 400-600 ℃, carrying out dust collection treatment on smoke gas in the roasting process to obtain smoke dust, and collecting roasting slag after roasting, wherein arsenic in the white smoke dust enters the smoke dust in a volatilization mode, and other elements in the white smoke dust are not volatilized and are left in the roasting slag;
s2: performing sulfuric acid leaching treatment on the roasting slag obtained in the step S1 by using 50-80g/L dilute sulfuric acid solution, wherein the temperature in the leaching process is 90-100 ℃, the liquid-solid ratio of dilute sulfuric acid to the roasting slag is 4:1, the leaching time is 2-3h, zinc and copper in the roasting slag enter a primary leaching solution, and lead, tin and indium in the roasting slag are retained in the primary leaching slag;
s3: adding zinc powder into the primary leaching solution obtained in the step S2 to perform zinc powder displacement reaction, and further forming copper sponge and primary displaced solution;
s4: the first-stage leaching residue after the step S2 is subjected to pressure acid leaching treatment, wherein the pressure acid leaching treatment process is to place the first-stage leaching residue in a sulfuric acid solution with the sulfuric acid concentration of 150-;
s5: mixing the primary replaced liquid obtained in the step S3 and the secondary replaced liquid obtained in the step S4, and concentrating by adopting an evaporation concentration method to obtain zinc sulfate heptahydrate after evaporation concentration is finished;
s6: after step S4 is finished, lead and tin in the secondary leaching slag are respectively in an enriched state, so that the secondary leaching slag can be directly used as a lead-tin smelting raw material, i.e. the recovery of valuable metals in the white smoke dust is completed.
Preferably, in step S1, the white smoke component is: 10-20% of arsenic, 3-8% of tin, 20-25% of zinc, 3-8% of copper, 25-35% of lead and 0.1-0.2% of indium.
Preferably, in step S1, the purity of arsenic trioxide in the smoke dust is 95-99%, and the arsenic content in the obtained roasting slag is reduced to 0.3-0.5%, i.e., in step S1, the removal rate of arsenic in the white smoke dust is 98-99.5%.
Preferably, after the completion of step S2, the contents of zinc and copper in the first-level leaching residue are both reduced to 0.5-0.1%, that is, the leaching rates of zinc and copper in step S2 are both 98-99%.
Preferably, in step S3, the copper content in the sponge copper is 50-70%.
Preferably, in step S4, the indium content in the primary leaching residue is reduced to 0.005-0.01%, that is, the leaching rate of indium is 98-99%, and further the indium content in the sponge indium is 70-75%.
Preferably, in step S6, the lead and tin contents in the secondary leaching residue are enriched to 38-50% and 12-20%, respectively.
The method for recovering valuable metals in white smoke has the beneficial effects that: this scheme is in the application and with this in-process that realizes the dialogue smoke and dust: 1. arsenic in the white smoke can be recovered in the form of arsenic trioxide, so that the generation of arsenic slag in the recovery process of valuable metals in the white smoke is avoided, and the environmental protection is facilitated; 2. further, copper and indium in the white smoke can be efficiently recovered respectively in a two-stage acid leaching and zinc powder replacement mode; 3. in the next step, zinc in the displaced liquid can be recovered in a zinc sulfate heptahydrate mode through evaporation and concentration, so that the zinc in the white smoke can be efficiently recovered; 4. finally, lead and tin in the obtained secondary leaching slag can be in an enrichment state, and further can be used as lead and tin smelting raw materials, namely the recovery of lead and tin in the white smoke dust is realized; and the whole recovery process can avoid polluting the environment while realizing the high-efficient recycle of the metal in the white smoke dust, thereby being beneficial to popularization and application.
Drawings
FIG. 1 is a schematic flow chart of a method for recovering valuable metals from white smoke according to the present invention.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments.
Referring to fig. 1, a method for recovering valuable metals from white smoke includes the following steps:
s1: selecting white smoke dust, fully slurrying the white smoke dust and concentrated sulfuric acid for 2-3h, roasting the slurried white smoke dust for 2-4h at the temperature of 400-600 ℃, carrying out dust collection treatment on smoke gas in the roasting process to obtain smoke dust, and collecting roasting slag after roasting, wherein arsenic in the white smoke dust enters the smoke dust in a volatilization mode, and other elements in the white smoke dust are not volatilized and are left in the roasting slag;
s2: performing sulfuric acid leaching treatment on the roasting slag obtained in the step S1 by using 50-80g/L dilute sulfuric acid solution, wherein the temperature in the leaching process is 90-100 ℃, the liquid-solid ratio of dilute sulfuric acid to the roasting slag is 4:1, the leaching time is 2-3h, zinc and copper in the roasting slag enter a primary leaching solution, and lead, tin and indium in the roasting slag are retained in the primary leaching slag;
s3: adding zinc powder into the primary leaching solution obtained in the step S2 to perform zinc powder displacement reaction, and further forming copper sponge and primary displaced solution;
s4: the first-stage leaching residue after the step S2 is subjected to pressure acid leaching treatment, wherein the pressure acid leaching treatment process is to place the first-stage leaching residue in a sulfuric acid solution with the sulfuric acid concentration of 150-;
s5: mixing the primary displaced liquid obtained in the step S3 and the secondary displaced liquid obtained in the step S4, and concentrating by adopting an evaporation concentration method to obtain zinc sulfate heptahydrate after evaporation concentration is finished, so that the recovery of zinc in the white smoke and zinc powder added in the zinc powder displacement treatment process is realized;
s6: after step S4 is finished, lead and tin in the secondary leaching slag are respectively in an enriched state, so that the secondary leaching slag can be directly used as a lead-tin smelting raw material, i.e. the recovery of valuable metals in the white smoke dust is completed.
In step S1, the white smoke component is: 10-20% of arsenic, 3-8% of tin, 20-25% of zinc, 3-8% of copper, 25-35% of lead and 0.1-0.2% of indium.
In step S1, the purity of arsenic trioxide in the smoke dust is 95-99%, and the arsenic content in the obtained roasting slag is reduced to 0.3-0.5%, that is, in step S1, the removal rate of arsenic in the white smoke dust is 98-99.5%, thereby realizing the recovery of arsenic in the white smoke dust.
After the step S2 is finished, the contents of zinc and copper in the primary leaching residue are both reduced to 0.5-0.1%, namely the leaching rates of zinc and copper in the step S2 are both 98-99%.
In step S3, the copper content in the sponge copper is 50-70%, and the copper in the white smoke is recovered.
In step S4, the indium content in the primary leaching residue is reduced to 0.005-0.01%, that is, the leaching rate of indium reaches 98-99%, and further the indium content in the sponge indium is 70-75%, thereby realizing the recovery of indium in the white smoke.
In step S6, the lead and tin contents in the secondary leaching residue are respectively enriched to 38-50% and 12-20%, thereby realizing the recycling of lead and tin in the white smoke.
In summary, the following steps: the invention is applied and realizes the process of white smoke dust by the method that: 1. arsenic in the white smoke can be recovered in the form of arsenic trioxide, so that the generation of arsenic slag in the recovery process of valuable metals in the white smoke is avoided, and the environmental protection is facilitated; 2. further, copper and indium in the white smoke can be efficiently recovered respectively in a two-stage acid leaching and zinc powder replacement mode; 3. in the next step, zinc in the displaced liquid can be recovered in a zinc sulfate heptahydrate mode through evaporation and concentration, so that the zinc in the white smoke can be efficiently recovered; 4. finally, lead and tin in the obtained secondary leaching slag can be in an enrichment state, and further can be used as lead and tin smelting raw materials, namely the recovery of lead and tin in the white smoke dust is realized; and the whole recovery process can avoid polluting the environment while realizing the high-efficient recycle of the metal in the white smoke dust, thereby being beneficial to popularization and application.
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 person skilled in the art should be considered to be within the technical scope of the present invention, and the technical solutions and the inventive concepts thereof according to the present invention should be equivalent or changed within the scope of the present invention.
Claims (7)
1. A method for recovering valuable metals from white smoke is characterized by comprising the following steps:
s1: selecting white smoke dust, fully slurrying the white smoke dust and concentrated sulfuric acid for 2-3h, roasting the slurried white smoke dust for 2-4h at the temperature of 400-600 ℃, carrying out dust collection treatment on smoke gas in the roasting process to obtain smoke dust, and collecting roasting slag after roasting, wherein arsenic in the white smoke dust enters the smoke dust in a volatilization mode, and other elements in the white smoke dust are not volatilized and are left in the roasting slag;
s2: performing sulfuric acid leaching treatment on the roasting slag obtained in the step S1 by using 50-80g/L dilute sulfuric acid solution, wherein the temperature in the leaching process is 90-100 ℃, the liquid-solid ratio of dilute sulfuric acid to the roasting slag is 4:1, the leaching time is 2-3h, zinc and copper in the roasting slag enter a primary leaching solution, and lead, tin and indium in the roasting slag are retained in the primary leaching slag;
s3: adding zinc powder into the primary leaching solution obtained in the step S2 to perform zinc powder displacement reaction, and further forming copper sponge and primary displaced solution;
s4: the first-stage leaching residue after the step S2 is subjected to pressure acid leaching treatment, wherein the pressure acid leaching treatment process is to place the first-stage leaching residue in a sulfuric acid solution with the sulfuric acid concentration of 150-;
s5: mixing the primary replaced liquid obtained in the step S3 and the secondary replaced liquid obtained in the step S4, and concentrating by adopting an evaporation concentration method to obtain zinc sulfate heptahydrate after evaporation concentration is finished;
s6: after step S4 is finished, lead and tin in the secondary leaching slag are respectively in an enriched state, so that the secondary leaching slag can be directly used as a lead-tin smelting raw material, i.e. the recovery of valuable metals in the white smoke dust is completed.
2. The method for recovering valuable metals from white smoke according to claim 1, wherein in step S1, the white smoke component is: 10-20% of arsenic, 3-8% of tin, 20-25% of zinc, 3-8% of copper, 25-35% of lead and 0.1-0.2% of indium.
3. The method of claim 1, wherein the purity of arsenic trioxide in the flue dust is 95-99% in step S1, and the arsenic content in the obtained roasting slag is reduced to 0.3-0.5%, that is, the arsenic removal rate of the white flue dust is 98-99.5% in step S1.
4. The method for recycling valuable metals from white smoke dust according to claim 1, wherein after step S2, the contents of Zn and Cu in the first-stage leaching residue are both reduced to 0.5-0.1%, that is, the leaching rates of Zn and Cu in step S2 are both 98-99%.
5. The method for recycling valuable metals from white smoke as claimed in claim 1, wherein the copper content in the copper sponge is 50-70% in step S3.
6. The method of claim 1, wherein in step S4, the indium content in the first leaching residue is reduced to 0.005-0.01%, i.e. the leaching rate of indium is 98-99%, and further the indium content in the sponge indium is 70-75%.
7. The method for recycling valuable metals from white smoke as claimed in claim 1, wherein in step S6, the contents of lead and tin in the secondary leaching residue are respectively enriched to 38-50% and 12-20%.
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| CN202010306692.8A CN111378845A (en) | 2020-04-17 | 2020-04-17 | Method for recovering valuable metals from white smoke |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN112609084A (en) * | 2020-12-22 | 2021-04-06 | 江西自立环保科技有限公司 | Comprehensive treatment method for smoke dust with high zinc, lead and tin contents in fuming furnace |
| CN114150156A (en) * | 2021-11-30 | 2022-03-08 | 西安建筑科技大学 | Process for extracting zinc from low-grade zinc-containing dust and preparing nano zinc oxide |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112609084A (en) * | 2020-12-22 | 2021-04-06 | 江西自立环保科技有限公司 | Comprehensive treatment method for smoke dust with high zinc, lead and tin contents in fuming furnace |
| CN114150156A (en) * | 2021-11-30 | 2022-03-08 | 西安建筑科技大学 | Process for extracting zinc from low-grade zinc-containing dust and preparing nano zinc oxide |
| CN114150156B (en) * | 2021-11-30 | 2023-10-13 | 西安建筑科技大学 | Low-grade zinc-containing dust zinc extraction and nano zinc oxide preparation process |
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Application publication date: 20200707 |