CN110983059A - Method for recovering copper and arsenic from copper smelting white smoke leachate and arsenic filter cake - Google Patents

Method for recovering copper and arsenic from copper smelting white smoke leachate and arsenic filter cake Download PDF

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CN110983059A
CN110983059A CN201911249945.6A CN201911249945A CN110983059A CN 110983059 A CN110983059 A CN 110983059A CN 201911249945 A CN201911249945 A CN 201911249945A CN 110983059 A CN110983059 A CN 110983059A
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arsenic
copper
filter cake
white smoke
following
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CN110983059B (en
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林泓富
吴健辉
周安梁
李田玉
罗伟金
李光明
林青
刘忠梅
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Heilongjiang Zijin Copper Co Ltd
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    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22BPRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B7/00Working 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
    • C22B7/02Working-up flue dust
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22BPRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B15/00Obtaining copper
    • C22B15/0063Hydrometallurgy
    • C22B15/0084Treating solutions
    • C22B15/0089Treating solutions by chemical methods
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22BPRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B19/00Obtaining zinc or zinc oxide
    • C22B19/20Obtaining zinc otherwise than by distilling
    • C22B19/26Refining solutions containing zinc values, e.g. obtained by leaching zinc ores
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22BPRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B30/00Obtaining antimony, arsenic or bismuth
    • C22B30/04Obtaining arsenic
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22BPRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B7/00Working 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
    • C22B7/006Wet processes
    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02PCLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P10/00Technologies related to metal processing
    • Y02P10/20Recycling

Abstract

The invention relates to a method for recovering copper and arsenic from copper smelting white smoke leachate and an arsenic filter cake, belonging to the technical field of comprehensive utilization of resources. The method comprises the following steps: a. a step of copper deposition under pressure; b. cooling and filtering; c. cooling and crystallizing; d. and refining the arsenic trioxide. The invention has the following advantages: the arsenic filter cake is recycled, the recovery rates of copper and arsenic are high, the whole process is circulated in a closed loop, and secondary pollution is avoided; meanwhile, sulfur dioxide is not needed for reduction, so that the production cost is saved, the production flow is shortened, and the time and the energy consumption are saved.

Description

Method for recovering copper and arsenic from copper smelting white smoke leachate and arsenic filter cake
Technical Field
The invention relates to a method for recovering copper and arsenic from copper smelting white smoke leachate and an arsenic filter cake, belonging to the technical field of comprehensive utilization of resources.
Background
The white smoke dust is collected in an electric dust collection process in a copper smelting process, contains elements such as copper, lead, zinc, arsenic, bismuth, antimony, gold, silver and the like, and is required to be opened from a system and separately recycled in order to ensure the normal operation of production and prevent the furnace condition from being deteriorated and even the quality of an electrolytic copper product from being influenced due to the cyclic accumulation of harmful impurities such as lead, arsenic, antimony, bismuth and the like.
The arsenic filter cake is arsenic sulfide slag obtained by performing sulfuration dearsenification on open-circuit waste acid in the flue gas washing and purifying process in the copper smelting process, and the main component of the arsenic sulfide slag is arsenic sulfide. The disposal method of arsenic-containing materials mainly comprises two main types: one is harmless disposal, and the arsenic is stored by calcium arsenate and ferric arsenate with stable performance; the other is resource utilization, namely, the arsenic-containing materials are comprehensively utilized to prepare arsenic products, and valuable metals such as copper, rhenium, bismuth and the like are comprehensively recovered.
In order to solve the problem of the coming out of arsenic filter cakes in the copper smelting process, in the early nineties of the last century, the Japan dong technology is introduced into Jiangtong Guixi smelting plants, copper powder is used as a raw material, the arsenic filter cakes are replaced after oxidation leaching to produce arsenic trioxide products and copper sulfide, the arsenic trioxide is sold, and the copper sulfide is returned to a system for smelting, so that the resource utilization of the arsenic filter cakes is realized, but the process has the defect of high production cost, 3.5-4.0 tons of copper powder are consumed for producing 1 ton of arsenic trioxide, and the process is changed into a high-pressure oxidation leaching process.
The Chinese invention patent application 'a comprehensive recovery method of arsenic sulfide slag and smoke dust leachate in copper smelting' (application publication No. CN 108249480A) discloses a process for treating an arsenic filter cake by using white smoke dust leachate and comprehensively recovering elements such as arsenic, copper, zinc and the like, and the main process comprises the steps of copper sulfide precipitation, liquid reduction after vulcanization, concentration, mixed crystallization, crystallization dissolution and refining.
Disclosure of Invention
The invention aims to provide a method for comprehensively recovering copper and arsenic from copper smelting white smoke leachate and an arsenic filter cake.
The technical scheme of the invention is as follows: a method for recovering copper and arsenic from copper smelting white smoke leachate and arsenic filter cake comprises the following steps:
a. step of copper deposition under pressure
According to the copper and arsenic components of the white smoke leachate and the arsenic filter cake, the dosage of the arsenic filter cake is controlled to be 0.4-1.0 time of the theoretical dosage for slurrying, and the slurrying liquid-solid ratio is controlled to be 9-12: 1, transferring the slurried material liquid into a high-pressure reaction kettle I, and carrying out copper deposition reaction under the atmosphere of nitrogen (or inert gas) under the following conditions: nitrogen (or inert gas) partial pressure is 0.1-1.0 MPa, the temperature is 90-150 ℃, the sulfuric acid degree is 1-150 g/l, the reaction time is 1-4 h, and after the reaction is finished, the autoclave is decompressed and cooled to 50-60 ℃;
b. cooling and filtering
B, filtering the feed liquid obtained in the step a to respectively obtain solid copper sulfide and copper precipitation liquid, and directly returning the copper sulfide to a copper smelting system;
c. cooling crystallization
C, transferring the copper-precipitated solution obtained in the step b into a crystallization tank II, continuously cooling and crystallizing to normal temperature to obtain crude arsenic trioxide crystals and a crystallization mother liquor, returning the crystallization mother liquor to white smoke dust for circular leaching, and if the crystallization mother liquor contains high zinc, opening a way to concentrate crystalline zinc sulfate;
d. refining of arsenic trioxide
And c, transferring the coarse arsenic trioxide crystals obtained in the step c into a crystallization tank III, washing with purified water, controlling the washing temperature to be 20-60 ℃, and filtering and drying to obtain national standard grade-1 arsenic trioxide.
In the step a, the dosage of the arsenic filter cake is 0.4-1.0 time of the theoretical amount, and the dosage is the required amount for carrying out copper deposition replacement reaction on arsenic sulfide and copper sulfate in the white smoke dust leachate.
In the step a, after the reaction is finished, the autoclave is decompressed and cooled to 50-60 ℃, namely, after the reaction is finished, the air inlet valve is closed, the pressure relief valve is opened to gradually release the pressure until the reading of the pressure gauge is 0, and meanwhile, the coil pipe cooling water in the autoclave is opened to cool the autoclave until the temperature of the feed liquid in the autoclave is lower than 60 ℃.
And in the step b, the copper sulfide is directly returned to a copper smelting system, namely the obtained copper sulfide and other copper concentrate raw materials are mixed according to smelting requirements.
And c, in the step c, the step of returning the crystallization mother liquor to the white smoke dust for cyclic leaching refers to the step of recycling the crystallization mother liquor, leaching is carried out according to the leaching condition of the white smoke dust, and in the mother liquor circulating process, if the zinc concentration reaches more than 40g/l, the zinc sulfate is recovered by opening a circuit and independently concentrating and crystallizing.
The main chemical reactions involved in the invention are as follows:
(1) pressurized copper deposition process
Figure 957142DEST_PATH_IMAGE001
The reaction of arsenic filter cake copper deposition is described above, most of arsenic in the white smoke leachate is in a +5 valence state, and under the pressurized condition, the following side reaction can occur with the arsenic filter cake:
Figure 694154DEST_PATH_IMAGE002
the reaction shows that the + 5-valent arsenic in the white smoke leachate can not be increased in the circulating process, and the + 5-valent arsenic can generate + 3-valent arsenous acid, so that reduction by sulfur dioxide is not needed.
(2) Cooling crystallization
Figure 903025DEST_PATH_IMAGE003
The arsenic filter cake comprises the following main components in percentage by mass: 5-50% of arsenic, 0.5-10% of copper and 20-50% of sulfur.
The white smoke dust leaching solution comprises the following main components: 1-40 g/l of copper, 1-50 g/l of arsenic, 1-40 g/l of zinc and 1-150 g/l of sulfuric acid.
Compared with the prior art, the invention has the following advantages:
the arsenic filter cake is recycled, the recovery rates of copper and arsenic are high, the whole process is circulated in a closed loop, and secondary pollution is avoided; meanwhile, sulfur dioxide is not needed for reduction, so that the production cost is saved, the production flow is shortened, and the time and the energy consumption are saved.
Drawings
FIG. 1 is a process flow diagram of the present invention.
Detailed Description
The present invention will be further explained with reference to the accompanying drawings.
A method for recovering copper and arsenic from copper smelting white smoke leachate and arsenic filter cake comprises the following steps:
a. step of copper deposition under pressure
According to the copper and arsenic components of the white smoke dust leachate and the arsenic filter cake, the dosage of the arsenic filter cake is controlled to be 0.4-1.0 time of the theoretical amount for slurrying, the slurried feed liquid is transferred into a high-pressure reaction kettle I, and the copper deposition reaction is carried out under the control of the following conditions under the atmosphere of nitrogen (or inert gas): nitrogen (or inert gas) partial pressure is 0.1-1.0 MPa, the temperature is 90-150 ℃, the sulfuric acid degree is 1-150 g/l, the reaction time is 1-4 h, and after the reaction is finished, the autoclave is decompressed and cooled to 50-60 ℃;
b. cooling and filtering
B, filtering the feed liquid obtained in the step a to respectively obtain solid copper sulfide and copper precipitation liquid, and directly returning the copper sulfide to a copper smelting system;
c. cooling crystallization
C, transferring the copper-precipitated solution obtained in the step b into a crystallization tank II, continuously cooling and crystallizing to normal temperature to obtain crude arsenic trioxide crystals and a crystallization mother liquor, returning the crystallization mother liquor to white smoke dust for circular leaching, and if the crystallization mother liquor contains high zinc, opening a way to concentrate crystalline zinc sulfate;
d. refining of arsenic trioxide
And c, transferring the coarse arsenic trioxide crystals obtained in the step c into a crystallization tank III, washing with purified water, controlling the washing temperature to be 20-60 ℃, and filtering and drying to obtain national standard grade-1 arsenic trioxide.
The following examples are illustrative of the present invention and are not intended to limit the scope of the present invention.
Taking arsenic filter cakes and white smoke dust leachate of a certain domestic copper smelting enterprise as an example, the main components of the raw materials are as follows:
Figure 332869DEST_PATH_IMAGE004
example 1
1. Pressure copper deposition
Carrying out copper precipitation reaction in a 2L high-pressure kettle under the conditions that the reaction temperature is 102 ℃, the reaction time is 2 hours, the nitrogen (or inert gas) pressure is 0.3MPa, the acidity of the white smoke dust leaching solution is 30g/L, and the dosage of the arsenic filter cake is 0.7 times of the theoretical amount, wherein the reaction is carried out before the reaction, and the components of the arsenic filter cake and the white smoke dust leaching solution are shown in the following table:
Figure 574494DEST_PATH_IMAGE005
2. cooling and filtering
After the reaction is finished, the solution after copper deposition and copper sulfide are obtained after pressure relief, cooling and filtration, and the related components are shown in the following table:
Figure 787301DEST_PATH_IMAGE006
3. cooling crystallization
The solution after copper deposition has low As concentration and is not saturated, and can not be crystallized in the cooling process, and the solution directly returns to the white smoke dust leaching process.
Example 2
1. Pressure copper deposition
Carrying out copper precipitation reaction in a 2L high-pressure kettle under the conditions that the reaction temperature is 115 ℃, the reaction time is 2 hours, the nitrogen (or inert gas) pressure is 0.3MPa, the acidity of the white smoke dust leaching solution is 80g/L, and the dosage of the arsenic filter cake is 1.05 times of the theoretical amount, wherein the reaction is carried out before the reaction, and the components of the arsenic filter cake and the white smoke dust leaching solution are shown in the following table:
Figure 430772DEST_PATH_IMAGE007
2. cooling and filtering
After the reaction is finished, filtering after pressure relief and cooling to obtain copper precipitation solution and copper sulfide, wherein the related components are shown in the following table:
Figure 765938DEST_PATH_IMAGE008
3. cooling crystallization
The filtered copper-precipitation solution is continuously stirred and cooled to room temperature to obtain crude arsenic trioxide crystals and a crystallization mother solution, and the crystallization mother solution
Returning to the white smoke dust for leaching, the mother liquor components are shown in the following table:
name (R) As Zn Cu H2SO4
Crystallization mother liquor (g/l) 13.2 6.8 0.55 75.2
4. Refining of arsenic trioxide
The crude arsenic trioxide crystals obtained by cooling crystallization are continuously stirred, washed, filtered and dried to obtain arsenic trioxide products
The main components are shown in the following table:
name (R) As2O3 Cu Zn Fe Pb Bi
As2O3Product (%) 99.65 0.003 0.0007 0.0012 0.0004 0.0003
Example 3.
1. Pressure copper deposition
Carrying out copper precipitation reaction in a 2L high-pressure kettle under the conditions that the reaction temperature is 125 ℃, the reaction time is 2 hours, the nitrogen (or inert gas) pressure is 0.3MPa, the acidity of the white smoke dust leaching solution is 100g/L, and the dosage of the arsenic filter cake is 0.7 times of the theoretical amount, wherein the components of the arsenic filter cake and the white smoke dust leaching solution before the reaction are shown in the following table:
Figure 681811DEST_PATH_IMAGE009
2. cooling and filtering
Figure 760625DEST_PATH_IMAGE010
3. Cooling crystallization
The filtered copper-precipitation solution is continuously stirred and cooled to room temperature to obtain crude arsenic trioxide crystals and a crystallization mother solution, and the crystallization mother solution
Returning to the white smoke dust for leaching, the mother liquor components are shown in the following table:
name (R) As Zn Cu H2SO4
Crystallization mother liquor (g/l) 14.2 4.3 2.55 86.52
4. Refining of arsenic trioxide
The crude arsenic trioxide crystals obtained by cooling crystallization are continuously stirred, washed, filtered and dried to obtain arsenic trioxide products
The main components are shown in the following table:
name (R) As2O3 Cu Zn Fe Pb Bi
As2O3Product (%) 99.70 0.0036 0.0006 0.0015 0.0003 0.0002

Claims (4)

1. A method for recovering copper and arsenic from copper smelting white smoke leachate and arsenic filter cake is characterized by comprising the following steps: the method comprises the following steps:
a. step of copper deposition under pressure
According to the copper and arsenic components of the white smoke leachate and the arsenic filter cake, the dosage of the arsenic filter cake is controlled to be 0.4-1.0 time of the theoretical dosage for slurrying, and the slurrying liquid-solid ratio is controlled to be 9-12: 1, transferring the slurried material liquid into a high-pressure reaction kettle I, and carrying out copper deposition reaction under the atmosphere of nitrogen or inert gas by controlling the following conditions: nitrogen or inert gas partial pressure of 0.1-1.0 MPa, temperature of 90-150 ℃, sulfuric acid degree of 1-150 g/l, reaction time of 1-4 h, after the reaction is finished, pressure relief and cooling of the autoclave to 50-60 ℃;
the main chemical reaction is as follows:
Figure DEST_PATH_IMAGE002
b. cooling and filtering
B, filtering the feed liquid obtained in the step a to respectively obtain solid copper sulfide and copper precipitation liquid, and directly returning the copper sulfide to a copper smelting system;
c. cooling crystallization
C, transferring the copper-precipitated solution obtained in the step b into a crystallization tank II, continuously cooling and crystallizing to normal temperature to obtain crude arsenic trioxide crystals and a crystallization mother liquor, returning the crystallization mother liquor to white smoke dust for circular leaching, and if the crystallization mother liquor contains high zinc, opening a way to concentrate crystalline zinc sulfate;
the main chemical reaction is as follows:
Figure DEST_PATH_IMAGE004
d. refining of arsenic trioxide
And c, transferring the coarse arsenic trioxide crystals obtained in the step c into a crystallization tank III, washing with purified water, controlling the washing temperature to be 20-60 ℃, and filtering and drying to obtain national standard grade-1 arsenic trioxide.
2. The method for recovering copper and arsenic from copper smelting white smoke leachate and arsenic filter cake according to claim 1, wherein the method comprises the following steps: the inert gas in the step a is: and argon gas.
3. The method for recovering copper and arsenic from copper smelting white smoke leachate and arsenic filter cake according to claim 1, wherein the method comprises the following steps: the arsenic filter cake comprises the following main components in percentage by mass: 5-50% of arsenic, 0.5-10% of copper and 20-50% of sulfur.
4. The method for recovering copper and arsenic from copper smelting white smoke leachate and arsenic filter cake according to claim 1, wherein the method comprises the following steps: the white smoke dust leaching solution comprises the following main components: 1-40 g/l of copper, 1-50 g/l of arsenic, 1-40 g/l of zinc and 1-150 g/l of sulfuric acid.
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CN114059077A (en) * 2021-10-27 2022-02-18 湖南有色金属研究院有限责任公司 Arsenic filter cake treatment method
CN115747500A (en) * 2022-11-14 2023-03-07 郴州金铖环保科技有限公司 Method for cooperatively removing chlorine in strong-acid arsenic solution from high-arsenic silver-containing smelting slag
WO2023030165A1 (en) * 2021-08-29 2023-03-09 中南大学 Method for co-processing copper-smelting arsenic sulfide slag and arsenic-containing soot
CN115821065A (en) * 2022-12-21 2023-03-21 黑龙江紫金铜业有限公司 Recycling method for recycling arsenic and leaching residues from black copper mud and arsenic filter cake

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2023030165A1 (en) * 2021-08-29 2023-03-09 中南大学 Method for co-processing copper-smelting arsenic sulfide slag and arsenic-containing soot
CN114059077A (en) * 2021-10-27 2022-02-18 湖南有色金属研究院有限责任公司 Arsenic filter cake treatment method
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CN115747500A (en) * 2022-11-14 2023-03-07 郴州金铖环保科技有限公司 Method for cooperatively removing chlorine in strong-acid arsenic solution from high-arsenic silver-containing smelting slag
CN115821065A (en) * 2022-12-21 2023-03-21 黑龙江紫金铜业有限公司 Recycling method for recycling arsenic and leaching residues from black copper mud and arsenic filter cake

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Address after: 161000 No. 1, Fujing Road, Fularji district electric power office, Qiqihar City, Heilongjiang Province

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Address before: 161000 Room 101, science and technology entrepreneurship center building, north end of Gongnong street, Fularji District, Qiqihar City, Heilongjiang Province

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