CN110983059B - 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 PDFInfo
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- CN110983059B CN110983059B CN201911249945.6A CN201911249945A CN110983059B CN 110983059 B CN110983059 B CN 110983059B CN 201911249945 A CN201911249945 A CN 201911249945A CN 110983059 B CN110983059 B CN 110983059B
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- RYGMFSIKBFXOCR-UHFFFAOYSA-N copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims abstract description 69
- 239000010949 copper Substances 0.000 title claims abstract description 67
- 229910052802 copper Inorganic materials 0.000 title claims abstract description 67
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 title claims abstract description 66
- 229910052785 arsenic Inorganic materials 0.000 title claims abstract description 66
- 239000000779 smoke Substances 0.000 title claims abstract description 37
- 239000012065 filter cake Substances 0.000 title claims abstract description 36
- 238000003723 Smelting Methods 0.000 title claims abstract description 23
- GOLCXWYRSKYTSP-UHFFFAOYSA-N arsenic trioxide Inorganic materials O1[As]2O[As]1O2 GOLCXWYRSKYTSP-UHFFFAOYSA-N 0.000 claims abstract description 37
- 229960002594 arsenic trioxide Drugs 0.000 claims abstract description 24
- 238000001816 cooling Methods 0.000 claims abstract description 23
- GCPXMJHSNVMWNM-UHFFFAOYSA-N Trihydroxyarsenite(Iii) Chemical compound O[As](O)O GCPXMJHSNVMWNM-UHFFFAOYSA-N 0.000 claims abstract description 17
- 238000001914 filtration Methods 0.000 claims abstract description 15
- 238000007670 refining Methods 0.000 claims abstract description 7
- 238000002425 crystallisation Methods 0.000 claims description 32
- 230000005712 crystallization Effects 0.000 claims description 32
- 238000006243 chemical reaction Methods 0.000 claims description 30
- 239000000428 dust Substances 0.000 claims description 23
- 238000002386 leaching Methods 0.000 claims description 19
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 18
- 239000012452 mother liquor Substances 0.000 claims description 14
- BWFPGXWASODCHM-UHFFFAOYSA-N Copper monosulfide Chemical compound [Cu]=S BWFPGXWASODCHM-UHFFFAOYSA-N 0.000 claims description 13
- 239000007788 liquid Substances 0.000 claims description 12
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 10
- 239000011261 inert gas Substances 0.000 claims description 10
- 238000001556 precipitation Methods 0.000 claims description 10
- 229910052757 nitrogen Inorganic materials 0.000 claims description 9
- 229940091251 Zinc Supplements Drugs 0.000 claims description 8
- HCHKCACWOHOZIP-UHFFFAOYSA-N zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 8
- 229910052725 zinc Inorganic materials 0.000 claims description 8
- 239000011701 zinc Substances 0.000 claims description 8
- 238000005406 washing Methods 0.000 claims description 7
- 230000035484 reaction time Effects 0.000 claims description 6
- 239000007787 solid Substances 0.000 claims description 5
- NWONKYPBYAMBJT-UHFFFAOYSA-L Zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 claims description 4
- 239000012141 concentrate Substances 0.000 claims description 4
- 239000000463 material Substances 0.000 claims description 4
- 229960001763 zinc sulfate Drugs 0.000 claims description 4
- 229910000368 zinc sulfate Inorganic materials 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 3
- 239000008213 purified water Substances 0.000 claims description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 3
- NINIDFKCEFEMDL-UHFFFAOYSA-N sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 2
- 229910052717 sulfur Inorganic materials 0.000 claims description 2
- 239000011593 sulfur Substances 0.000 claims description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims 2
- 229910052786 argon Inorganic materials 0.000 claims 1
- 239000007789 gas Substances 0.000 claims 1
- 238000000034 method Methods 0.000 abstract description 17
- 238000004519 manufacturing process Methods 0.000 abstract description 6
- RAHZWNYVWXNFOC-UHFFFAOYSA-N sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 abstract description 6
- 238000011084 recovery Methods 0.000 abstract description 3
- 238000005265 energy consumption Methods 0.000 abstract description 2
- 239000000243 solution Substances 0.000 description 15
- 239000000047 product Substances 0.000 description 7
- UKUVVAMSXXBMRX-UHFFFAOYSA-N 2,4,5-trithia-1,3-diarsabicyclo[1.1.1]pentane Chemical group S1[As]2S[As]1S2 UKUVVAMSXXBMRX-UHFFFAOYSA-N 0.000 description 5
- 239000010413 mother solution Substances 0.000 description 4
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 3
- 229910052797 bismuth Inorganic materials 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 239000002893 slag Substances 0.000 description 3
- 229910017518 Cu Zn Inorganic materials 0.000 description 2
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 2
- 229910052787 antimony Inorganic materials 0.000 description 2
- 125000004122 cyclic group Chemical group 0.000 description 2
- 239000011133 lead Substances 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- RMBBSOLAGVEUSI-UHFFFAOYSA-H Calcium arsenate Chemical compound [Ca+2].[Ca+2].[Ca+2].[O-][As]([O-])([O-])=O.[O-][As]([O-])([O-])=O RMBBSOLAGVEUSI-UHFFFAOYSA-H 0.000 description 1
- ARUVKPQLZAKDPS-UHFFFAOYSA-L Copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 1
- WUAPFZMCVAUBPE-UHFFFAOYSA-N Rhenium Chemical compound [Re] WUAPFZMCVAUBPE-UHFFFAOYSA-N 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- XHTRYVMKFMUJLU-UHFFFAOYSA-N arsenous acid Chemical compound O[As]=O XHTRYVMKFMUJLU-UHFFFAOYSA-N 0.000 description 1
- 229940103357 calcium arsenate Drugs 0.000 description 1
- UGFAIRIUMAVXCW-UHFFFAOYSA-N carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- 239000000498 cooling water Substances 0.000 description 1
- 229910000365 copper sulfate Inorganic materials 0.000 description 1
- 238000005137 deposition process Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000003546 flue gas Substances 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- BMWMWYBEJWFCJI-UHFFFAOYSA-K iron(3+);trioxido(oxo)-$l^{5}-arsane Chemical compound [Fe+3].[O-][As]([O-])([O-])=O BMWMWYBEJWFCJI-UHFFFAOYSA-K 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 229910052702 rhenium Inorganic materials 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- 238000005987 sulfurization reaction Methods 0.000 description 1
- 238000004073 vulcanization Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Classifications
-
- 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
-
- 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
-
- 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
- C22B19/26—Refining solutions containing zinc values, e.g. obtained by leaching zinc ores
-
- 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
-
- 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
-
- 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 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
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
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:
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
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:
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 components of the arsenic filter cake and the white smoke dust leaching solution before the reaction are shown in the following table:
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:
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:
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:
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:
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 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:
2. cooling and filtering
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:
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 and reaction time of 1-4 h, and after the reaction is finished, the autoclave is decompressed and cooled to 50-60 ℃;
the main chemical reaction is as follows:
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 liquid obtained in the step b into a crystallization tank II, continuously cooling and crystallizing to normal temperature to obtain crude arsenic trioxide crystals and crystallization mother liquor, returning the crystallization mother liquor to white smoke dust for circular leaching, or opening a way to concentrate crystalline zinc sulfate, wherein the zinc content of the crystallization mother liquor is high;
the main chemical reaction is as follows:
；
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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| CN201911249945.6A CN110983059B (en) | 2019-12-09 | 2019-12-09 | Method for recovering copper and arsenic from copper smelting white smoke leachate and arsenic filter cake |
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Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1033396A (en) * | 1987-12-02 | 1989-06-14 | 周作才 | The double decomposition beneficiation of copper oxide ore |
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| WO2009019955A1 (en) * | 2007-08-09 | 2009-02-12 | Dowa Metals & Mining Co., Ltd. | Method for treatment of arsenic-containing nonferrous smelting intermediate product |
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| CN110331300A (en) * | 2019-06-28 | 2019-10-15 | 东营方圆有色金属有限公司 | A kind of method of Copper making industry waste acid and the comprehensive extraction arsenic of flue dust |
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