CN115044778B - Method for leaching zinc oxide and copper white smoke dust in mixed mode - Google Patents
Method for leaching zinc oxide and copper white smoke dust in mixed mode Download PDFInfo
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- CN115044778B CN115044778B CN202210667812.6A CN202210667812A CN115044778B CN 115044778 B CN115044778 B CN 115044778B CN 202210667812 A CN202210667812 A CN 202210667812A CN 115044778 B CN115044778 B CN 115044778B
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- 239000010949 copper Substances 0.000 title claims abstract description 153
- 238000002386 leaching Methods 0.000 title claims abstract description 145
- 229910052802 copper Inorganic materials 0.000 title claims abstract description 133
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims abstract description 122
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 title claims abstract description 74
- 238000000034 method Methods 0.000 title claims abstract description 58
- 239000000428 dust Substances 0.000 title claims abstract description 42
- 239000000779 smoke Substances 0.000 title claims abstract description 42
- 239000011787 zinc oxide Substances 0.000 title claims abstract description 37
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 188
- 229910052785 arsenic Inorganic materials 0.000 claims abstract description 87
- 239000002253 acid Substances 0.000 claims abstract description 83
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 claims abstract description 78
- 229910052742 iron Inorganic materials 0.000 claims abstract description 70
- 238000001556 precipitation Methods 0.000 claims abstract description 67
- 239000002893 slag Substances 0.000 claims abstract description 57
- 239000011701 zinc Substances 0.000 claims abstract description 52
- 239000007788 liquid Substances 0.000 claims abstract description 42
- 230000007935 neutral effect Effects 0.000 claims abstract description 42
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 37
- 230000008569 process Effects 0.000 claims abstract description 35
- 238000006298 dechlorination reaction Methods 0.000 claims abstract description 32
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 24
- BMWMWYBEJWFCJI-UHFFFAOYSA-K iron(3+);trioxido(oxo)-$l^{5}-arsane Chemical compound [Fe+3].[O-][As]([O-])([O-])=O BMWMWYBEJWFCJI-UHFFFAOYSA-K 0.000 claims abstract description 21
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 20
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 20
- 239000001301 oxygen Substances 0.000 claims abstract description 20
- 239000003792 electrolyte Substances 0.000 claims abstract description 12
- 239000002699 waste material Substances 0.000 claims abstract description 12
- 238000002156 mixing Methods 0.000 claims abstract description 11
- 238000000746 purification Methods 0.000 claims abstract description 6
- 238000001914 filtration Methods 0.000 claims abstract description 4
- 238000005266 casting Methods 0.000 claims abstract description 3
- 238000005868 electrolysis reaction Methods 0.000 claims abstract description 3
- 230000035484 reaction time Effects 0.000 claims description 17
- 239000000460 chlorine Substances 0.000 claims description 15
- 235000021110 pickles Nutrition 0.000 claims description 6
- 229910052801 chlorine Inorganic materials 0.000 claims description 5
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 4
- 238000005137 deposition process Methods 0.000 claims 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 abstract description 16
- 230000000694 effects Effects 0.000 abstract description 16
- 230000001698 pyrogenic effect Effects 0.000 abstract description 3
- 238000007711 solidification Methods 0.000 abstract description 3
- 230000008023 solidification Effects 0.000 abstract description 3
- 238000009854 hydrometallurgy Methods 0.000 abstract description 2
- 239000000243 solution Substances 0.000 description 54
- 238000007654 immersion Methods 0.000 description 24
- 238000005554 pickling Methods 0.000 description 14
- 230000000052 comparative effect Effects 0.000 description 10
- 239000003795 chemical substances by application Substances 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 4
- 239000003984 copper intrauterine device Substances 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002244 precipitate Substances 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 238000005265 energy consumption Methods 0.000 description 3
- 150000002739 metals Chemical class 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- 238000003723 Smelting Methods 0.000 description 2
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 230000006978 adaptation Effects 0.000 description 2
- 229960002594 arsenic trioxide Drugs 0.000 description 2
- GOLCXWYRSKYTSP-UHFFFAOYSA-N arsenic trioxide Inorganic materials O1[As]2O[As]1O2 GOLCXWYRSKYTSP-UHFFFAOYSA-N 0.000 description 2
- KTTMEOWBIWLMSE-UHFFFAOYSA-N diarsenic trioxide Chemical compound O1[As](O2)O[As]3O[As]1O[As]2O3 KTTMEOWBIWLMSE-UHFFFAOYSA-N 0.000 description 2
- 229910052745 lead Inorganic materials 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 238000009853 pyrometallurgy Methods 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 1
- JEMGLEPMXOIVNS-UHFFFAOYSA-N arsenic copper Chemical compound [Cu].[As] JEMGLEPMXOIVNS-UHFFFAOYSA-N 0.000 description 1
- CUGMJFZCCDSABL-UHFFFAOYSA-N arsenic(3+);trisulfide Chemical compound [S-2].[S-2].[S-2].[As+3].[As+3] CUGMJFZCCDSABL-UHFFFAOYSA-N 0.000 description 1
- 229910000365 copper sulfate Inorganic materials 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
- OMZSGWSJDCOLKM-UHFFFAOYSA-N copper(II) sulfide Chemical compound [S-2].[Cu+2] OMZSGWSJDCOLKM-UHFFFAOYSA-N 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000004070 electrodeposition Methods 0.000 description 1
- 238000005363 electrowinning Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000003546 flue gas Substances 0.000 description 1
- 229910052595 hematite Inorganic materials 0.000 description 1
- 239000011019 hematite Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- -1 iron ions Chemical class 0.000 description 1
- LIKBJVNGSGBSGK-UHFFFAOYSA-N iron(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Fe+3].[Fe+3] LIKBJVNGSGBSGK-UHFFFAOYSA-N 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 230000008520 organization Effects 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000011946 reduction process Methods 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
- C22B19/00—Obtaining zinc or zinc oxide
- C22B19/34—Obtaining zinc oxide
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
- B09B—DISPOSAL OF SOLID WASTE
- B09B3/00—Destroying solid waste or transforming solid waste into something useful or harmless
- B09B3/40—Destroying solid waste or transforming solid waste into something useful or harmless involving thermal treatment, e.g. evaporation
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
- B09B—DISPOSAL OF SOLID WASTE
- B09B3/00—Destroying solid waste or transforming solid waste into something useful or harmless
- B09B3/70—Chemical treatment, e.g. pH adjustment or oxidation
-
- 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
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25C—PROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
- C25C1/00—Electrolytic production, recovery or refining of metals by electrolysis of solutions
- C25C1/16—Electrolytic production, recovery or refining of metals by electrolysis of solutions of zinc, cadmium or mercury
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
- B09B—DISPOSAL OF SOLID WASTE
- B09B2101/00—Type of solid waste
- B09B2101/30—Incineration ashes
-
- 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 belongs to the technical field of hydrometallurgy, and particularly relates to a method for leaching zinc oxide and copper white smoke dust in a mixing way. The method for leaching zinc oxide and copper white smoke dust in a mixing way comprises the following steps: (1) Mixing zinc oxide with copper white smoke dust, adding acid leaching solution, and performing neutral leaching to obtain neutral leaching solution and neutral leaching slag; (2) Adding iron powder into the neutral leaching solution, carrying out copper precipitation and dechlorination, and filtering to obtain copper slag and copper precipitation and dechlorination liquid; adding waste electrolyte and sulfuric acid into the intermediate leaching slag to perform acid leaching to obtain acid leaching slag and acid leaching liquid; (3) Introducing oxygen into the solution after copper precipitation and dechlorination to perform oxygen pressure iron precipitation and arsenic removal to obtain ferric arsenate slag and solution after iron precipitation and arsenic removal; removing arsenic from the solution after iron precipitation, and delivering the solution to remove iron for purification, electrolysis and casting to produce electro-zinc; and sending the ferric arsenate slag to a pyrogenic process for solidification treatment. The invention can treat the white smoke dust with low copper content by up to 50%. The leaching rate of zinc can reach more than 98%, the leaching rate of copper can reach more than 95%, and the arsenic removal effect can reach 99%.
Description
Technical Field
The invention belongs to the technical field of nonferrous hydrometallurgy, and particularly relates to a method for leaching zinc oxide and copper white smoke dust in a mixing way.
Background
Copper white smoke dust with higher arsenic content is generated in the copper pyrometallurgy process, generally 5-18% of copper content, 9-18% of arsenic content and less than 8% of copper content can be called low copper white smoke dust, and conversely high copper white smoke dust. The arsenic in the copper white smoke requires to be discharged from the open circuit of a copper smelting system, so that normal production of the system can be ensured, at present, the copper white smoke is mostly treated by adopting a wet method to discharge arsenic outside the open circuit, namely, the copper white smoke is subjected to acid leaching, copper is converted into a copper sulfate solution, arsenic sulfide slag is added to deposit copper to form copper sulfide slag, sulfur dioxide flue gas is introduced into the arsenic-containing solution to carry out arsenic reduction, and white arsenic products are produced through crystallization. The method can realize the separation of copper and arsenic, but a large amount of sulfuric acid is produced in the reduction process of copper precipitation and arsenic, the redundant sulfuric acid needs to be neutralized and treated, a large amount of neutralization slag is produced to be treated, and the white arsenic product has limited sales market and needs to be stored in a warehouse for a long time.
Disclosure of Invention
The invention aims to provide a method for mixed leaching of zinc oxide and copper white smoke dust, which can separate copper and arsenic and discharge arsenic solidified slag, and solves the technical problems of copper and arsenic separation and arsenic solidification harmlessness.
In order to solve the technical problems, the technical scheme of the invention is as follows:
a method for leaching zinc oxide and copper white smoke dust in a mixing way comprises the following steps:
(1) Mixing zinc oxide with copper white smoke dust, adding acid leaching solution, and performing neutral leaching to obtain neutral leaching solution and neutral leaching slag;
(2) Adding iron powder into the neutral leaching solution, carrying out copper precipitation and dechlorination, and filtering to obtain copper slag and copper precipitation and dechlorination liquid;
adding waste electrolyte and sulfuric acid into the intermediate leaching slag to perform acid leaching to obtain acid leaching slag and acid leaching liquid;
(3) Introducing oxygen into the solution after copper precipitation and dechlorination to perform oxygen pressure iron precipitation and arsenic removal to obtain ferric arsenate slag and solution after iron precipitation and arsenic removal;
removing arsenic from the solution after iron precipitation, and delivering the solution to remove iron for purification, electrolysis and casting to produce electro-zinc; and sending the ferric arsenate slag to a pyrogenic process for solidification treatment.
In the invention, the reason why the zinc oxide and low copper white smoke mixed leaching adopts neutral leaching instead of oxygen pressure leaching is that the zinc-containing phase of the zinc oxide is ZnO, and if oxygen pressure leaching is adopted, on one hand, the energy consumption is high, and the leaching rate is not obviously increased. On the other hand, the concentration of iron in the oxygen-bearing leachate is not sufficient to completely precipitate arsenic due to the low iron and high arsenic in the copper white dust.
Preferably, the acid concentration of the pickle liquor is 80-100 g/L H 2 SO 4 。
In the invention, zinc oxide and low copper white dust are treated by adopting the combination of neutral leaching, acid leaching and oxygen pressure leaching. The acid leaching solution obtained after leaching slag in acid leaching is used as a leaching agent for neutral leaching, and the initial acid concentration is 80-100 g/L sulfuric acid. This amount of sulfuric acid is sufficient to leach Zn, cu, fe, as from the zinc oxide and low copper white dust into solution.
However, if the initial acid concentration of the pickling solution is too low, the leaching agent is too low, so that the valuable metals in the neutral leaching slag are too much, and after acidic leaching, the valuable metals in the pickling slag are higher, namely the metal recovery rate is reduced.
If the starting acid concentration is too high, the leaching agent is excessive, so that the acidity in the immersion liquid is increased, and the consumption of iron powder is increased when the copper precipitation and dechlorination process is performed.
Preferably, the pH of the neutral leaching end point is controlled to be 1.0-1.5.
If the pH is less than 1, the acid content of the leaching solution is high at the moment, and the consumption of iron powder is increased when the copper precipitation and dechlorination process is carried out.
If the pH is greater than 1.5, the iron in the immersion liquid may be precipitated, which is disadvantageous for the subsequent arsenic removal process.
Preferably, the temperature is controlled to be 60-70 ℃ and the time is controlled to be 1-2 h in the neutral leaching process.
Too low temperature, too short time, low Cu and Zn leaching rate, too high temperature, no more improvement of leaching effect, and excessive energy consumption.
Preferably, the zinc oxide comprises the following main components in percentage by mass: 45-65% of Zn, 0-3% of Fe, 0.05-0.8% of As and 1-15% of Pb.
Preferably, the copper white smoke dust comprises the following main components in percentage by mass: 1.5 to 8 percent of Cu, 2 to 15 percent of Zn, 4.5 to 20 percent of As, 1 to 5 percent of Fe and 5 to 20 percent of Pb.
Preferably, in the step (1), the mass ratio of the zinc oxide to the copper white smoke is 1 (20% -50%).
The amount of white dust is small, on the one hand, the amount of copper white dust which can be treated is small, on the other hand, the iron source for precipitating arsenic in the immersion liquid is small, and after the iron powder copper precipitation and chlorine removal process, the iron content of the solution is still low, so that As in the solution cannot be completely removed by generating ferric arsenate. If the adding amount is too large, the arsenic content and copper content of the immersed solution are high, and for copper precipitation, the iron powder to be added is increased, and the adding amount exceeds the iron amount required by arsenic removal, so that only arsenic can be removed in the process of iron precipitation and arsenic removal, but the iron content of the solution after the arsenic removal of the precipitated iron is still high, and a large iron removal load is brought to the subsequent iron removal.
In addition, the grade of zinc oxide is reduced by adding white smoke dust, so that the zinc concentration in the leaching liquid is reduced, and the white smoke dust is not suitable to be added too much, so that the reduction of the zinc concentration in an original zinc system is avoided.
The highest proportion of the white smoke dust is about 50%, iron introduced by copper removal is replaced by iron powder mainly according to the Cu and As contents carried in the zinc oxide and copper white smoke dust, and the leached iron in the immersion liquid is combined with the As of the white smoke dust to generate ferric arsenate.
Preferably, in the step (2), the addition amount of the iron powder is 1.5 to 5 times the Cu content (mass) of the immersion liquid.
Preferably, in the step (2), the conditions of copper removal and dechlorination by adding iron powder are pH 1.0-1.5, the temperature is 70-80 ℃, and the reaction time is 3-4 hours.
The purpose of the step (2) is to deeply remove Cu and Cl contents in the leaching solution by adding a copper removing agent, namely iron powder.
Cu, as, zn, fe in zinc oxide and copper white smoke dust enters into solution in neutral leaching process, and Fe in the leaching solution is Fe 2+ As and Fe are therefore incapable of producing ferric arsenate precipitates. Then adding iron powder into the immersion liquid to perform copper precipitation and dechlorination, wherein the reaction (3) and the reaction (4) mainly occur in the process to obtain copper slag, and returning the copper slag to a copper pyrometallurgy system. The solution after copper precipitation and dechlorination contains a large amount of Fe 2+ And As. Since Fe powder can also react with acid in the copper precipitation dechlorination process, the pH value range of the immersion liquid needs to be controlled, and the pH value of the immersion liquid is ensured to be 1.0-1.5, so that the consumption of the Fe powder directly reacted with the acid is extremely low. And then, controlling the pH value, the temperature and the reaction time of the solution to remove copper and chlorine in the solution.
When the pH value of the medium immersion liquid is less than 1, the consumption of the reaction of the iron powder and the acid is too large, so that the addition of the iron powder is too large, the iron content in the solution is greater than the iron required by arsenic removal, the solution after arsenic removal by iron precipitation also needs further iron removal treatment, and when the pH value is greater than 1.5, the iron content in the medium immersion liquid can be reduced, and the subsequent arsenic removal effect is affected.
Too low temperature and time control result in poor removal effect, too high energy consumption and insignificant increase in removal effect.
Preferably, in the step (2), the concentration of the starting acid in the acid leaching process is controlled to be 220-240 g/L H 2 SO 4 。
When the concentration of the starting acid is too low, the leaching agent is insufficient to leach most of Zn and Cu in the intermediate leaching slag.
The excessive initial acid concentration causes the acid consumption to be increased, so that the final acid concentration in the pickling liquid is too high, and after the pickling liquid returns to neutral leaching, the initial acid in the process is too high, so that the control requirement of the pH value of the neutral leaching end point cannot be met, the final acid concentration of the pickling liquid is too high, and the consumption of iron powder is increased.
Preferably, in the step (2), the final acid concentration is controlled to be 80-100 g/L H in the acid leaching process 2 SO 4 。
This step is to control the final acid concentration, i.e. the acid concentration of the pickling solution. Since the pickling solution is used as a leaching agent for neutral leaching, the final acid concentration is actually the starting acid concentration of neutral leaching, and the influence of the high and low concentration control is the same as the reason for controlling the starting acid of neutral leaching in step (1).
Preferably, in the step (2), the temperature is controlled to be 80-90 ℃ and the time is controlled to be 5-6 h in the acid leaching process.
The temperature and the time are important factors influencing the acid leaching effect, the temperature is too low, the time is too short, the leaching rate is insufficient, the temperature is too high, the time is too long, and the leaching rate is not increased greatly.
Preferably, in the step (2), the acid refers to a waste electrolyte or a mixed solution of the waste electrolyte and sulfuric acid. The sulfuric acid addition is controlled according to the starting acid concentration.
Preferably, in the step (2), after the neutral leaching residue is added with the waste electrolyte and sulfuric acid for acidic leaching, the method further comprises: and (3) carrying out dense filtration on the product to obtain pickling liquid and pickling slag.
Preferably, the acid leaching slag is lead slag, and is sent for sale; the pickle liquor returns to neutral leaching. The returned pickle liquor can completely meet the requirement of the use amount of neutral leaching, and can realize countercurrent circulation in the mixed leaching process.
Preferably, in the step (3), oxygen with the concentration of 99% is introduced into the solution after copper precipitation and dechlorination.
The oxygen pressure leaching process requires a high oxygen potential, and the higher the oxygen concentration, the more favorable is for iron precipitation and arsenic removal.
Preferably, in the step (3), the temperature is controlled to be 145-155 ℃ and the pressure is controlled to be 1.0-1.2 Mpa in the arsenic removal process of the oxygen pressure iron, and the reaction time is 120-160 min.
This particular temperature, pressure, time range may be sufficient for arsenic to precipitate as ferric arsenate. The conditions of iron arsenate production are not met due to the fact that the temperature is too high, the pressure is too high and the reaction time is prolonged, the iron removal effect can be achieved only, and the As content is still high. Too low temperature, too low pressure and too short reaction time have less influence on the valence state of iron, and Fe is more Fe 2+ There is a difficulty in generating ferric arsenate precipitates.
Therefore, reasonable temperature, pressure and time parameters need to be controlled.
The invention is further explained as follows:
according to the invention, zinc oxide and low copper white smoke dust are mixed and leached, the middle leaching liquid adopts iron powder to replace copper precipitation, meanwhile, arsenic and chlorine in the solution are removed, most of arsenic is remained in the solution, ferric arsenate precipitation is formed by the iron which enters the solution through an autoclave, and the main chemical reaction principle is as follows:
ZnO+H 2 SO 4 →ZnSO 4 +H 2 O (1)
CuSO 4 (S)→Cu 2+ (aq)+SO 4 2- (aq) (2)
2Cu 2+ +2Cl - +nFe→Cu 2 Cl 2 ↓+nFe 2+ (3)
Cu 2+ +Fe→Cu↓+nFe 2+ (4)
2FeSO 4 +H 2 SO 4 +0.5O 2 →Fe 2 (SO 4 ) 3 +H 2 O (5)
Fe 2 (SO 4 ) 3 +(x+3)H 2 O→Fe 2 O 3 ·xH 2 O+3H 2 SO 4 (6)
2H 3 AsO 3 +O 2 →2H 3 AsO 4 (7)
H 3 AsO 4 +Fe(OH) 3 →FeAsO 4 ↓+3H 2 O (8)
in the invention, low copper white smoke dust is added in neutral leaching of zinc oxide, so the method has obvious influence on the treatment process, and is specifically characterized in that:
the zinc oxide contains less Cu and As, and after neutral leaching is carried out As a single raw material, the concentration of Cu and As in the leaching solution is low, and the pH value is usually controlled to be 5-5.4 in the working procedure, so that the zinc electrowinning requirement can be met only by carrying out the conventional iron removal and purification working procedure on the leaching solution. However, after zinc oxide is added into low copper white smoke dust, the content of Cu and As in the raw materials is high, and in order to reasonably utilize iron in the raw materials, neutral leaching final acid needs to be controlled to be pH 1-1.5. In the invention, the copper content in the copper white dust cannot be too high because the copper of the high copper white dust is greatly improved, cu 2+ Introducing too much into the immersion liquidThe amount of iron powder to be added is also increased sharply, and the effect of removing arsenic from the precipitated iron cannot be achieved. In addition, the conventional neutral leaching is neutral leaching-low acid leaching-high acid leaching, and the process is simplified only by neutral leaching-high acid leaching. The concentration of Cu and As in the immersion liquid is obviously higher than the capability range of Cu and As removal by conventional purification, so that the method skillfully adopts iron powder to precipitate copper and dechlorinate, then takes iron entering the solution As an iron source to remove arsenic in the solution after copper precipitation and dechlorination, and the generated ferric arsenate slag is subjected to innocent treatment by a pyrogenic process.
The invention has the advantages and technical effects that:
(1) The invention adopts zinc oxide and low copper white smoke dust mixed leaching, can reduce arsenic of the low copper white smoke dust to be taken away along with copper slag in the copper precipitation process, and most of arsenic is removed from oxygen pressure, thereby improving the copper-arsenic separation effect and being capable of treating the low copper white smoke dust by up to 50 percent. The leaching rate of zinc can reach more than 98%, the leaching rate of copper can reach more than 95%, and the arsenic removal effect can reach 99%.
(2) The iron powder is adopted to replace copper precipitation, and the iron ions entering the solution are utilized to remove arsenic, so that the process of removing arsenic by iron precipitation is completed in one autoclave.
(3) The ferric arsenate slag produced by the autoclave is sent to a rotary kiln of a conventional zinc leaching method for fire treatment together with zinc leaching slag, arsenic is solidified in the slag along with iron to be changed into harmless slag, the effect that the arsenic is solidified in the slag instead of being discharged by an arsenic product is achieved, and the harmless environmental protection problem of the arsenic is solved.
Drawings
FIG. 1 is a flow chart of the present invention.
Detailed Description
The present invention will be described in further detail by way of examples, but the scope of the present invention is not limited to the above.
Example 1
Mixing zinc oxide 9t (Zn 62%, fe 2%, as 0.5%, pb 10%) and low copper white smoke 4t (Zn 10%, fe 2%, cu 7%, as 15%, pb 12%) 13t, adding pickling solution to perform neutral leaching, controlling starting acid 80g/L, end point pH 1.4, temperature 60 ℃ for 1h, and obtaining the final productImmersion liquid 70m 3 (129 g/L of Zn, 2g/L of Fe, 3.5g/L of Cu, 8g/L of As and 0.4g/L of Cl), adding the produced intermediate leaching slag into waste electrolyte and sulfuric acid (volume ratio of 50:1) to perform acid leaching, controlling 220g/L of starting acid, 80g/L of final acid, and controlling the temperature to 80 ℃ for 5 hours, thereby producing 3.5t (Pb 39%, zinc leaching rate of 98.2% and copper leaching rate of 95.3%) of acid leaching slag. Copper precipitation and dechlorination are carried out on the immersion liquid, iron powder (2 times of Cu in the immersion liquid) is added, pH is controlled to be 1.4, the temperature is 70 ℃, the reaction time is 3 hours, copper slag is produced to be 0.37t (Cu 65%), and 70m of copper precipitation and dechlorination post-liquid is produced 3 (Zn 129g/L, fe 7g/L, cu 0.04g/L, as 7g/L and Cl 0.2 g/L) is fed into an autoclave for iron precipitation and arsenic removal, the temperature is controlled at 145 ℃, the pressure is 1.0Mpa, the reaction time is 120min, and 70m of solution after the iron precipitation and the arsenic removal is produced 3 (Zn 129g/L, fe 1g/L, cu 0.04g/L, as 0.04g/L, cl 0.2 g/L), ferric arsenate slag 1.62t, and arsenic removal efficiency 99.4%.
Comparative example 1
13t (62% Zn, 2% Fe, 0.5% As and 10% Pb) of zinc oxide is added into pickle liquor to carry out neutral leaching, the temperature is 60 ℃ and the time is 1h. 70m of medium-immersed liquid is produced 3 (pH 3.4, zn 160g/L, fe 0.8g/L, as 0.8g/L and Cl 0.4 g/L), adding the produced intermediate leaching residue into waste electrolyte to perform acid leaching, controlling the starting acid to 220g/L, controlling the final acid to 80g/L, and controlling the temperature to 80 ℃ for 5 hours to produce 2.8t (Pb 42% and zinc leaching rate to 98%) of acid leaching residue.
In this comparative example, the zinc leaching rate was not much different from that of example 1. Since all of the comparative examples used zinc oxide, in which the iron content in the immersion liquid was low and the zinc oxide was substantially free of copper, the iron powder copper precipitation dechlorination process was not required, and the As content was also low, and therefore, only the immersion liquid was sent to the subsequent deep purification and electrodeposition process. The same mass of zinc oxide consumed more acid than copper white dust, so the endpoint pH of the immersion liquid of comparative example 1 was higher and the iron concentration was lower.
Comparative example 2
Adding 13t (Zn 10%, fe 2%, cu 7%, as 15%, pb 12%) of copper white smoke dust into pickling solution for neutral leaching, controlling the initial acid to 80g/L, the end point pH to 1.0, the temperature to 60 ℃ for 1h, and obtaining the intermediate leaching solution 70m 3 (Zn 64g/L，Cu 11g/L，Fe 2g/L，As 24gAnd (3) adding the produced intermediate leaching residues into waste electrolyte to perform acid leaching, controlling the starting acid to be 220g/L, controlling the final acid to be 80g/L, controlling the temperature to be 80 ℃ and the time to be 5 hours, and producing 3.7t (Pb 37%, zinc leaching rate to be 98.4% and copper leaching rate to be 95.6%) of acid leaching residues. Copper precipitation and dechlorination are carried out on the immersion liquid, iron powder (2 times of Cu in the immersion liquid) is added, pH is controlled to be 1.4, the temperature is 70 ℃, the reaction time is 3 hours, copper slag is produced to be 1.20t (Cu 64%), and 70m of copper precipitation and dechlorination post-liquid is produced 3 (Zn 64g/L, fe 16g/L, cu 0.08g/L, as 22g/L and Cl 0.2 g/L) is fed into an autoclave for iron precipitation and arsenic removal, the temperature is controlled at 145 ℃, the pressure is 1.0Mpa, the reaction time is 120min, and 70m of solution after iron precipitation and arsenic removal is produced 3 (Zn 64g/L, fe 0.8g/L, cu 0.08g/L, as 5g/L, cl 0.2 g/L), iron arsenate slag 4.0t, and arsenic removal efficiency 77.3%.
In this comparative example, both the endpoint pH and Zn concentration of the resulting immersion liquid were lower than in example 1, due to the total use of copper white dust. The method is characterized in that the copper white smoke dust has low iron content and high arsenic content, after neutral leaching-iron powder copper precipitation dechlorination process, the copper precipitation dechlorination solution As is high, the iron content is still insufficient, and only part of arsenic can be removed when the subsequent oxygen pressure iron precipitation arsenic removal process is carried out, and the arsenic with higher concentration can not be removed.
Comparative example 3
Mixing zinc oxide 9t (Zn 62%, fe 2%, as 0.5%, pb 10%) and low copper white smoke 4t (Zn 10%, fe 2%, cu 7%, as 15%, pb 12%) 13t, adding pickling solution to perform neutral leaching, controlling initial acid 80g/L, end point pH 1.4, temperature 60 ℃ for 1h, and yielding intermediate leaching solution 70m 3 (129 g/L of Zn, 2g/L of Fe, 3.5g/L of Cu, 8g/L of As and 0.4g/L of Cl), adding the produced intermediate leaching slag into waste electrolyte and sulfuric acid to perform acid leaching, controlling the starting acid to 220g/L, controlling the final acid to 80g/L, and controlling the temperature to 80 ℃ for 5 hours to produce 3.5t (Pb 39%, zinc leaching rate to 98.2% and copper leaching rate to 95.3%) of acid leaching slag. Copper precipitation and dechlorination are carried out on the immersion liquid, iron powder (2 times of Cu in the immersion liquid) is added, pH is controlled to be 1.4, the temperature is 70 ℃, the reaction time is 3 hours, copper slag is produced to be 0.37t (Cu 65%), and 70m of copper precipitation and dechlorination post-liquid is produced 3 (Zn 129g/L, fe 7g/L, cu 0.04g/L, as 7g/L, cl 0.2 g/L) is fed into an autoclave for iron precipitation and arsenic removal, the temperature is controlled at 120 ℃, the pressure is controlled at 0.4Mpa, and the reaction time is 120min, 70m of solution after removing arsenic from precipitated iron is produced 3 (Zn 129g/L, fe 6.8g/L, cu 0.04g/L, as 6.9g/L, cl 0.2 g/L), ferric arsenate slag 0.01t, and arsenic removal efficiency 1.4%.
In this comparative example, the temperature in the iron precipitation and arsenic removal process is lower than that in example 1, and the effect of removing arsenic from the iron precipitation is substantially absent. The main reason is that Fe in the liquid after copper precipitation and dechlorination in the oxygen pressure iron precipitation and arsenic removal process is still ferrous iron (Fe) 2+ ) It is difficult to combine with As to form ferric arsenate, so that the arsenic removal effect is not obvious.
Comparative example 4
Mixing zinc oxide 9t (Zn 62%, fe 2%, as 0.5%, pb 10%) and low copper white smoke 4t (Zn 10%, fe 2%, cu 7%, as 15%, pb 12%) 13t, adding pickling solution to perform neutral leaching, controlling initial acid 80g/L, end point pH 1.4, temperature 60 ℃ for 1h, and yielding intermediate leaching solution 70m 3 (129 g/L of Zn, 2g/L of Fe, 3.5g/L of Cu, 8g/L of As and 0.4g/L of Cl), adding the produced intermediate leaching slag into waste electrolyte and sulfuric acid to perform acid leaching, controlling the starting acid to 220g/L, controlling the final acid to 80g/L, and controlling the temperature to 80 ℃ for 5 hours to produce 3.5t (Pb 39%, zinc leaching rate to 98.2% and copper leaching rate to 95.3%) of acid leaching slag. Copper precipitation and dechlorination are carried out on the immersion liquid, iron powder (2 times of Cu in the immersion liquid) is added, pH is controlled to be 1.4, the temperature is 70 ℃, the reaction time is 3 hours, copper slag is produced to be 0.37t (Cu 65%), and 70m of copper precipitation and dechlorination post-liquid is produced 3 (Zn 129g/L, fe 7g/L, cu 0.04g/L, as 7g/L and Cl 0.2 g/L) is fed into an autoclave for iron precipitation and arsenic removal, the temperature is controlled at 170 ℃, the pressure is 1.5Mpa, the reaction time is 120min, and 70m of solution after the iron precipitation and arsenic removal is produced 3 (Zn 129g/L, fe 2g/L, cu 0.04g/L, as 6.9g/L, cl 0.2 g/L), iron slag 0.70t, and arsenic removal efficiency 1.4%.
In this comparative example, the temperature and pressure in the iron precipitation and arsenic removal process were too high, but the iron precipitation effect was not achieved, as compared with example 1. The main reason is that Fe dissolved under the condition can form Fe in the process of removing arsenic from the solution after copper precipitation and dechlorination in the oxygen pressure iron precipitation 2 O 3 Enters a slag phase, namely iron is removed in the form of hematite, and the Fe cannot be combined with As to form ferric arsenate precipitate, so that the arsenic removal effect is poor.
Example 2
Zinc oxide is added9t (Zn 62%, fe 2%, as 0.5%, pb 10%) and low copper white smoke 4t (Zn 10%, fe 2%, cu 5%, as 17%, pb 12%) 13t, adding pickling solution to perform neutral leaching, controlling starting acid 90g/L, end point pH 1.2, temperature 70 ℃ for 1.5h, and yielding intermediate leaching solution 70m 3 (130 g/L of Zn, 2g/L of Fe, 2.7g/L of Cu, 9g/L of As and 0.4g/L of Cl), adding the produced intermediate leaching slag into waste electrolyte and sulfuric acid to perform acid leaching, controlling 230g/L of starting acid, 90g/L of final acid, and 90 ℃ for 5.5 hours, thereby producing 3.5t of acid leaching slag (Pb 39%, 98.3% of zinc leaching rate and 95.6% of copper leaching rate). Copper precipitation and dechlorination are carried out on the leaching solution, iron powder (3 times of copper in mass) is added, pH is controlled to be 1.2, the temperature is 80 ℃, the reaction time is 3.5 hours, copper slag is produced to be 0.3t, and 70m of copper precipitation and dechlorination solution is produced 3 (Zn 130g/L, fe 7g/L, cu 0.04g/L, as 8g/L and Cl 0.2 g/L) is fed into an autoclave for iron precipitation and arsenic removal, the temperature is controlled at 150 ℃, the pressure is 1.1Mpa, the reaction time is 140min, and 70m of solution after iron precipitation and arsenic removal is produced 3 (Zn 130g/L, fe 1g/L, cu 0.04g/L, as 0.05g/L, cl 0.2 g/L), ferric arsenate slag 1.68t, and arsenic removal efficiency 99.3%.
The method for removing arsenic from copper smelting smoke dust and recycling valuable metals provided by the invention is described in detail. The principles and embodiments of the present invention have been described herein with reference to specific examples, but the above examples are merely intended to aid in the organization of the methods and core concepts of the invention. It should be noted that it will be apparent to those skilled in the art that various modifications and adaptations of the invention can be made without departing from the principles of the invention and these modifications and adaptations are intended to be within the scope of the invention as defined in the following claims.
Claims (3)
1. The method for leaching zinc oxide and copper white smoke dust in a mixing way is characterized by comprising the following steps of:
(1) Mixing zinc oxide with copper white smoke dust, adding acid leaching solution, and performing neutral leaching to obtain neutral leaching solution and neutral leaching slag;
(2) Adding iron powder into the neutral leaching solution, carrying out copper precipitation and dechlorination, and filtering to obtain copper slag and copper precipitation and dechlorination liquid;
adding waste electrolyte and sulfuric acid into the intermediate leaching slag to perform acid leaching to obtain acid leaching slag and acid leaching liquid; returning the pickle liquor to neutral leaching;
(3) Introducing oxygen into the solution after copper precipitation and dechlorination to perform oxygen pressure iron precipitation and arsenic removal to obtain ferric arsenate slag and solution after iron precipitation and arsenic removal;
removing arsenic from the solution after iron precipitation, and delivering the solution to remove iron for purification, electrolysis and casting to produce electro-zinc; carrying out fire curing treatment on ferric arsenate slag;
the acid concentration of the pickle liquor is 80-100 g/L H 2 SO 4 The method comprises the steps of carrying out a first treatment on the surface of the Controlling the pH of the neutral leaching end point to be 1.0-1.5;
in the step (2), adding iron powder to remove copper and chlorine, wherein the pH value is 1.0-1.5, the temperature is 70-80 ℃, and the reaction time is 3-4 hours;
the zinc oxide comprises the following main components in percentage by mass: 45-65% of Zn, 0-3% of Fe, 0.05-0.8% of As and 1-15% of Pb; the copper white smoke dust comprises the following main components in percentage by mass: 1.5-8% of Cu, 2-15% of Zn, 4.5-20% of As, 1-5% of Fe and 5-20% of Pb;
in the step (1), the mass ratio of the zinc oxide to the copper white smoke dust is 1 (20% -50%);
in the step (2), the addition amount of the iron powder is 1.5-5 times of the mass of Cu;
in the step (3), the temperature is controlled to be 145-155 ℃ and the pressure is controlled to be 1.0-1.2 mpa in the process of removing arsenic in the oxygen pressure iron deposition process, and the reaction time is 120-160 min.
2. The method of claim 1, wherein in the step (2), the concentration of the starting acid is controlled to be 220-240 g/L H in the acid leaching process 2 SO 4 The method comprises the steps of carrying out a first treatment on the surface of the In the step (2), the temperature is controlled to be 80-90 ℃ and the time is controlled to be 5-6 hours in the acid leaching process.
3. The method of claim 1, wherein the acid leaching residue is lead residue and is sent for sale.
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