CN116397102A - Method for harmless recovery of copper and germanium from high-iron high-copper solution - Google Patents
Method for harmless recovery of copper and germanium from high-iron high-copper solution Download PDFInfo
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- CN116397102A CN116397102A CN202310353023.XA CN202310353023A CN116397102A CN 116397102 A CN116397102 A CN 116397102A CN 202310353023 A CN202310353023 A CN 202310353023A CN 116397102 A CN116397102 A CN 116397102A
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- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 title claims abstract description 329
- 239000010949 copper Substances 0.000 title claims abstract description 170
- 229910052802 copper Inorganic materials 0.000 title claims abstract description 168
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims abstract description 167
- 229910052742 iron Inorganic materials 0.000 title claims abstract description 166
- 229910052732 germanium Inorganic materials 0.000 title claims abstract description 163
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 title claims abstract description 163
- 238000000034 method Methods 0.000 title claims abstract description 72
- 238000011084 recovery Methods 0.000 title claims abstract description 36
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims abstract description 107
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 105
- 239000011701 zinc Substances 0.000 claims abstract description 105
- 239000002184 metal Substances 0.000 claims abstract description 86
- 229910052751 metal Inorganic materials 0.000 claims abstract description 86
- 239000002893 slag Substances 0.000 claims abstract description 85
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 50
- 238000002386 leaching Methods 0.000 claims abstract description 50
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical compound [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 claims abstract description 36
- 239000002253 acid Substances 0.000 claims abstract description 31
- 239000012141 concentrate Substances 0.000 claims abstract description 30
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 claims abstract description 27
- 238000009854 hydrometallurgy Methods 0.000 claims abstract description 19
- 150000002739 metals Chemical class 0.000 claims abstract description 18
- 229910052709 silver Inorganic materials 0.000 claims abstract description 14
- 239000004332 silver Substances 0.000 claims abstract description 14
- 239000002699 waste material Substances 0.000 claims abstract description 12
- 230000003472 neutralizing effect Effects 0.000 claims abstract description 11
- 239000007788 liquid Substances 0.000 claims description 80
- 238000006386 neutralization reaction Methods 0.000 claims description 43
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 35
- HSYFJDYGOJKZCL-UHFFFAOYSA-L zinc;sulfite Chemical compound [Zn+2].[O-]S([O-])=O HSYFJDYGOJKZCL-UHFFFAOYSA-L 0.000 claims description 35
- 238000001914 filtration Methods 0.000 claims description 34
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 claims description 26
- 229910052785 arsenic Inorganic materials 0.000 claims description 25
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 24
- 238000010438 heat treatment Methods 0.000 claims description 24
- 239000003638 chemical reducing agent Substances 0.000 claims description 22
- 230000003647 oxidation Effects 0.000 claims description 18
- 238000007254 oxidation reaction Methods 0.000 claims description 18
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 claims description 16
- 238000001556 precipitation Methods 0.000 claims description 15
- YBMRDBCBODYGJE-UHFFFAOYSA-N germanium dioxide Chemical compound O=[Ge]=O YBMRDBCBODYGJE-UHFFFAOYSA-N 0.000 claims description 14
- 238000003756 stirring Methods 0.000 claims description 14
- 238000001179 sorption measurement Methods 0.000 claims description 11
- 229910001111 Fine metal Inorganic materials 0.000 claims description 10
- 238000006243 chemical reaction Methods 0.000 claims description 9
- 229910001447 ferric ion Inorganic materials 0.000 claims description 9
- 238000004064 recycling Methods 0.000 claims description 9
- 230000001105 regulatory effect Effects 0.000 claims description 8
- 239000003513 alkali Substances 0.000 claims description 7
- 229940119177 germanium dioxide Drugs 0.000 claims description 7
- 230000001590 oxidative effect Effects 0.000 claims description 7
- 235000008733 Citrus aurantifolia Nutrition 0.000 claims description 6
- 235000011941 Tilia x europaea Nutrition 0.000 claims description 6
- 239000004571 lime Substances 0.000 claims description 6
- 238000007885 magnetic separation Methods 0.000 claims description 6
- 239000000463 material Substances 0.000 claims description 6
- 230000003311 flocculating effect Effects 0.000 claims description 5
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims description 5
- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical compound O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 claims description 5
- 239000003795 chemical substances by application Substances 0.000 claims description 4
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims description 2
- 239000003546 flue gas Substances 0.000 claims description 2
- 230000008021 deposition Effects 0.000 claims 2
- 238000000926 separation method Methods 0.000 abstract description 19
- 238000006722 reduction reaction Methods 0.000 abstract description 18
- 238000004519 manufacturing process Methods 0.000 abstract description 14
- 239000007787 solid Substances 0.000 abstract description 12
- 230000007935 neutral effect Effects 0.000 abstract description 11
- 230000001603 reducing effect Effects 0.000 abstract description 9
- LWUVWAREOOAHDW-UHFFFAOYSA-N lead silver Chemical compound [Ag].[Pb] LWUVWAREOOAHDW-UHFFFAOYSA-N 0.000 abstract description 5
- 238000006073 displacement reaction Methods 0.000 abstract description 4
- 239000002912 waste gas Substances 0.000 abstract description 2
- 239000002351 wastewater Substances 0.000 abstract description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 12
- 230000000694 effects Effects 0.000 description 9
- 238000005189 flocculation Methods 0.000 description 6
- 230000016615 flocculation Effects 0.000 description 6
- 239000011593 sulfur Substances 0.000 description 6
- 229910052717 sulfur Inorganic materials 0.000 description 6
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 5
- 229910052799 carbon Inorganic materials 0.000 description 5
- 239000007789 gas Substances 0.000 description 5
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical group [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 4
- 238000005868 electrolysis reaction Methods 0.000 description 4
- 230000035484 reaction time Effects 0.000 description 4
- 239000002002 slurry Substances 0.000 description 4
- 238000003723 Smelting Methods 0.000 description 3
- VETKVGYBAMGARK-UHFFFAOYSA-N arsanylidyneiron Chemical compound [As]#[Fe] VETKVGYBAMGARK-UHFFFAOYSA-N 0.000 description 3
- 238000004364 calculation method Methods 0.000 description 3
- 230000007613 environmental effect Effects 0.000 description 3
- 239000012535 impurity Substances 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- 239000003607 modifier Substances 0.000 description 3
- 231100000331 toxic Toxicity 0.000 description 3
- 230000002588 toxic effect Effects 0.000 description 3
- RBFQJDQYXXHULB-UHFFFAOYSA-N arsane Chemical compound [AsH3] RBFQJDQYXXHULB-UHFFFAOYSA-N 0.000 description 2
- 238000000151 deposition Methods 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- 239000013067 intermediate product Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 230000000630 rising effect Effects 0.000 description 2
- 159000000000 sodium salts Chemical class 0.000 description 2
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 description 2
- 238000009858 zinc metallurgy Methods 0.000 description 2
- 239000011787 zinc oxide Substances 0.000 description 2
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 1
- ONJMCYREMREKSA-UHFFFAOYSA-N [Cu].[Ge] Chemical compound [Cu].[Ge] ONJMCYREMREKSA-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000009977 dual effect Effects 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- MRZMQYCKIIJOSW-UHFFFAOYSA-N germanium zinc Chemical compound [Zn].[Ge] MRZMQYCKIIJOSW-UHFFFAOYSA-N 0.000 description 1
- 238000009856 non-ferrous metallurgy Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000000779 smoke Substances 0.000 description 1
- 235000010265 sodium sulphite Nutrition 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 229910001656 zinc mineral Inorganic materials 0.000 description 1
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Classifications
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B15/00—Obtaining copper
- C22B15/0063—Hydrometallurgy
- C22B15/0084—Treating solutions
- C22B15/0089—Treating solutions by chemical methods
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B03—SEPARATION OF SOLID MATERIALS USING LIQUIDS OR USING PNEUMATIC TABLES OR JIGS; MAGNETIC OR ELECTROSTATIC SEPARATION OF SOLID MATERIALS FROM SOLID MATERIALS OR FLUIDS; SEPARATION BY HIGH-VOLTAGE ELECTRIC FIELDS
- B03C—MAGNETIC OR ELECTROSTATIC SEPARATION OF SOLID MATERIALS FROM SOLID MATERIALS OR FLUIDS; SEPARATION BY HIGH-VOLTAGE ELECTRIC FIELDS
- B03C1/00—Magnetic separation
- B03C1/02—Magnetic separation acting directly on the substance being separated
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
- B22F1/14—Treatment of metallic powder
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F9/00—Making metallic powder or suspensions thereof
- B22F9/16—Making metallic powder or suspensions thereof using chemical processes
- B22F9/18—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds
- B22F9/24—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds starting from liquid metal compounds, e.g. solutions
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B15/00—Obtaining copper
- C22B15/0063—Hydrometallurgy
- C22B15/0084—Treating solutions
- C22B15/0089—Treating solutions by chemical methods
- C22B15/0091—Treating solutions by chemical methods by cementation
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B41/00—Obtaining germanium
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
- C22B7/006—Wet processes
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
Abstract
The invention discloses a method for harmless recovery of copper and germanium from a high-iron high-copper solution, which comprises the following steps: the slag of the primary neutral leaching of the zinc hydrometallurgy zinc roasting ore is subjected to secondary low-acid leaching, the slag of the secondary low-acid leaching liquid-solid separation is subjected to tertiary high-temperature high-acid leaching to recover valuable metals zinc, copper and germanium, lead-silver concentrate is produced and sold to lead and silver, and the liquor after the tertiary high-temperature high-acid leaching contains sulfuric acid, iron, copper, zinc and germanium, the iron is mainly ferric iron, and the solution is a high-iron and high-copper solution. The invention is completed by one step of neutralizing acid and reducing ferric iron, realizes the selective reduction, displacement and separation of copper and germanium, and has high recovery rate of valuable metals and low cost. No new waste water, waste gas and waste residue are generated in the process, and green production can be realized.
Description
Technical Field
The invention belongs to the technical field of nonferrous metallurgy, and particularly relates to a method for harmless recovery of copper and germanium from a high-iron and high-copper solution.
Background
Along with continuous impoverishment of zinc mineral resources and continuous rising of zinc smelting raw materials and auxiliary materials, national environmental awareness is continuously improved, waste residues immersed in zinc hydrometallurgy are required to be reduced and discharged, and comprehensive recovery rate of valuable metals in the residues is required to be continuously improved.
Zinc hydrometallurgy is carried out, zinc roasting ore is subjected to primary sulfuric acid neutral leaching, secondary low leaching is carried out on neutral leaching slag, and then neutralization and filtration are carried out. In addition, due to the continuous rising of the coal price in recent years, the secondary slag is sent to a volatilizing kiln to volatilize, so that the production cost is higher, the energy consumption is high, and the environmental protection pressure is high. Therefore, the secondary slag needs to be leached at high temperature and high acid to realize slag reduction treatment, lead-silver concentrate and high-iron high-copper solution are produced, the lead-silver concentrate mainly contains lead and silver for sale, the high-iron high-copper solution mainly contains high iron, high copper, germanium and zinc, and iron is mainly ferric iron, and if the high-iron high-copper solution is returned to primary neutral leaching to be used as slurry, valuable metal loss and liquid-solid separation difficulty after primary neutral leaching are caused, and the production flow is blocked. Therefore, the method is an important link for restricting the innovative development of the wet zinc smelting industry.
Taking zinc hydrometallurgy of Yunnan corporation as an example, the high-iron and high-copper solution mainly contains 20-26 g/L of total iron, 19-25 g/L of ferric iron, 0.3-1.5 g/L of copper, 0.020-0.04 g/L of germanium, 40-60 g/L of zinc, 20-40 g/L of sulfuric acid and 0.01-0.5 g/L of arsenic.
The problems currently existing include:
(1) Returning the high-iron high-copper solution to the primary neutral leaching to prepare slurry, thereby causing valuable metal loss and difficulty in liquid-solid separation after the primary neutral leaching, and causing the production flow to be blocked;
(2) The high-iron and high-copper solution is neutralized for iron removal, then copper, germanium and zinc are recovered, the neutralization slag amount is large, the cost is high, and the recovery rate of valuable metals is low;
(3) The high-iron high-copper solution mainly contains high ferric iron, and the conventional redox method for recovering copper and germanium is adopted, so that the consumption of a reducing agent is high, the cost is high, the grade of copper and germanium in the produced copper-germanium slag is low, and the next step of recovering the copper and germanium in the valuable metal is difficult and the cost is high.
The following methods are mainly used for treating the high-iron and high-copper solution at present:
1. the conventional treatment of the high-iron high-copper solution is to return to one-time neutral leaching to prepare slurry;
2. chinese patent CN102031371a discloses a method for enriching germanium from zinc hydrometallurgy system, which adopts the following technical scheme: (1) The neutralizing agent is zinc oxide calcine, zinc oxide smoke dust, iron powder, zinc suboxide and scrap iron. (2) The ferric ion reducing agent is zinc powder, zinc suboxide, sodium sulfite, iron powder and SO 2 Or iron filings, depending on the amount of ferric ions in the solution, a small excess may be used. (3) The substituting agent of germanium is zinc powder, zinc sheet, iron powder or iron filings. (4) replacing to produce germanium slag;
3. chinese patent CN106834693a discloses a wet comprehensive recycling method for zinc metallurgy displacement slag, which adopts extraction separation to recycle copper;
4. chinese patent CN110093506a discloses a method for efficiently extracting and reducing valuable metals in germanium-containing zinc leaching residues, which adopts the following technical scheme: (1) the reducing agent for ferric ions is germanium zinc concentrate; (2) The reducing agent for replacing valuable metals copper and germanium is iron powder, and the addition amount of the iron powder is 0.5-5 times of the mass of ferric iron metal in the pre-neutralized liquid, 0.9-1.3 times of the mass of copper metal in the pre-neutralized liquid and 10-30 times of the mass of germanium metal in the pre-neutralized liquid; and (3) replacing to obtain germanium-precipitating copper slag.
In a word, the existing treatment method for the wet zinc smelting high-iron high-copper solution has high treatment cost, low recovery rate of valuable metal copper and germanium grade, and the use of sodium salt as a reducing agent can bring impurity harm to a zinc production system, and the use of the metal zinc reducing agent can generate toxic and harmful gas, so that the method is difficult to be applied to actual production. Therefore, no good and practical method for treating the high-iron and high-copper solution in the zinc hydrometallurgy process exists at present, and aiming at the problems, a method for harmless recovery of copper and germanium in the high-iron and high-copper solution is required to be invented.
Disclosure of Invention
The present invention aims to overcome the following drawbacks and/or disadvantages of the prior art:
(1) Returning the high-iron high-copper solution to the primary neutral leaching to prepare slurry, so that valuable metal is lost, and liquid-solid separation is difficult after the primary neutral leaching, so that the production flow is blocked;
(2) The use of the sodium salt as a reducing agent brings impurity hazard to a zinc production system;
(3) The use of metallic zinc as a reducing agent can produce toxic and harmful gas arsine gas;
(4) The extraction method is adopted, so that a great amount of organic matters with people bring great harm to zinc electrolysis;
(5) The method for reducing the ferric iron by adopting the negative divalent sulfur in the germanium-containing zinc concentrate causes sulfur loss, and the larger the mass ratio of the divalent sulfur in the germanium-containing zinc concentrate to iron in the material is, the larger the consumption of the germanium-containing zinc concentrate is, the larger the sulfur loss is, the larger the lead-silver-sulfur slag is, and the higher the valuable metal lead-silver depletion rate is. On the contrary, the mass ratio of the divalent sulfur in the germanium-containing zinc concentrate to the iron in the material is smaller, the reduction of the trivalent iron is incomplete, a large amount of reducing agent is consumed in the next process of reducing copper, the production cost is high, the economy is poor, the amount of waste residues is large, and the recycling, reduction and harmless treatment of the residues are difficult to realize;
(6) The germanium is replaced by iron powder, the consumption of the iron powder is 10-30 times of the total mass of germanium metal in the pre-neutralized liquid, the iron powder consumes a large amount of iron slag, and a large amount of iron slag is generated during the iron treatment in the next process, so that the production cost is high, the economy is high, and the purpose of reducing the slag is not achieved.
In order to overcome the defects and/or shortcomings, the invention provides a novel method for harmless recovery of copper and germanium from a high-iron high-copper solution, which is used for solving the problem of harmless recovery of copper and germanium due to high ferric iron, high copper and high zinc in the high-iron high-copper solution in the zinc hydrometallurgy process.
The method is realized as follows: the slag of the primary neutral leaching of the zinc hydrometallurgy zinc roasting ore is subjected to secondary low-acid leaching, the slag of the secondary low-acid leaching liquid-solid separation is subjected to tertiary high-temperature high-acid leaching to recover valuable metals zinc, copper and germanium, lead-silver concentrate is produced and sold to lead and silver, and the liquor after the tertiary high-temperature high-acid leaching contains sulfuric acid, iron, copper, zinc and germanium, the iron is mainly ferric iron, and the solution is a high-iron and high-copper solution. The method specifically comprises the following steps:
(1) The method adopts intermediate product zinc sulfite slag generated in the zinc hydrometallurgy production process as a neutralizing agent and a reducing agent. Zinc sulfite slag is added into a high-iron and high-copper solution to neutralize acid and reduce high-valence iron, and when the pH value of the acidity of the neutralized solution is 1.5-2.0 and the content of ferric ions is below 0.2 g/L, liquid-solid separation is carried out to obtain neutralized slag and neutralized solution. The neutralized slag is returned to the secondary low-acid leaching slag and then subjected to three times of high-temperature high-acid leaching to recover valuable metals, and the neutralized liquid contains zinc, copper, germanium and ferrous iron;
(2) And (3) separating copper and germanium by selective reduction and replacement of the neutralized liquid. Adding a reducing agent metal iron powder into the neutralized solution to replace copper, and obtaining coarse metal copper powder and replaced solution after liquid-solid separation. The crude metal copper powder also contains metal iron powder, and the crude metal copper powder is purified by adopting a method of absorbing the iron powder by a magnet, so that the grade of the crude metal copper powder is improved. The liquid after displacement contains zinc and germanium, and is sent to a neutralization adsorption flocculation germanium recovery system;
(3) And (3) neutralizing, adsorbing and flocculating the replaced liquid to recover germanium, heating to a temperature of between 60 and 70 ℃ until the pH value of the replaced liquid is between 2.0 and 2.5, regulating the pH value of the acidity to between 3.0 and 4.0 by using a neutralizer sodium hydroxide, adding activated carbon, stirring for 1.0 to 2.0 hours, separating liquid from solid to obtain a germanium-precipitated liquid and germanium concentrate, delivering the germanium concentrate to a germanium recovery system to produce germanium dioxide, oxidizing and removing iron from the germanium-precipitated liquid by air, and delivering the iron-removed liquid to a roasting ore leaching system to recover zinc. The application of the method can realize the purpose of harmless recovery of copper and germanium in the whole process of the high-iron high-copper solution in the zinc hydrometallurgy industry, and creatively searches a process trend for the high-iron high-copper solution in the zinc hydrometallurgy industry; the application of the method can provide a subsequent technical support for recycling, reducing and harmless treatment of the zinc-containing leaching slag.
The method is realized by the following steps:
1) Neutralization reduction of high-valence iron: heating the high-iron high-copper solution to 60-70 ℃, slowly adding zinc sulfite slag, recovering sulfuric acid by a sulfuric acid delivering system for releasing sulfur dioxide in the process, controlling the charging time to be 1.0-1.5 hours, filtering I when the terminal pH=1.5-2.0 and the ferric ion content is below 0.2 g/L, filtering I to obtain No. 1 neutralization slag and No. 1 neutralization solution, and merging the No. 1 neutralization slag into secondary low-acid leaching slag of a leaching workshop, and then carrying out three times of high-temperature high-acid leaching to recover valuable metals;
2) And (3) separating copper and germanium by selective reduction replacement of the neutralized solution: heating the neutralized solution 1 to 40-60 ℃, slowly adding a reducing agent metal iron powder to replace copper, wherein the addition amount of the iron powder is 0.9-1.1 times of the mass of copper metal in the neutralized solution, filtering II after the reaction time is 0.5-1.0 hours, and filtering II to obtain coarse copper powder 2 and replaced solution 2. The liquid after the replacement of the No. 2 is sent to neutralize, absorb and flocculate to recycle germanium;
3) Magnetic separation of crude copper powder: and recovering the metal iron powder from the No. 2 crude metal copper powder by adopting a magnet adsorption method to improve the grade of the crude metal copper powder, and separating to obtain the No. 3 metal iron powder and the No. 3 fine metal copper powder. The No. 3 metal iron powder is returned to the copper replacement process for reuse, and the No. 3 refined metal copper powder is sold;
4) Neutralizing, adsorbing and flocculating to recover germanium by using the replaced liquid alkali, heating to raise the pH value of the replaced liquid to between 2.0 and 2.5, heating to between 60 and 70 ℃, regulating the pH value of the acidity to between 3.0 and 4.0 by using a neutralizer sodium hydroxide, adding active carbon with the addition of 0.1 to 0.5 gram of the active carbon per liter of the replaced liquid, stirring for 1.0 to 2.0 hours, filtering III to obtain a germanium-precipitating liquid No. 3 and germanium concentrate No. 4, feeding the germanium concentrate No. 4 into a germanium recovery system to produce germanium dioxide, oxidizing and removing iron from the germanium-precipitating liquid No. 3 by using air, and recovering iron;
5) Air oxidation and iron removal are carried out on the solution after germanium precipitation, heating and heating are carried out on the solution after germanium precipitation No. 3, when the temperature is raised to 85-90 ℃, compressed air ferric oxide is introduced, after the oxidation time is 1.0-1.5 hours, lime is added for neutralization and iron removal, the pH value of a neutralization end point is=2.5-3.0, stirring is continued for 0.5-1.0 hour, IV is filtered, and the solution after air oxidation of No. 4 and iron slag No. 5 are obtained through IV filtration. No. 5 iron slag is sold to achieve the aim of opening an iron circuit, and the liquid after No. 4 air oxidation is sent to a roasting ore leaching system to recover zinc.
Preferably:
the zinc sulfite slag in the step (1) is waste slag generated by zinc hydrometallurgy, and is a product generated by absorbing sulfur dioxide in the flue gas of a volatilizing kiln by adopting zinc-containing materials in the volatilizing kiln to recover valuable metals, wherein the zinc-containing materials mainly contain 25-40 wt% of zinc, 20-35 wt% of zinc sulfite, 1.0-4.0 wt% of iron, 0.02-0.04 wt% of germanium, 2.0-4.0 wt% of lead, 0.001-0.006 wt% of silver and 0.2-1.0 wt% of copper;
in the step (1), the high-iron and high-copper solution mainly contains 20-26 g/L of total iron, 19-25 g/L of ferric iron, 1.0-3.0 g/L of copper, 0.020-0.040 g/L of germanium, 40-60 g/L of zinc, 20-40 g/L of sulfuric acid and 0.01-0.5 g/L of arsenic;
in the step (1), the No. 1 neutralization slag mainly contains 5.0 to 13 weight percent of zinc, 1.0 to 4.5 weight percent of iron, 0.005 to 0.015 weight percent of germanium, 4.0 to 10.0 weight percent of lead, 0.002 to 0.02 weight percent of silver and 0.1 to 0.3 weight percent of copper;
in the step (1), the neutralized solution of No. 1 mainly contains 20-28 g/L of total iron, 0.01-0.2 g/L of ferric iron, 1.0-4.0 g/L of copper, 0.060-0.090 g/L of germanium and 70-120 g/L of zinc;
in the step (2), the liquid after the replacement of the No. 2 mainly contains 21 to 32 g/L of total iron, 0.01 to 0.10 g/L of ferric iron, 0.05 to 0.25 g/L of copper, 0.040 to 0.090 g/L of germanium and 70 to 120 g/L of zinc;
in the step (3), the No. 3 fine metal copper powder contains 75 to 85 percent of copper;
in the step (4), the germanium concentrate No. 4 contains 1.0-3.0% of germanium, 5.0-15% of zinc and 50-70% of iron;
in the step (5), the iron slag No. 5 contains 60-70% of iron, 0.5-5.0% of zinc and 0.1-0.4% of arsenic.
The invention is researched and found in experiments:
(1) The active carbon not only improves slag property and facilitates liquid-solid separation, but also has the double effects of assisting iron flocculation and germanium adsorption;
(2) When the addition amount of the reducing agent iron powder is controlled to be only 0.8 to 1.1 times of the mass of copper metal in the neutralized liquid and the acidity pH value is controlled to be 1.5 to 2.5, the selective reduction, replacement and separation of copper and germanium can be realized;
(3) The metal iron powder is used as the reducing agent, so that no toxic and harmful gas arsine gas is generated.
The mechanism of the invention mainly comprises:
(1) The zinc sulfite reacts with sulfuric acid to neutralize sulfuric acid, and the reaction of the zinc sulfite and sulfuric acid is utilized;
ion reaction formula: SO (SO) 3 2- +2H + →SO 2 ↑+H 2 O
(2) Zinc sulfite and ferric iron are subjected to a reduction reaction, and zinc sulfite has a reducing effect;
ion reaction formula: SO (SO) 3 2- +2Fe 3+ →SO 4 2- +2Fe 2+
(3) The substitution reaction of the metallic iron powder and the bivalent copper utilizes the reducibility of the iron powder and the oxidability of the bivalent copper.
Ion reaction formula: fe+Cu 2+ →Fe 2+ +Cu↓。
The beneficial effects of the invention include:
(1) The active carbon is adopted as the slag modifier, so that not only the performance of slag is improved and the liquid-solid separation is easy, but also the dual effects of assisting iron, flocculating and adsorbing germanium are achieved;
(2) Realize the selective reduction displacement separation of copper and germanium, and has high recovery rate of valuable metals and low cost;
(3) The method for improving the grade of the crude metal copper powder by adopting the magnet to adsorb and recycle the metal iron powder has high iron powder utilization rate and low cost, and the grade of the product of the refined metal copper powder is 75-85 percent higher than copper;
(4) The germanium is recovered by adopting an alkali neutralization adsorption flocculation method, so that the method is free of human and organic matters, simple in process and easy to operate;
(5) The method realizes the creative realization of a flow trend for the high-iron high-copper solution in the wet zinc metallurgy industry;
(6) The method solves the problems that secondary slag cannot be leached at high temperature and high acid in the zinc hydrometallurgy production process for a long time, and only can be sent to a volatilizing kiln for volatilizing and recovering valuable metals;
(7) The method is completed by one step of neutralizing acid and reducing ferric iron, so that the flow can be shortened, and the cost can be reduced;
(8) The reducing agent of the method is zinc sulfite, zinc in the zinc sulfite is main element of zinc hydrometallurgy, and the addition of the reducing agent does not bring impurities to a system;
(9) The zinc sulfite slag of the method is an intermediate product of zinc hydrometallurgy, zinc sulfite in the zinc sulfite slag is used as a reducing agent, the cost is not increased, and the method is economical and efficient;
(10) The method realizes harmless recovery of copper and germanium in a zinc hydrometallurgy system under the condition of high iron and high copper solution and high ferric iron;
(11) The method does not need new equipment, is simple and convenient to operate, has low investment cost and production cost, and is a method for harmless recovery of copper and germanium in the high-iron and high-copper solution with better industrialization prospect;
(12) The method does not generate new waste water, waste gas and waste residue any more, has beautiful operation environment, can realize green production, and meets the requirements of national environmental protection, comprehensive recycling of limited resources and sustainable development.
Drawings
FIG. 1 is a process flow diagram of a method for the harmless recovery of copper and germanium from a high-iron and high-copper solution according to the present invention.
Detailed Description
Taking zinc hydrometallurgy of Yunnan corporation as an example: the high-iron and high-copper solution mainly contains 20-26 g/L of total iron, 19-25 g/L of ferric iron, 1-3 g/L of copper, 0.020-0.04 g/L of germanium, 40-60 g/L of zinc, 20-40 g/L of sulfuric acid and 0.01-0.5 g/L of arsenic; the zinc sulfite slag comprises the following main components: 25 to 40 weight percent of zinc, 20 to 35 weight percent of zinc sulfite, 1.0 to 4.0 weight percent of iron, 0.02 to 0.04 weight percent of germanium, 2.0 to 4.0 weight percent of lead, 0.001 to 0.006 weight percent of silver and 0.2 to 1.0 weight percent of copper.
The method of the invention can be realized by the following steps:
(1) Adding zinc sulfite slag into the high-iron and high-copper solution produced in a zinc hydrometallurgy roasting ore leaching workshop, neutralizing sulfuric acid, reducing ferric iron, and delivering sulfur dioxide released in the reaction process to a sulfuric acid system for recycling to prepare acid. The filtered neutralization slag is merged into secondary low-acid leaching slag in a leaching workshop, and then three times of high-temperature high-acid leaching are carried out to recover valuable metals, and copper and germanium are separated by selective reduction and replacement of the neutralization liquid;
(2) And (3) separating copper and germanium by selective reduction replacement of the neutralized solution: slowly adding a reducing agent metal iron powder into the neutralized solution to replace copper, and filtering to obtain coarse metal copper powder and replaced solution;
(3) Magnetic separation of crude copper powder: the crude metal copper powder is recovered by adopting a magnet adsorption method to recover the metal iron powder, so that the grade of the crude metal copper powder is improved, and the metal iron powder and the refined metal copper powder are obtained through separation. The metallic iron powder is returned to the copper replacement process for reuse, and the refined metallic copper powder is sold.
(4) And (3) neutralizing, adsorbing and flocculating the replaced liquid alkali to recover germanium: heating the replaced liquid, regulating the acidity pH value to 3.0-4.0 by using a neutralizer sodium hydroxide, adding active carbon, stirring for 1.0-2.0 hours, filtering to obtain a germanium-precipitating liquid and germanium concentrate, delivering the germanium concentrate to a germanium recovery system to produce germanium dioxide, oxidizing the germanium-precipitating liquid with air to remove iron, and recovering iron.
(5) Liquid air oxidation deironing after germanium precipitation: heating the germanium-precipitating solution, introducing compressed air to oxidize iron for 1.0-1.5 hours, adding lime to neutralize and remove iron, stirring for 0.5-1.0 hour at the neutralization end point pH=2.5-3.0, and filtering to obtain air oxidized solution and iron slag. And (3) selling iron slag, and delivering the air oxidized solution to a roasting ore leaching system to recover zinc.
Example 1
10000 g of zinc sulfite residue produced by a certain company in Yunnan is taken and dried for standby, wherein the zinc sulfite residue contains 7.5 wt% of water, 24.5wt% of zinc, 20.1wt% of zinc sulfite, 1.8wt% of iron, 0.029wt% of germanium, 2.6wt% of lead, 0.0035wt% of silver and 0.8wt% of copper; (2) 30 liters of high-iron high-copper solution mainly containing 22 g/liter of total iron, 20 g/liter of ferric iron, 1.5 g/liter of copper, 0.03 g/liter of germanium, 45 g/liter of zinc, 25 g/liter of sulfuric acid and 0.05 g/liter of arsenic; (3) 10 liters of an electrolytic waste liquid containing 42 g/liter of zinc and 143 g/liter of sulfuric acid.
1) Neutralization reduction of high-valence iron: 30 liters of high-iron and high-copper solution is taken, heated to 60-70 ℃, zinc sulfite slag is slowly added, sulfuric acid is recycled by a sulfuric acid feeding system for sulfur dioxide released in the process, the feeding time is controlled to be 1.0-1.5 hours, the pH value of the reaction process can be controlled to be 1.5-2.0 by using electrolytic waste liquid to adjust acidity, filtering I is carried out when the content of ferric ions is ensured to be less than 0.2 g/liter, 5650 g of zinc sulfite slag is shared, 2805 g of No. 1 neutralization slag and 28.2 liters of No. 1 neutralization liquid are obtained after the No. 1 neutralization slag is filtered, the water content of No. 1 neutralization slag is 17.3wt%, zinc is 12.3wt%, iron is 1.2wt%, germanium is 0.0110wt%, lead is 6.3wt%, silver is 0, 0085wt% and copper is 0.19wt%. The neutralized liquid of No. 1 contained 26.0 g/liter of total iron, 0.05 g/liter of trivalent iron, 3.04 g/liter of copper, 0.081 g/liter of germanium, 86.8 g/liter of zinc, and 0.06 g/liter of arsenic. And (3) merging the No. 1 neutralization slag into secondary low-acid leaching slag in a leaching workshop, and then carrying out three times of high-temperature high-acid leaching to recover valuable metals.
2) And (3) separating copper and germanium by selective reduction replacement of the neutralized solution: taking 27 liters of neutralized solution 1, heating to 40-60 ℃, slowly adding 74 grams of reducer metal iron powder to replace copper, wherein the addition amount of the iron powder is 0.9 times of the mass of copper metal in the neutralized solution, filtering II after the reaction time is 0.5-1.0 hour, and obtaining 109 grams of coarse metal copper powder 2 and 27 liters of replaced solution 2 by filtering II. The No. 2 crude copper powder contains 73.4wt% of copper and 6.4wt% of iron, and the No. 2 replaced liquid contains 28.4 g/L of total iron, 0.04 g/L of ferric iron, 0.08 g/L of copper, 0.080 g/L of germanium, 85.5 g/L of zinc and 0.06 g/L of arsenic. And (2) delivering the liquid after the replacement to neutralize, absorb and flocculate to recycle germanium.
3) Magnetic separation of crude copper powder: 100 g of No. 2 coarse metal copper powder is taken, the grade of the coarse metal copper powder is improved by adopting magnet to adsorb and recycle the metal iron powder, and 6 g of No. 3 metal iron powder and 94 g of No. 3 fine metal copper powder are obtained through separation. The No. 3 metal iron powder is returned to the copper replacement process for reuse, and the No. 3 fine metal copper powder contains 78.1 weight percent of copper and is sold.
4) And (3) carrying out neutralization adsorption flocculation on the replaced liquid alkali to recover germanium, taking 26 liters of the replaced liquid No. 2, heating to 60-70 ℃, regulating the acidity pH value to 3.0-4.0 by using a neutralizer sodium hydroxide, adding 2.6 g of activated carbon, adding 0.1 g of activated carbon into each liter of replaced liquid, stirring for 1.0-2.0 hours, filtering III to obtain 25.5 liters of the germanium-precipitating liquid No. 3 and 152 g of germanium concentrate No. 4, wherein the germanium concentrate No. 4 mainly contains 15.0wt% of water, 8.3wt% of zinc, 1.5wt% of germanium and 65.3wt% of iron, and the germanium-precipitating liquid No. 3 mainly contains 25.1 g/liter of total iron, 0.05 g/liter of copper, 0.004 g/liter of germanium and 85.1 g/liter of zinc and 0.05 g/liter of arsenic. Germanium concentrate No. 4 is sent to a germanium recovery system to produce germanium dioxide, and liquid air is oxidized to remove iron after germanium precipitation No. 3 to recover iron.
5) Liquid air oxidation deironing after germanium precipitation: and (3) taking 25 liters of solution after germanium precipitation No. 3, heating to 85-90 ℃, introducing compressed air ferric oxide, oxidizing for 1.0-1.5 hours, adding lime to neutralize and remove iron, continuously stirring for 0.5-1.0 hour at the neutralization end point pH=2.5-3.0, filtering IV, and filtering IV to obtain 24.6 liters of solution after air oxidation No. 4 and 900 g of iron slag No. 5. The No. 5 iron slag mainly contains 25 weight percent of water, 65 weight percent of iron, 2.3 weight percent of zinc and 0.17 weight percent of arsenic, and the No. 4 air oxidized liquid mainly contains 7.7 g/L of total iron, 0.04 g/L of copper, 85.8 g/L of zinc and 0.004 g/L of arsenic. The No. 5 iron slag is sold to achieve the aim of opening an iron-arsenic circuit, and the liquid after No. 4 air oxidation is sent to a roasting ore leaching system to recycle zinc.
In this embodiment, each technical economic index is obtained by calculation as follows:
1. the direct yield of germanium is 85.5%;
2. the copper direct yield is 90.3%.
Example 2
10000 g of zinc sulfite residue produced by a certain company in Yunnan is taken and dried for standby, wherein the zinc sulfite residue contains 7.0 percent of water, 29.1 percent of zinc, 27.6 percent of zinc sulfite, 2.3 percent of iron, 0.034 percent of germanium, 3.4 percent of lead, 0.0048 percent of silver and 0.75 percent of copper; (2) 30 liters of high-iron high-copper solution mainly containing 24 g/liter of total iron, 23 g/liter of ferric iron, 2.2 g/liter of copper, 0.032 g/liter of germanium, 49 g/liter of zinc, 31 g/liter of sulfuric acid and 0.06 g/liter of arsenic; (3) 10 liters of an electrolytic waste liquid containing 43 g/liter of zinc and 145 g/liter of sulfuric acid.
1) Neutralization reduction of high-valence iron: 30 liters of high-iron and high-copper solution is taken, heated to 60-70 ℃, zinc sulfite slag is slowly added, sulfur dioxide released in the process is sent to a sulfuric acid system for recycling to prepare acid, the feeding time is controlled to be 1.0-1.5 hours, the pH value of the reaction process can be controlled to be 1.5-2.0 by using electrolysis waste liquid to adjust acidity, filtering I is carried out when the content of ferric ions is ensured to be less than 0.2 g/liter, 5600 g of zinc sulfite slag is shared, 2782 g of No. 1 neutralization slag and 27.6 liters of No. 1 neutralization liquid are obtained after No. 1 neutralization, the water content of No. 1 neutralization slag is 17.1wt%, 10.5wt% of zinc, 4.1wt% of iron, 0.008wt% of germanium, 7.6wt% of lead, 0.0108 wt% of silver and 0.12wt% of copper. The neutralized liquid of No. 1 contained 27.0 g/liter of total iron, 0.05 g/liter of trivalent iron, 3.7 g/liter of copper, 0.092 g/liter of germanium, 99.4 g/liter of zinc, and 0.05 g/liter of arsenic. And (3) merging the No. 1 neutralization slag into secondary low-acid leaching slag in a leaching workshop, and then carrying out three times of high-temperature high-acid leaching to recover valuable metals.
2) And (3) separating copper and germanium by selective reduction replacement of the neutralized solution: taking 27 liters of the neutralized solution 1, heating to 40-60 ℃, slowly adding 100 grams of reducer metal iron powder to replace copper, wherein the addition amount of the iron powder is 1.0 time of the mass of copper metal in the neutralized solution, filtering II after the reaction time is 0.5-1.0 hour, and obtaining 123 grams of coarse metal copper powder 2 and 27 liters of the replaced solution 2 by filtering II. Copper 78.8wt% and iron 8.8wt% of No. 2 crude copper powder, and the No. 2 replaced liquid contains 30.7 g/L of total iron, 0.03 g/L of ferric iron, 0.11 g/L of copper, 0.091 g/L of germanium, 98.7 g/L of zinc and 0.05 g/L of arsenic. And (2) delivering the liquid after the replacement to neutralize, absorb and flocculate to recycle germanium.
3) Magnetic separation of crude copper powder: 110 g of No. 2 coarse metal copper powder is taken, the metal iron powder is recovered by magnet adsorption to improve the grade of the coarse metal copper powder, and 7 g of No. 3 metal iron powder and 103 g of No. 3 fine metal copper powder are obtained by separation. The No. 3 metal iron powder is returned to the copper replacement process for reuse, and the No. 3 fine metal copper powder contains 84.1 weight percent of copper and is sold.
4) And (3) carrying out neutralization adsorption flocculation on the replaced liquid alkali to recover germanium, taking 26 liters of the replaced liquid No. 2, heating to 60-70 ℃, regulating the acidity pH value to 3.0-4.0 by using a neutralizer sodium hydroxide, adding 5.2 g of activated carbon, adding 0.2 g of activated carbon into each liter of replaced liquid, stirring for 1.0-2.0 hours, filtering III to obtain 25.2 liters of the germanium-precipitating liquid No. 3 and 156 grams of germanium concentrate No. 4, wherein the germanium concentrate No. 4 mainly contains 14.7 weight percent of water, 7.8 weight percent of zinc, 1.7 weight percent of germanium and 64 weight percent of iron, and the germanium-precipitating liquid No. 3 mainly contains 28.3 g/liter of total iron, 0.1 g/liter of copper, 0.0037 g/liter of germanium and 101 g/liter of zinc and 0.05 g/liter of arsenic. Germanium concentrate No. 4 is sent to a germanium recovery system to produce germanium dioxide, and liquid air is oxidized to remove iron after germanium precipitation No. 3 to recover iron.
5) Liquid air oxidation deironing after germanium precipitation: and (3) taking 25 liters of solution after germanium precipitation No. 3, heating to 85-90 ℃, introducing compressed air ferric oxide, oxidizing for 1.0-1.5 hours, adding lime to neutralize and remove iron, continuously stirring for 0.5-3.0 hours at the end of neutralization, filtering IV, and filtering IV to obtain 24.2 liters of solution after air oxidation No. 4 and 930 g of iron slag No. 5. The No. 5 iron slag mainly contains 20.6 weight percent of water, 68 weight percent of iron, 3.4 weight percent of zinc and 0.16 weight percent of arsenic, and the No. 4 air oxidized liquid mainly contains 8.9 g/L of total iron, 0.07 g/L of copper, 103 g/L of zinc and 0.003 g/L of arsenic. The No. 5 iron slag is sold to achieve the aim of opening an iron-arsenic circuit, and the liquid after No. 4 air oxidation is sent to a roasting ore leaching system to recycle zinc.
In this embodiment, each technical economic index is obtained by calculation as follows:
1. the direct yield of germanium is 89.7%;
2. the copper direct yield was 94.1%.
Example 3
10000 g of zinc sulfite residue produced by a certain company in Yunnan is taken and dried for standby, wherein the zinc sulfite residue contains 8.3wt% of water, 34.8wt% of zinc, 32.7wt% of zinc sulfite, 1.4wt% of iron, 0.038wt% of germanium, 3.8wt% of lead, 0.0053wt% of silver and 0.92wt% of copper; (2) 30 liters of high-iron high-copper solution mainly containing 23 g/liter of total iron, 21 g/liter of ferric iron, 2.7 g/liter of copper, 0.026 g/liter of germanium, 53 g/liter of zinc, 34 g/liter of sulfuric acid and 0.08 g/liter of arsenic; (3) 10 liters of electrolysis waste liquid containing 47 g/liter of zinc and 141 g/liter of sulfuric acid.
1) Neutralization reduction of high-valence iron: 30 liters of high-iron and high-copper solution is taken, heated to 60-70 ℃, zinc sulfite slag is slowly added, sulfur dioxide released in the process is sent to a sulfuric acid system for recycling to prepare acid, the feeding time is controlled to be 1.0-1.5 hours, the pH value of the reaction process can be controlled to be 1.5-2.0 by using electrolysis waste liquid to adjust acidity, filtering I is carried out when the content of ferric ions is ensured to be less than 0.2 g/liter, 5280 g of zinc sulfite slag is shared, 2410 g of No. 1 neutralization slag and 28.1 liters of liquid after No. 1 neutralization are obtained by filtering I, the water content of No. 1 neutralization slag is 16.2wt%, 13.0wt% of zinc, 3.4wt% of iron, 0.006wt% of germanium, 9.1wt% of lead, 0.0126 wt% of silver and 0.24wt% of copper. The neutralized liquid of No. 1 contained 24.5 g/l of total iron, 0.03 g/l of ferric iron, 4.2 g/l of copper, 0.089 g/l of germanium, 107.2 g/l of zinc and 0.08 g/l of arsenic. And (3) merging the No. 1 neutralization slag into secondary low-acid leaching slag in a leaching workshop, and then carrying out three times of high-temperature high-acid leaching to recover valuable metals.
2) And (3) separating copper and germanium by selective reduction replacement of the neutralized solution: taking 27 liters of the neutralized solution 1, heating to 40-60 ℃, slowly adding 125 grams of reducing agent metal iron powder to replace copper, wherein the addition amount of the iron powder is 1.1 times of the mass of copper metal in the neutralized solution, filtering II after the reaction time is 0.5-1.0 hour, and obtaining 160 grams of coarse copper powder 2 and 27 liters of the replaced solution 2 by filtering II. Copper 69.9wt% of No. 2 crude copper powder, 13.8wt% of iron, and the No. 2 replaced liquid contains 28.3 g/L of total iron, 0.01 g/L of ferric iron, 0.06 g/L of copper, 0.083 g/L of germanium, 104.6 g/L of zinc and 0.08 g/L of arsenic. And (2) delivering the liquid after the replacement to neutralize, absorb and flocculate to recycle germanium.
3) Magnetic separation of crude copper powder: 150 g of No. 2 coarse metal copper powder is subjected to magnetic adsorption to recover metal iron powder, so that the grade of the coarse metal copper powder is improved, and 12 g of No. 3 metal iron powder and 138 g of No. 3 fine metal copper powder are obtained through separation. The No. 3 metal iron powder is returned to the copper replacement process for reuse, and the No. 3 fine metal copper powder contains 76.0 weight percent of copper and is sold.
4) And (3) carrying out neutralization adsorption flocculation on the replaced liquid alkali to recover germanium, taking 27 liters of the replaced liquid No. 2, heating to 60-70 ℃, regulating the acidity pH value to 3.0-4.0 by using a neutralizer sodium hydroxide, adding 13.5 g of activated carbon, adding 0.5 g of activated carbon into each liter of replaced liquid, stirring for 1.0-2.0 hours, filtering III to obtain 26.1 liters of the germanium-depositing liquid No. 3 and 118 grams of germanium concentrate No. 4, wherein the germanium concentrate No. 4 mainly contains 12.3 weight percent of water, 6.3 weight percent of zinc, 2.12 weight percent of germanium and 51 weight percent of iron, and the germanium-depositing liquid No. 3 mainly contains 27.3 grams/liter of total iron, 0.06 grams/liter of copper, 0.0022 grams/liter of germanium and 107.9 grams/liter of arsenic and 0.08 grams/liter of arsenic. Germanium concentrate No. 4 is sent to a germanium recovery system to produce germanium dioxide, and liquid air is oxidized to remove iron after germanium precipitation No. 3 to recover iron.
5) Liquid air oxidation deironing after germanium precipitation: and (3) taking 25 liters of solution after germanium precipitation No. 3, heating to 85-90 ℃, introducing compressed air ferric oxide, oxidizing for 1.0-1.5 hours, adding lime to neutralize and remove iron, continuously stirring for 0.5-3.0 hours at the end of neutralization, filtering IV, and filtering IV to obtain 24.4 liters of solution after air oxidation No. 4 and 915 g of iron slag No. 5. The No. 5 iron slag mainly contains 19.0wt% of water, 75wt% of iron, 2.7wt% of zinc and 0.26wt% of arsenic, and the No. 4 air oxidized liquid mainly contains 5.3 g/L of total iron, 0.04 g/L of copper, 109.7 g/L of zinc and 0.002 g/L of arsenic. The No. 5 iron slag is sold to achieve the aim of opening an iron-arsenic circuit, and the liquid after No. 4 air oxidation is sent to a roasting ore leaching system to recycle zinc.
In this embodiment, each technical economic index is obtained by calculation as follows:
1. the direct yield of germanium is 92.9%;
2. the copper direct yield was 94.6%.
Example 4
Example 4 is a comparison of the unexpected effect of the technology of the present invention with respect to moisture content, germanium grade, and germanium recovery of germanium concentrate, compared to the effect without added activated carbon, as shown in the following table.
| Sequence number | Activated carbon addition (g/L solution) | Germanium concentrate moisture (%) | Grade of germanium (%) | Germanium recovery (%) |
| 1 | 0 | 29.8 | 0.6 | 76.2 |
| 2 | 0 | 31.1 | 0.5 | 71.4 |
| 3 | 0.1 | 15.0 | 1.5 | 85.5 |
| 4 | 0.2 | 14.7 | 1.7 | 89.7 |
| 5 | 0.5 | 12.3 | 2.12 | 92.9 |
| 6 | 0.6 | 12.2 | 2.19 | 93.0 |
It can be seen from the table that the addition of the modifier activated carbon not only has the effect of improving the slag performance and facilitating the liquid-solid separation, but also has the double effect of assisting iron to flocculate and adsorb germanium.
Effect summary of examples 1-4
1. From examples 1, 2, 3 it can be derived that: the average germanium direct yield is up to 89.1%, and the average copper direct yield is up to 93.0%;
2. from example 4 it can be derived that: the addition of the modifier activated carbon not only has the effect of improving the slag performance and facilitating the liquid-solid separation, but also has the double effect of assisting iron to flocculate and adsorb germanium; and the addition amount of the activated carbon is 0.1 to 0.5 gram of the activated carbon added into each liter of the replaced liquid, so that the optimal effect can be achieved.
Claims (10)
1. A method for harmless recovery of copper and germanium from a high-iron and high-copper solution, which is characterized by comprising the following steps:
step 1, neutralization and reduction of high-valence iron: the high-iron high-copper solution is heated and heated, zinc sulfite slag is slowly added, sulfur dioxide released in the process is sent to a sulfuric acid system for recycling to prepare acid, the terminal pH=1.5-2.0, when the content of ferric ions is below 0.2 g/L, filtering I is carried out, no. 1 neutralization slag and No. 1 neutralization solution are obtained, no. 1 neutralization slag is merged into a leaching workshop for secondary low-acid leaching slag, and then three times of high-temperature high-acid leaching are carried out to recycle valuable metals;
step 2, separating copper and germanium by selective reduction and replacement of the neutralized liquid: heating the neutralized solution 1, slowly adding a reducing agent metal iron powder to replace copper, wherein the addition amount of the iron powder is 0.9-1.1 times of the mass of copper metal in the neutralized solution, and filtering II after full reaction to obtain crude copper powder 2 and replaced solution 2; the liquid after the replacement of the No. 2 is sent to neutralize, absorb and flocculate to recycle germanium;
step 3, magnetic separation of crude copper powder: recovering metal iron powder from the No. 2 crude metal copper powder by adopting a magnet adsorption method to improve the grade of the crude metal copper powder, and separating to obtain No. 3 metal iron powder and No. 3 fine metal copper powder; the No. 3 metal iron powder is returned to the copper replacement process for reuse, and the No. 3 refined metal copper powder is sold;
and step 4, neutralizing, adsorbing and flocculating the replaced liquid alkali to recover germanium: the pH value of the solution after the replacement of No. 2 is 2.0-2.5, heating and heating, and regulating the pH value of the solution with a neutralizing agent sodium hydroxide to be 3.0-4.0, adding activated carbon with the addition amount of 0.1-0.5 g of activated carbon per liter of the solution after the replacement, stirring, filtering III to obtain solution after the germanium deposition of No. 3 and germanium concentrate No. 4, feeding the germanium concentrate No. 4 into a germanium recovery system to produce germanium dioxide, oxidizing and removing iron from the solution after the germanium deposition of No. 3 by air, and recovering iron;
step 5, removing iron by liquid air oxidation after germanium precipitation: heating the solution after the germanium precipitation No. 3, heating and introducing compressed air ferric oxide, adding lime to neutralize and deironing after oxidation, continuously stirring and filtering IV after the neutralization end point pH=2.5-3.0, and filtering IV to obtain solution after the air oxidation No. 4 and iron slag No. 5; no. 5 iron slag is sold to achieve the aim of opening an iron circuit, and the liquid after No. 4 air oxidation is sent to a roasting ore leaching system to recover zinc.
2. The method for harmless recovery of copper and germanium from high-iron and high-copper solutions according to claim 1, wherein in step 1:
the zinc sulfite slag is waste slag generated by zinc hydrometallurgy, and is a product generated by absorbing sulfur dioxide in the flue gas of the volatilizing kiln by adopting zinc-containing materials in the process of volatilizing and recycling valuable metals in the volatilizing kiln, wherein the product comprises 25-40 wt% of zinc, 20-35 wt% of zinc sulfite, 1.0-4.0 wt% of iron, 0.02-0.04 wt% of germanium, 2.0-4.0 wt% of lead, 0.001-0.006 wt% of silver and 0.2-1.0 wt% of copper.
3. The method for harmless recovery of copper and germanium from high-iron and high-copper solutions according to claim 1, wherein in step 1:
the high-iron and high-copper solution comprises 20-26 g/L of total iron, 19-25 g/L of ferric iron, 1.0-3.0 g/L of copper, 0.020-0.040 g/L of germanium, 40-60 g/L of zinc, 20-40 g/L of sulfuric acid and 0.01-0.5 g/L of arsenic.
4. The method for harmless recovery of copper and germanium from high-iron and high-copper solutions according to claim 1, wherein in step 1:
the No. 1 neutralization slag comprises 5.0 to 13 weight percent of zinc, 1.0 to 4.5 weight percent of iron, 0.005 to 0.015 weight percent of germanium, 4.0 to 10.0 weight percent of lead, 0.002 to 0.02 weight percent of silver and 0.1 to 0.3 weight percent of copper.
5. The method for harmless recovery of copper and germanium from high-iron and high-copper solutions according to claim 1, wherein in step 1:
the neutralizing solution 1 comprises 20-28 g/L of total iron, 0.01-0.2 g/L of ferric iron, 1.0-4.0 g/L of copper, 0.060-0.090 g/L of germanium and 70-120 g/L of zinc.
6. The method for harmless recovery of copper and germanium from high-iron and high-copper solutions according to claim 1, wherein in step 2:
the No. 2 liquid after replacement comprises 21-32 g/L of total iron, 0.01-0.10 g/L of ferric iron, 0.05-0.25 g/L of copper, 0.040-0.090 g/L of germanium and 70-120 g/L of zinc.
7. The method for harmless recovery of copper and germanium from high-iron and high-copper solutions according to claim 1, wherein in step 3:
and 75-85% of copper is contained in the No. 3 fine metal copper powder.
8. The method for harmless recovery of copper and germanium from high-iron and high-copper solutions according to claim 1, wherein in step 4:
the germanium concentrate No. 4 contains 1.0-3.0% of germanium, 5.0-15% of zinc and 50-70% of iron.
9. The method for harmless recovery of copper and germanium from high-iron and high-copper solutions according to claim 1, wherein in step 5:
the No. 5 iron slag contains 60 to 70 percent of iron, 0.5 to 5.0 percent of zinc and 0.1 to 0.4 percent of arsenic.
10. The method for harmless recovery of copper and germanium from high-iron high-copper solution according to any one of claims 1 to 9, wherein:
in the step 1, the high-iron high-copper solution is heated to 60-70 ℃ and the charging time is controlled to be 1.0-1.5 hours.
In the step 2, the neutralized solution of the No. 1 is heated to 40-60 ℃ for 0.5-1.0 hour.
In the step 4, the acidity is regulated by a neutralizer sodium hydroxide after heating to 60-70 ℃.
In the step 5, the solution after the germanium precipitation No. 3 is heated to 85-90 ℃ and oxidized for 1.0-1.5 hours; the stirring time is continuously 0.5 to 1.0 hour.
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| CN116732356A (en) * | 2023-08-15 | 2023-09-12 | 昆明理工大学 | Method for synchronously leaching and precipitating germanium in zinc suboxide smoke dust |
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| CN116732356A (en) * | 2023-08-15 | 2023-09-12 | 昆明理工大学 | Method for synchronously leaching and precipitating germanium in zinc suboxide smoke dust |
| CN116732356B (en) * | 2023-08-15 | 2023-10-03 | 昆明理工大学 | Method for synchronously leaching and precipitating germanium in zinc suboxide smoke dust |
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