CN109609754B - Waste recovery process generated in precious metal extraction process - Google Patents
Waste recovery process generated in precious metal extraction process Download PDFInfo
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- CN109609754B CN109609754B CN201910022781.7A CN201910022781A CN109609754B CN 109609754 B CN109609754 B CN 109609754B CN 201910022781 A CN201910022781 A CN 201910022781A CN 109609754 B CN109609754 B CN 109609754B
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- 238000000605 extraction Methods 0.000 title claims abstract description 74
- 239000002699 waste material Substances 0.000 title claims abstract description 40
- 238000011084 recovery Methods 0.000 title claims abstract description 27
- 239000010970 precious metal Substances 0.000 title claims abstract description 19
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 126
- 229910052802 copper Inorganic materials 0.000 claims abstract description 126
- 239000010949 copper Substances 0.000 claims abstract description 126
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 claims abstract description 41
- 229910052711 selenium Inorganic materials 0.000 claims abstract description 41
- 239000011669 selenium Substances 0.000 claims abstract description 41
- 239000004094 surface-active agent Substances 0.000 claims abstract description 30
- 229910000365 copper sulfate Inorganic materials 0.000 claims abstract description 26
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 claims abstract description 26
- 229910052751 metal Inorganic materials 0.000 claims abstract description 25
- 239000002184 metal Substances 0.000 claims abstract description 25
- 239000002253 acid Substances 0.000 claims abstract description 24
- 239000000463 material Substances 0.000 claims abstract description 21
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims abstract description 18
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 claims abstract description 18
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 claims abstract description 18
- 229910052938 sodium sulfate Inorganic materials 0.000 claims abstract description 18
- 235000011152 sodium sulphate Nutrition 0.000 claims abstract description 18
- 229920000742 Cotton Polymers 0.000 claims abstract description 13
- 239000003365 glass fiber Substances 0.000 claims abstract description 13
- 229920003023 plastic Polymers 0.000 claims abstract description 13
- 239000004033 plastic Substances 0.000 claims abstract description 13
- 230000001180 sulfating effect Effects 0.000 claims abstract description 13
- 238000010025 steaming Methods 0.000 claims abstract description 12
- 239000013078 crystal Substances 0.000 claims abstract description 9
- 239000007788 liquid Substances 0.000 claims description 80
- 239000000243 solution Substances 0.000 claims description 58
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 52
- 239000011259 mixed solution Substances 0.000 claims description 46
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 44
- JPJALAQPGMAKDF-UHFFFAOYSA-N selenium dioxide Chemical compound O=[Se]=O JPJALAQPGMAKDF-UHFFFAOYSA-N 0.000 claims description 40
- 238000010438 heat treatment Methods 0.000 claims description 32
- 238000002156 mixing Methods 0.000 claims description 32
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical group CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 30
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 27
- 238000000926 separation method Methods 0.000 claims description 27
- 238000002386 leaching Methods 0.000 claims description 25
- 238000000034 method Methods 0.000 claims description 23
- 229910052759 nickel Inorganic materials 0.000 claims description 22
- 238000003756 stirring Methods 0.000 claims description 21
- 239000012074 organic phase Substances 0.000 claims description 20
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 claims description 20
- 239000003945 anionic surfactant Substances 0.000 claims description 18
- 229940000207 selenious acid Drugs 0.000 claims description 18
- MCAHWIHFGHIESP-UHFFFAOYSA-N selenous acid Chemical compound O[Se](O)=O MCAHWIHFGHIESP-UHFFFAOYSA-N 0.000 claims description 18
- 239000002736 nonionic surfactant Substances 0.000 claims description 17
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 11
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 11
- 229910052737 gold Inorganic materials 0.000 claims description 11
- 239000010931 gold Substances 0.000 claims description 11
- 238000000227 grinding Methods 0.000 claims description 11
- 239000003350 kerosene Substances 0.000 claims description 11
- 229910052709 silver Inorganic materials 0.000 claims description 11
- 239000004332 silver Substances 0.000 claims description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 11
- 238000004070 electrodeposition Methods 0.000 claims description 10
- 238000005868 electrolysis reaction Methods 0.000 claims description 10
- 238000005086 pumping Methods 0.000 claims description 10
- 235000010265 sodium sulphite Nutrition 0.000 claims description 10
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical group [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 claims description 9
- 239000013504 Triton X-100 Substances 0.000 claims description 9
- 229920004890 Triton X-100 Polymers 0.000 claims description 9
- 238000002425 crystallisation Methods 0.000 claims description 9
- 230000008025 crystallization Effects 0.000 claims description 9
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims description 8
- 238000005660 chlorination reaction Methods 0.000 claims description 8
- 239000003546 flue gas Substances 0.000 claims description 8
- 238000006243 chemical reaction Methods 0.000 claims description 7
- VEQPNABPJHWNSG-UHFFFAOYSA-N Nickel(2+) Chemical compound [Ni+2] VEQPNABPJHWNSG-UHFFFAOYSA-N 0.000 claims description 6
- 238000007599 discharging Methods 0.000 claims description 6
- 238000009713 electroplating Methods 0.000 claims description 6
- 229910001453 nickel ion Inorganic materials 0.000 claims description 6
- 239000002893 slag Substances 0.000 claims description 6
- 239000010802 sludge Substances 0.000 claims description 6
- 239000003795 chemical substances by application Substances 0.000 claims description 5
- 238000001914 filtration Methods 0.000 claims description 5
- 238000003825 pressing Methods 0.000 claims description 5
- 239000008237 rinsing water Substances 0.000 claims description 5
- 239000007787 solid Substances 0.000 claims description 5
- 239000011343 solid material Substances 0.000 claims description 5
- 238000000498 ball milling Methods 0.000 claims description 2
- 230000005587 bubbling Effects 0.000 claims 2
- QYHFIVBSNOWOCQ-UHFFFAOYSA-N selenic acid Chemical compound O[Se](O)(=O)=O QYHFIVBSNOWOCQ-UHFFFAOYSA-N 0.000 claims 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims 1
- 238000010521 absorption reaction Methods 0.000 claims 1
- 239000002131 composite material Substances 0.000 claims 1
- 239000003085 diluting agent Substances 0.000 claims 1
- 238000012163 sequencing technique Methods 0.000 claims 1
- 229910052717 sulfur Inorganic materials 0.000 claims 1
- 239000011593 sulfur Substances 0.000 claims 1
- 150000002739 metals Chemical class 0.000 abstract description 14
- 238000001704 evaporation Methods 0.000 abstract description 12
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 abstract description 10
- 239000003153 chemical reaction reagent Substances 0.000 abstract description 4
- 238000004519 manufacturing process Methods 0.000 abstract description 2
- 239000003960 organic solvent Substances 0.000 abstract description 2
- 230000001988 toxicity Effects 0.000 abstract 1
- 231100000419 toxicity Toxicity 0.000 abstract 1
- 239000000203 mixture Substances 0.000 description 14
- 230000008020 evaporation Effects 0.000 description 11
- 238000004064 recycling Methods 0.000 description 6
- 238000001816 cooling Methods 0.000 description 5
- 238000005485 electric heating Methods 0.000 description 5
- 150000002736 metal compounds Chemical class 0.000 description 5
- 239000006096 absorbing agent Substances 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- 230000019635 sulfation Effects 0.000 description 4
- 238000005670 sulfation reaction Methods 0.000 description 4
- 238000005303 weighing Methods 0.000 description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 3
- 238000003723 Smelting Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 239000002910 solid waste Substances 0.000 description 3
- 230000007613 environmental effect Effects 0.000 description 2
- 238000003837 high-temperature calcination Methods 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 239000002574 poison Substances 0.000 description 2
- 231100000614 poison Toxicity 0.000 description 2
- 239000000779 smoke Substances 0.000 description 2
- 229910000342 sodium bisulfate Inorganic materials 0.000 description 2
- 238000005728 strengthening Methods 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000003034 coal gas Substances 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B1/00—Preliminary treatment of ores or scrap
- C22B1/02—Roasting processes
- C22B1/06—Sulfating roasting
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B19/00—Selenium; Tellurium; Compounds thereof
- C01B19/02—Elemental selenium or tellurium
-
- 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
- C22B11/00—Obtaining noble metals
- C22B11/06—Chloridising
-
- 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
- C22B15/00—Obtaining copper
- C22B15/0063—Hydrometallurgy
- C22B15/0084—Treating 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
- C22B23/00—Obtaining nickel or cobalt
- C22B23/04—Obtaining nickel or cobalt by wet processes
- C22B23/0407—Leaching processes
- C22B23/0415—Leaching processes with acids or salt solutions except ammonium salts 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
- C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
- C22B3/20—Treatment or purification of solutions, e.g. obtained by leaching
- C22B3/26—Treatment or purification of solutions, e.g. obtained by leaching by liquid-liquid extraction using organic compounds
- C22B3/40—Mixtures
- C22B3/409—Mixtures at least one compound being an organo-metallic compound
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
- C22B7/006—Wet processes
- C22B7/007—Wet processes by acid leaching
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Mechanical Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Geology (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Environmental & Geological Engineering (AREA)
- Geochemistry & Mineralogy (AREA)
- Inorganic Chemistry (AREA)
- Manufacture And Refinement Of Metals (AREA)
Abstract
The invention discloses a waste recovery process generated in the precious metal extraction process, which grinds the waste generated in the precious metal extraction process, adds sodium sulfate in sulfating roasting, and enables the complex state of valuable metals in the materials to be more fully converted into the state of soluble sulfate; the electric rotary kiln is used for replacing the traditional roasting furnace for selenium steaming, so that the selenium recovery rate is improved; the copper sulfate solution is extracted and back-extracted by reasonably using the copper extractant, the surfactant and the boosting surfactant, so that the high-efficiency enrichment and recovery of copper are realized; evaporating raffinate by adding nickel sulfate crystal seeds to obtain nickel sulfate, wherein the generated waste acid can be recycled; the volatilization of the organic solvent is effectively reduced by utilizing the polyhedral plastic balls and the glass fiber cotton, so that the production cost is reduced, and the pollution and the toxicity of chemical reagents to the surrounding environment and personnel are reduced.
Description
Technical Field
The invention relates to the field of resource recycling, in particular to a process technology for recovering metals such as copper, selenium, nickel, gold, silver and the like from waste generated in a precious metal extraction process.
Background
The metal smelting industry can generate a large amount of waste materials, the solid waste materials contain valuable elements such as copper, selenium, nickel, gold, silver and the like, the solid waste materials are widely applied to various fields, whether the solid waste materials can be efficiently and comprehensively recycled has important significance for driving the utilization of renewable resources in the nonferrous metal industry, the metallurgical industry in China is seriously restricted by resources, energy sources, ecological environment and the like, and the cyclic utilization of the resources is a necessary choice for the development of the metallurgical industry in China in order to ensure the sustainable development of the economy in China, relieve the pressure of the resources, the energy sources and the environment and develop the resource recycling.
The traditional process comprises the steps of sulfating and roasting wastes, performing ball milling, then leaching with hot water, wherein a leaching solution, namely a copper sulfate solution, generally contains 45g/L of copper, then replacing with iron powder to produce sponge copper, removing iron, neutralizing and depositing nickel in a replaced solution, and then discharging for triple effect evaporation; the product of the whole process is sponge copper and returns to a copper smelting system, copper in the sponge copper contains a large amount of impurities, the availability and the processing performance are not high, a large amount of waste residues can be produced in the process, and heavy metal elements contained in the waste residues can be randomly stacked to cause a plurality of environmental problems and great environmental risks.
In order to solve the problems, the invention develops a waste recovery process generated in the precious metal extraction process, in particular to a process technology for recovering metals such as copper, selenium, nickel and the like from the waste generated in the precious metal extraction process, sodium sulfate is added into waste materials in sulfating roasting, the reaction process is strengthened, the complex state of valuable metals in the waste materials is more fully converted into the state of soluble sulfate, and selenium is efficiently recovered; then the copper sulfate solution is extracted and back-extracted by reasonably using a copper extractant, a surfactant, a boosting surfactant and the like to enrich the copper sulfate solution; meanwhile, the volatilization of the reagent is reduced by utilizing the polyhedral plastic balls and the glass fiber cotton, the pollution and the poison of the chemical reagent to the surrounding environment and personnel are reduced, the recovery rate of each metal is improved, and the added value of the product is increased.
Disclosure of Invention
The invention aims to provide a waste recovery process generated in the precious metal extraction process. The invention comprises the following steps:
(1) grinding: grinding waste generated in the precious metal extraction process by using a ball mill, wherein the fineness of the waste is required to be 200-400 meshes;
(2) multi-metal sulfating roasting: mixing the ball-milled materials with 93% concentrated sulfuric acid according to the mass ratio of 1: 0.8-1, adding a proper amount of sodium sulfate, wherein the addition amount of the sodium sulfate is 3-6% of the weight of dry ore, putting the mixture into a slurrying kettle for stirring, heating to about 220-300 ℃, adopting electric heating as a heat source, reacting most of metals and metal compounds in waste with sulfuric acid in the slurrying kettle to generate sulfate, converting selenium into selenium dioxide, volatilizing and separating the selenium dioxide more thoroughly, reducing the emission of coal or natural gas tail gas, reducing carbon emission, saving energy, protecting environment, and carrying the sodium sulfateUnder the action of concentrated sulfuric acid, at low temperature, the sodium sulfate absorbs the excessive concentrated sulfuric acid to react to generate NaHSO4NaHSO at high temperature calcination4And decomposing to provide a sulfating agent for the sulfation process, thereby greatly strengthening the reaction process and leading the metal sulfation to be more sufficient. In addition, the sodium sulfate is not consumed in the reaction process and can be recycled for multiple times;
(3) steaming selenium crude preparation: putting the material processed in the step (2) into an electric rotary kiln, putting the rotary kiln into a rotary kiln for selenium steaming, roasting the rotary kiln, heating the rotary kiln to 300-400 ℃ at a heating rate of 60 ℃/h, preserving heat for 2h, then continuously heating the rotary kiln to 580-620 ℃ at a heating rate of 45 ℃/h, preserving heat for 1h, sublimating selenium in the form of selenium dioxide into roasting smoke, introducing the roasting smoke into a bubbler filled with water, reacting the selenium dioxide with water to generate selenious acid, absorbing the selenious dioxide by a two-stage bubbler, completely converting the selenium dioxide into selenious acid, discharging selenious acid solution in a bubbler absorber, adding sodium sulfite, reacting for 2h, wherein the mass ratio of the sodium sulfite to the selenious acid is 1.2:1, and reacting and filtering to obtain selenium;
(4) selective leaching: adding the solid material treated in the step (3) into a leaching tank in a thermal state, pumping rinsing water and dilute acid, wherein the solid-to-liquid ratio is 1: 1-3, mechanically stirring for 2 hours, pumping into a filter press for liquid-solid separation, rinsing and filter pressing for 3-5 times to obtain copper separating liquid, and carrying out centralized treatment on obtained filter residues;
(5) extraction and back extraction: uniformly mixing the mixed solution A and the mixed solution B according to the mass ratio of 4-6: 1 to obtain an extract liquid; the mixed solution A is prepared by mixing a saponified copper extractant and sulfonated kerosene in a mass ratio of 1: 6-8, wherein the copper extractant is prepared by mixing P204 and M5640 in a mass ratio of 1: 0.8-1.2, and the copper extractant is saponified by using an equal amount of NaOH; the mixed solution B is a mixture of a nonionic surfactant and a boosting surfactant according to the mass ratio of 1: 1-3, the nonionic surfactant is Triton X-100, and the boosting surfactant is n-butyl alcohol;
extracting copper in the copper separating liquid by using an extraction liquid, wherein the ratio of the copper separating liquid to the extraction liquid is 1-3: 1, adding polyhedral plastic balls to cover the liquid surface, stirring for 5-10 min at 150r/min, performing multi-stage extraction at the temperature of 45-55 ℃, standing for layering, and performing multi-stage oil-liquid separation to obtain a copper-loaded organic phase and a raffinate; collecting copper-loaded organic phases, preparing a mixed solution of 8-15% of dilute sulfuric acid and 0.007-0.011 mol/L of anionic surfactant, adding glass fiber cotton to cover the liquid surface, carrying out repeated back extraction in stages to obtain a copper sulfate solution, returning the copper sulfate solution to an electrolysis workshop, recovering copper by electrodeposition, and purifying the extractant solution for repeated use, wherein the anionic surfactant is sodium dodecyl sulfate;
(6) and (3) nickel recovery: directly heating raffinate for evaporation, finishing evaporation concentration when the end-point acidity of the solution reaches 1000g/L, naturally cooling the material to be not higher than 50 ℃ by adding nickel sulfate seed crystals, when the concentration of nickel ions in the solution is reduced to be lower than 8g/L, finishing crystallization, dehydrating nickel sulfate by a centrifugal machine, bagging, weighing and selling, wherein the centrifugal liquid contains about 50% of sulfuric acid, can be used for the acid leaching stage of electroplating sludge, and can be used for treating residual nickel in the acid leaching stage and recycling the acid;
(7) and (4) carrying out chlorination gold separation and silver separation on the copper separation slag obtained in the step (4).
The invention has the beneficial effects that: the waste generated in the precious metal extraction process is ground and sulfated and roasted to convert the complex state of valuable metals in the waste into the state of soluble sulfate, the electric rotary kiln is used for replacing the traditional roasting furnace to evaporate selenium, the selenium recovery rate is improved, copper sulfate solution is extracted and back extracted through reasonable application of a copper extractant, a surfactant and a boosting surfactant, the high-efficiency enrichment and recovery of copper are realized, then the raffinate is evaporated and added with seed crystals to obtain nickel sulfate; the produced copper separating slag enters a gold and silver separating process by chlorination;
the sodium sulfate can carry concentrated sulfuric acid, and at low temperature, the sodium sulfate absorbs excessive concentrated sulfuric acid to react to generate NaHSO4NaHSO at high temperature calcination4And decomposing to provide a sulfating agent for the sulfation process, thereby greatly strengthening the reaction process and leading the metal sulfation to be more sufficient. In addition, the sodium sulfate is not consumed in the reaction process and can be recycled for multiple times;
the use of the polyhedral plastic balls and the glass fiber cotton in the process increases the reaction contact area in the extraction and back extraction processes, reduces the reaction time, effectively reduces the volatilization of the organic solvent, reduces the production cost, and lightens the pollution and the poison of chemical reagents to the surrounding environment and personnel.
The invention can comprehensively recover various metals in the waste, improves the recovery rate of nonferrous metals such as copper, selenium, nickel, gold, silver and the like, and increases the added value of products; the process is shortened, the smelting cost is greatly reduced, the operation is simple, and the continuous operation is easy; the pollution to the surrounding environment is reduced, the wastewater of the whole process is recycled, and zero discharge is achieved.
Detailed Description
The waste generated in the precious metal extraction process of our factory is used for processing and researching.
Example 1
(1) Grinding: grinding waste generated in the precious metal extraction process by using a ball mill, wherein the fineness of the waste is required to be 200 meshes;
(2) multi-metal sulfating roasting: mixing the ball-milled materials with 93% concentrated sulfuric acid according to the mass ratio of 1: 0.9, adding a proper amount of sodium sulfate, wherein the addition amount of the sodium sulfate is 5 percent of the dry ore weight, putting the mixture into a slurrying kettle for stirring, heating the mixture to about 260 ℃, adopting electric heating as a heat source, reacting most of metals and metal compounds in the waste with sulfuric acid in the slurrying kettle to generate sulfate, and converting selenium into selenium dioxide to be volatilized and separated more thoroughly;
(3) steaming selenium crude preparation: putting the material processed in the step (2) into an electric rotary kiln, putting the rotary kiln into a rotary kiln for selenium steaming, heating the rotary kiln to 300-400 ℃ at a heating rate of 60 ℃/h, preserving heat for 2h, then continuously heating to 580-620 ℃ at a heating rate of 45 ℃/h, preserving heat for 1h, sublimating selenium in the form of selenium dioxide into roasting flue gas, introducing the roasting flue gas into a bubbler filled with water, reacting the selenium dioxide with water to generate selenious acid, absorbing the selenious dioxide by a two-stage bubbler, completely converting the selenium dioxide into selenious acid, discharging selenious acid solution in a bubbler absorber, adding sodium sulfite, reacting for 2h, wherein the mass ratio of the sodium sulfite to the selenious acid is 1.2:1, and reacting and filtering to obtain selenium;
(4) selective leaching: adding the solid material treated in the step (3) into a leaching tank in a thermal state, pumping rinsing water and dilute acid, wherein the solid-to-liquid ratio is 1:2, mechanically stirring for 2 hours, pumping into a filter press for liquid-solid separation, rinsing and filter pressing for 4 times to obtain copper separating liquid, and carrying out centralized treatment on obtained filter residues;
(5) extraction and back extraction: uniformly mixing the mixed solution A and the mixed solution B according to the mass ratio of 5: 1; the mixed solution A is prepared by mixing a saponified copper extractant and sulfonated kerosene according to a mass ratio of 1:7, wherein the copper extractant is prepared by mixing P204 and M5640 according to a mass ratio of 1:1, and the copper extractant is saponified by using an equal amount of NaOH; wherein the mixed solution B is a mixture of a nonionic surfactant and a boosting surfactant according to the mass ratio of 1:2, the nonionic surfactant is Triton X-100, and the boosting surfactant is n-butyl alcohol;
extracting copper in the copper separating liquid by using an extraction liquid, wherein the ratio of the copper separating liquid to the extraction liquid is 2:1, adding polyhedral plastic balls to cover the liquid surface, stirring for 8min at 150r/min, performing multi-stage extraction at the temperature of 50 ℃, standing for layering, and performing multi-stage oil-liquid separation to obtain a copper-loaded organic phase and a raffinate; collecting copper-loaded organic phase, preparing mixed solution of 10% dilute sulfuric acid and 0.009mol/L anionic surfactant, adding glass fiber cotton to cover the liquid surface, carrying out back extraction for multiple times in a subsection manner to obtain copper sulfate solution, returning the copper sulfate solution to an electrolysis workshop, recovering copper by electrodeposition, and purifying the extractant solution for multiple times of repeated use, wherein the anionic surfactant is sodium dodecyl sulfate;
(6) and (3) nickel recovery: directly heating raffinate for evaporation, finishing evaporation concentration when the end-point acidity of the solution reaches 1000g/L, naturally cooling the material to be not higher than 50 ℃ by adding nickel sulfate seed crystals, when the concentration of nickel ions in the solution is reduced to be lower than 8g/L, finishing crystallization, dehydrating nickel sulfate by a centrifugal machine, bagging, weighing and selling, wherein the centrifugal liquid contains about 50% of sulfuric acid, can be used for the acid leaching stage of electroplating sludge, and can be used for treating residual nickel in the acid leaching stage and recycling the acid;
(7) and (4) carrying out chlorination gold separation and silver separation on the copper separation slag obtained in the step (4).
Example 2
(1) Grinding: grinding waste generated in the precious metal extraction process by using a ball mill, wherein the fineness of the waste is required to be 200 meshes;
(2) multi-metal sulfating roasting: mixing the ball-milled materials with 93% concentrated sulfuric acid according to the mass ratio of 1:0.8, adding a proper amount of sodium sulfate, wherein the addition amount of the sodium sulfate is 6 percent of the weight of the dry ore, putting the mixture into a slurrying kettle for stirring, heating the mixture to about 220 ℃, adopting electric heating as a heat source, reacting most of metals and metal compounds in the waste with sulfuric acid in the slurrying kettle to generate sulfate, and converting selenium into selenium dioxide to be volatilized and separated more thoroughly;
(3) steaming selenium crude preparation: putting the material processed in the step (2) into an electric rotary kiln, putting the rotary kiln into a rotary kiln for selenium steaming, heating the rotary kiln to 300-400 ℃ at a heating rate of 60 ℃/h, preserving heat for 2h, then continuously heating to 580-620 ℃ at a heating rate of 45 ℃/h, preserving heat for 1h, sublimating selenium in the form of selenium dioxide into roasting flue gas, introducing the roasting flue gas into a bubbler filled with water, reacting the selenium dioxide with water to generate selenious acid, absorbing the selenious dioxide by a two-stage bubbler, completely converting the selenium dioxide into selenious acid, discharging selenious acid solution in a bubbler absorber, adding sodium sulfite, reacting for 2h, wherein the mass ratio of the sodium sulfite to the selenious acid is 1.2:1, and reacting and filtering to obtain selenium;
(4) selective leaching: adding the solid material treated in the step (3) into a leaching tank in a thermal state, pumping rinsing water and dilute acid, wherein the solid-to-liquid ratio is 1:1, mechanically stirring for 2 hours, pumping into a filter press for liquid-solid separation, rinsing and filter pressing for 3 times to obtain copper separating liquid, and carrying out centralized treatment on obtained filter residues;
(5) extracting and back extracting, namely uniformly mixing the mixed solution A and the mixed solution B according to the mass ratio of 6: 1; the mixed solution A is prepared by mixing a saponified copper extractant and sulfonated kerosene according to the mass ratio of 1:6, wherein the copper extractant is prepared by mixing P204 and M5640 according to the mass ratio of 1:0.8, and the copper extractant is saponified by using the same amount of NaOH; wherein the mixed solution B is a mixture of a nonionic surfactant and a boosting surfactant according to the mass ratio of 1:3, the nonionic surfactant is Triton X-100, and the boosting surfactant is n-butyl alcohol;
extracting copper in the copper separating liquid by using an extraction liquid, wherein the ratio of the copper separating liquid to the extraction liquid is 3:1, adding polyhedral plastic balls to cover the surface of the liquid, stirring for 5min at 150r/min, performing multi-stage extraction at the temperature of 45 ℃, standing for layering, and performing multi-stage oil-liquid separation to obtain a copper-loaded organic phase and a raffinate; collecting copper-loaded organic phase, preparing mixed solution of 15% dilute sulfuric acid and 0.007mol/L anionic surfactant, adding glass fiber cotton to cover the liquid surface, carrying out repeated stripping in stages to obtain copper sulfate solution, returning the copper sulfate solution to an electrolysis workshop, recovering copper by electrodeposition, and purifying the extractant solution for repeated use, wherein the anionic surfactant is sodium dodecyl sulfate;
(6) and (3) nickel recovery: directly heating raffinate for evaporation, finishing evaporation concentration when the end-point acidity of the solution reaches 1000g/L, naturally cooling the material to be not higher than 50 ℃ by adding nickel sulfate seed crystals, when the concentration of nickel ions in the solution is reduced to be lower than 8g/L, finishing crystallization, dehydrating nickel sulfate by a centrifugal machine, bagging, weighing and selling, wherein the centrifugal liquid contains about 50% of sulfuric acid, can be used for the acid leaching stage of electroplating sludge, and can be used for treating residual nickel in the acid leaching stage and recycling the acid;
(7) and (4) carrying out chlorination gold separation and silver separation on the copper separation slag obtained in the step (4).
Example 3
(1) Grinding: grinding waste generated in the precious metal extraction process by using a ball mill, wherein the fineness of the waste is required to be 400 meshes;
(2) multi-metal sulfating roasting: mixing the ball-milled materials with 93% concentrated sulfuric acid according to a mass ratio of 1:1, adding a proper amount of sodium sulfate, wherein the addition amount of the sodium sulfate is 3% of the weight of dry ore, putting the mixture into a slurrying kettle, stirring, heating to about 300 ℃, adopting electric heating as a heat source, reacting most of metals and metal compounds in waste with sulfuric acid in the slurrying kettle to generate sulfate, and converting selenium into selenium dioxide to be volatilized and separated more thoroughly;
(3) steaming selenium crude preparation: putting the material processed in the step (2) into an electric rotary kiln, putting the rotary kiln into a rotary kiln for selenium steaming, heating the rotary kiln to 300-400 ℃ at a heating rate of 60 ℃/h, preserving heat for 2h, then continuously heating to 580-620 ℃ at a heating rate of 45 ℃/h, preserving heat for 1h, sublimating selenium in the form of selenium dioxide into roasting flue gas, introducing the roasting flue gas into a bubbler filled with water, reacting the selenium dioxide with water to generate selenious acid, absorbing the selenious dioxide by a two-stage bubbler, completely converting the selenium dioxide into selenious acid, discharging selenious acid solution in a bubbler absorber, adding sodium sulfite, reacting for 2h, wherein the mass ratio of the sodium sulfite to the selenious acid is 1.2:1, and reacting and filtering to obtain selenium;
(4) selective leaching: adding the solid material treated in the step (3) into a leaching tank in a thermal state, pumping rinsing water and dilute acid, wherein the solid-to-liquid ratio is 1:3, mechanically stirring for 2 hours, pumping into a filter press for liquid-solid separation, rinsing and filter pressing for 5 times to obtain copper separating liquid, and carrying out centralized treatment on obtained filter residues;
(5) extraction and back extraction: uniformly mixing the mixed solution A and the mixed solution B according to the mass ratio of 4: 1; the mixed solution A is prepared by mixing a saponified copper extractant and sulfonated kerosene according to a mass ratio of 1:8, wherein the copper extractant is prepared by mixing P204 and M5640 according to a mass ratio of 1:1.2, and the copper extractant is saponified by using an equal amount of NaOH; wherein the mixed solution B is a mixture of a nonionic surfactant and a boosting surfactant according to the mass ratio of 1:1, the nonionic surfactant is Triton X-100, and the boosting surfactant is n-butyl alcohol;
extracting copper in the copper separating liquid by using an extraction liquid, wherein the ratio of the copper separating liquid to the extraction liquid is 1:1, adding polyhedral plastic balls to cover the surface of the liquid, stirring for 15min at 150r/min, performing multi-stage extraction at the temperature of 55 ℃, standing for layering, and performing multi-stage oil-liquid separation to obtain a copper-loaded organic phase and a raffinate; collecting copper-loaded organic phase, preparing mixed solution of 8% dilute sulfuric acid and 0.011mol/L anionic surfactant, adding glass fiber cotton to cover the liquid surface, carrying out repeated back extraction in stages to obtain copper sulfate solution, returning the copper sulfate solution to an electrolysis workshop, recovering copper by electrodeposition, and purifying the extractant solution for repeated use, wherein the anionic surfactant is sodium dodecyl sulfate;
(6) and (3) nickel recovery: directly heating raffinate for evaporation, finishing evaporation concentration when the end-point acidity of the solution reaches 1000g/L, naturally cooling the material to be not higher than 50 ℃ by adding nickel sulfate seed crystals, when the concentration of nickel ions in the solution is reduced to be lower than 8g/L, finishing crystallization, dehydrating nickel sulfate by a centrifugal machine, bagging, weighing and selling, wherein the centrifugal liquid contains about 50% of sulfuric acid, can be used for the acid leaching stage of electroplating sludge, and can be used for treating residual nickel in the acid leaching stage and recycling the acid;
(7) and (4) carrying out chlorination gold separation and silver separation on the copper separation slag obtained in the step (4).
Example 4
(2) Multi-metal sulfating roasting: mixing the ball-milled materials with 93% concentrated sulfuric acid according to the mass ratio of 1: 0.9, stirring, putting into a slurrying kettle, heating to about 260 ℃, adopting electric heating as a heat source, reacting most metals and metal compounds in the waste with sulfuric acid in the slurrying kettle to generate sulfate, so that copper and nickel are converted into soluble sulfate more completely, selenium is converted into selenium dioxide, and the volatilization and separation are more complete, and the rest steps are the same as those in example 1.
Example 5
(5) Extraction and back extraction: uniformly mixing the mixed solution A and the mixed solution B according to the mass ratio of 5: 1; the mixed solution A is prepared by mixing a copper extractant and sulfonated kerosene according to a mass ratio of 1:7, wherein the copper extractant is prepared by mixing P204 and M5640 according to a mass ratio of 1: 1; wherein the mixed solution B is a mixture of a nonionic surfactant and a boosting surfactant according to the mass ratio of 1:2, the nonionic surfactant is Triton X-100, and the boosting surfactant is n-butyl alcohol;
extracting copper in the copper separating liquid by using an extraction liquid, wherein the ratio of the copper separating liquid to the extraction liquid is 2:1, adding polyhedral plastic balls to cover the surface of the liquid, stirring for 8min at 150r/min, performing multi-stage extraction at the temperature of 50 ℃, standing for layering, and performing multi-stage oil-liquid separation to obtain a copper-loaded organic phase and a raffinate; collecting copper-loaded organic phase, preparing mixed solution of 10% dilute sulfuric acid and 0.009mol/L anionic surfactant, adding glass fiber cotton to cover the liquid surface, carrying out back extraction for multiple times in a subsection manner to obtain copper sulfate solution, returning the copper sulfate solution to an electrolysis workshop, recovering copper by electrodeposition, and purifying the extractant solution for multiple times of repeated use, wherein the anionic surfactant is sodium dodecyl sulfate; the rest of the procedure was the same as in example 1.
Example 6
Uniformly mixing the mixed solution A and the mixed solution B according to the mass ratio of 5: 1; the mixed solution A is prepared by mixing a saponified copper extractant and sulfonated kerosene according to a mass ratio of 1:7, wherein the copper extractant is P204, and the copper extractant is saponified by using the same amount of NaOH; wherein the mixed solution B is a mixture of a nonionic surfactant and a boosting surfactant according to the mass ratio of 1:2, the nonionic surfactant is Triton X-100, and the boosting surfactant is n-butyl alcohol;
extracting copper in the copper separating liquid by using an extraction liquid, wherein the ratio of the copper separating liquid to the extraction liquid is 2:1, adding polyhedral plastic balls to cover the surface of the liquid, stirring for 8min at 150r/min, performing multi-stage extraction at the temperature of 50 ℃, standing for layering, and performing multi-stage oil-liquid separation to obtain a copper-loaded organic phase and a raffinate; collecting copper-loaded organic phase, preparing mixed solution of 10% dilute sulfuric acid and 0.009mol/L anionic surfactant, adding glass fiber cotton to cover the liquid surface, carrying out back extraction for multiple times in a subsection manner to obtain copper sulfate solution, returning the copper sulfate solution to an electrolysis workshop, recovering copper by electrodeposition, and purifying the extractant solution for multiple times of repeated use, wherein the anionic surfactant is sodium dodecyl sulfate; the rest of the procedure was the same as in example 1.
Example 7
Uniformly mixing the mixed solution A and the mixed solution B according to the mass ratio of 5: 1; the mixed solution A is prepared by mixing a saponified copper extractant and sulfonated kerosene according to a mass ratio of 1:7, wherein the copper extractant is M5640, and the copper extractant is saponified by using the same amount of NaOH; wherein the mixed solution B is a mixture of a nonionic surfactant and a boosting surfactant according to the mass ratio of 1:2, the nonionic surfactant is Triton X-100, and the boosting surfactant is n-butyl alcohol;
extracting copper in the copper separating liquid by using an extraction liquid, wherein the ratio of the copper separating liquid to the extraction liquid is 2:1, adding polyhedral plastic balls to cover the surface of the liquid, stirring for 8min at 150r/min, performing multi-stage extraction at the temperature of 50 ℃, standing for layering, and performing multi-stage oil-liquid separation to obtain a copper-loaded organic phase and a raffinate; collecting copper-loaded organic phase, preparing mixed solution of 10% dilute sulfuric acid and 0.009mol/L anionic surfactant, adding glass fiber cotton to cover the liquid surface, carrying out back extraction for multiple times in a subsection manner to obtain copper sulfate solution, returning the copper sulfate solution to an electrolysis workshop, recovering copper by electrodeposition, and purifying the extractant solution for multiple times of repeated use, wherein the anionic surfactant is sodium dodecyl sulfate; the rest of the procedure was the same as in example 1.
Example 8
Mixing a saponified copper extractant and sulfonated kerosene according to the mass ratio of 1:7, wherein the copper extractant is prepared by mixing P204 and M5640 according to the mass ratio of 1:1, the copper extractant is saponified by using equal amount of NaOH, extracting copper in a copper separating solution by using a mixed solution, the ratio of the copper separating solution to the extracting solution is 2:1, adding a polyhedral plastic ball to cover the surface of the liquid, stirring for 8min at 150r/min, performing multi-stage extraction at the temperature of 50 ℃, standing for layering, and obtaining a copper-loaded organic phase and a raffinate through a multi-stage oil-liquid separator; the copper-loaded organic phase is collected, 10% dilute sulfuric acid is prepared and added into the glass fiber cotton to cover the liquid surface, copper sulfate solution is obtained through back extraction for multiple times in a sectional manner, the copper sulfate solution returns to an electrolysis workshop to recover copper by electrodeposition, the extractant solution can be reused for multiple times after being purified, and the rest steps are the same as those in the example 1.
Example 9
(6) And (3) nickel recovery: directly heating raffinate for evaporation, finishing evaporation concentration when the final acidity of the solution reaches 1000g/L, naturally cooling, finishing crystallization when the concentration of nickel ions in the solution is reduced to be below 8g/L, dehydrating nickel sulfate by a centrifugal machine, bagging and selling the nickel sulfate by pounds, wherein the centrifugate contains about 50 percent of sulfuric acid and can be used in the acid leaching stage of electroplating sludge, the residual nickel can be treated in the acid leaching stage, the acid is recycled, and the rest steps are the same as those in the embodiment 1.
Example 10
(5) Extraction and back extraction: uniformly mixing the mixed solution A and the mixed solution B according to the mass ratio of 5: 1; the mixed solution A is prepared by mixing a saponified copper extractant and sulfonated kerosene according to a mass ratio of 1:7, wherein the copper extractant is prepared by mixing P204 and M5640 according to a mass ratio of 1:1, and the copper extractant is saponified by using an equal amount of NaOH; wherein the mixed solution B is a mixture of a nonionic surfactant and a boosting surfactant according to the mass ratio of 1:2, the nonionic surfactant is Triton X-100, and the boosting surfactant is n-butyl alcohol;
extracting copper in the copper separating liquid by using an extraction liquid, wherein the ratio of the copper separating liquid to the extraction liquid is 2:1, stirring for 8min at 150r/min, performing multistage extraction at the temperature of 50 ℃, standing for layering, and passing through a multistage oil-liquid separator to obtain a copper-loaded organic phase and a raffinate; collecting the copper-loaded organic phase, preparing a mixed solution of 10% dilute sulfuric acid and 0.009mol/L anionic surfactant, carrying out back extraction for multiple times in a sectional manner to obtain a copper sulfate solution, returning the copper sulfate solution to an electrolysis workshop, recovering copper by electrodeposition, and purifying the extractant solution for multiple times of repeated use, wherein the anionic surfactant is sodium dodecyl sulfate, and the rest steps are the same as those in example 1.
The recovery rates of selenium, copper and nickel prepared in examples 1 to 10 were measured; separating time of extract liquor; extractant consumption (copper extractant consumed for 1t waste treatment)
| Examples | Percent recovery of selenium (%) | Copper recovery (%) | Nickel recovery (%) | Time (min) for separating extractive solution | Consumption of extractant (kg) |
| 1 | 98.9 | 98.3 | 95.7 | 10 | 18.6 |
| 2 | 98.8 | 97.9 | 95.3 | 12 | 18.6 |
| 3 | 98.7 | 98.0 | 95.4 | 11 | 18.6 |
| 4 | 97.5 | 96.8 | 94.7 | 12 | 18.6 |
| 5 | 98.7 | 97.1 | 95.0 | 15 | 18.6 |
| 6 | 98.6 | 96.5 | 94.5 | 14 | 18.6 |
| 7 | 98.7 | 96.8 | 94.4 | 13 | 18.6 |
| 8 | 98.7 | 95.5 | 94.1 | 20 | 18.6 |
| 9 | 98.7 | 97.9 | 94.8 | 12 | 18.6 |
| 10 | 98.6 | 97.6 | 95.0 | 15 | 20.4 |
As can be seen from the analysis of the data in the tables, examples 1-3 employ the patented technology of the present invention, with example 1 being the most preferred; example 4 sulfating roasting without adding sodium sulfate, the recovery of the visible metals is greatly reduced; example 5 the extractant was not saponified and the copper recovery was low; in example 6, the recovery rates of copper and nickel are lower than the combined use effect of the copper extractant when the copper extractant is used as P204 alone and the copper extractant is used as M5640 alone in example 7; example 8 does not use surface active agent and boosting surface active agent, the extraction effect is not ideal and the extraction and back extraction takes long time; in the crystallization process of the nickel sulfate in the example 9, no seed crystal is added, and the nickel sulfate has slow crystallization rate and less crystallization; in the embodiment 10, no polyhedral plastic ball or glass fiber cotton is added, so that the consumption of the extracting agent is obviously increased; therefore, the method can be concluded that the waste generated in the precious metal extraction process is ground and sulfated and roasted to convert the complex state of valuable metals in the waste into the state of soluble sulfate, the electric rotary kiln is used for replacing the traditional roasting furnace to evaporate selenium, the selenium recovery rate is improved, the copper sulfate solution is extracted and back extracted through reasonable application of a copper extracting agent, a surfactant and a boosting surfactant, the high-efficiency extraction and recovery of copper are realized, and then the residual liquid is evaporated and added into seed crystals to obtain the nickel sulfate.
Claims (3)
1. A waste recovery process generated in a precious metal extraction process is characterized in that: comprises (1) grinding (2) polymetallic sulfur
Acidifying and roasting (3), steaming selenium crude (4), selectively leaching (5), extracting, back extracting (6), recovering nickel (7), and separating gold and silver by chlorination;
wherein, the grinding specific process in the step (1) comprises the following steps: grinding waste generated in the precious metal extraction process by ball milling, wherein the fineness of the waste is 200
Mesh 400 to mesh;
wherein, the specific process of the multi-metal sulfating roasting in the step (2) comprises the following steps: mixing the ball-milled materials with 93% concentrated sulfuric acid according to a mass ratio of 1:
0.8-1, adding sodium sulfate, stirring in a slurrying kettle, electrically heating as a heat source, and
heating to about 220-300 ℃;
wherein, the specific process for steaming the crude selenium in the step (3) comprises the following steps: putting the material processed in the step (2) into an electric rotary kiln, and feeding
Steaming selenium, heating the roasted selenium in a rotary kiln at a heating rate of 60 ℃/h to 300-400 ℃, preserving heat for 2h, then continuously heating the roasted selenium in a heating rate of 45 ℃/h to 580-620 ℃, preserving heat for 1h, sublimating the selenium in the form of selenium dioxide into roasting flue gas, absorbing the roasting flue gas through two-stage bubbling, reacting the selenium dioxide and water to generate selenious acid dissolved in water, and periodically carrying out bubbling on the selenious acid in an absorption kettle
Discharging the selenic acid solution, adding sodium sulfite for reaction for 2 hours, wherein the mass ratio of the sodium sulfite to the selenic acid is 1.2:1, and reacting and filtering to obtain selenium;
wherein, the step (4) is selective leaching: adding the solid material treated in the step (3) into a leaching tank in a thermal state, and pumping
Adding rinsing water and dilute acid, wherein the solid-to-liquid ratio is 1: 1-3, mechanically stirring for 2 hours, pumping into a filter press for liquid-solid separation, rinsing and filter pressing for 3-5 times to obtain copper separating liquid, and carrying out centralized treatment on obtained filter residues;
wherein, the extraction and back extraction in the step (5) are as follows: uniformly mixing the mixed solution A and the mixed solution B according to the mass ratio of 4-6: 1; wherein the mixed solution A is formed by mixing the saponified copper extractant and the sulfonated kerosene; the mixed solution B is mixed with a nonionic surfactant and a boosting surfactant; the saponified copper extractant is prepared by saponifying a composite extractant of P204 and M5640 with the mass ratio of 1: 0.8-1.2 by using the same amount of NaOH; the non-ionic surface active agent is Triton X-100, the boosting surface active agent is n-butyl alcohol, and the mass ratio of the n-butyl alcohol to the boosting surface active agent is 1: 1-3;
extracting copper in the copper separating liquid by using an extraction liquid, wherein the ratio of the copper separating liquid to the extraction liquid is 1-3: 1, adding polyhedral plastic balls to cover the surface of the liquid, stirring for 5-10 min at 150r/min, performing multi-stage extraction at the temperature of 45-55 ℃, standing for layering, and performing multi-stage oil-liquid separation to obtain a copper-loaded organic phase and a raffinate; collecting copper-loaded organic phases, preparing a mixed solution of 8-15% of dilute sulfuric acid and 0.007-0.011 mol/L of anionic surfactant, adding glass fiber cotton to cover the liquid surface, carrying out repeated back extraction in stages to obtain a copper sulfate solution, returning the copper sulfate solution to an electrolysis workshop, recovering copper by electrodeposition, and purifying the extractant solution for repeated use; the anionic surfactant is sodium dodecyl sulfate;
wherein, the specific process for recovering nickel in the step (6) comprises the following steps: the raffinate is directly heated and concentrated, and is evaporated when the end-point acidity of the solution reaches 1000g/L
After the concentration is finished, the nickel sulfate crystal seeds are added into the material after the material is naturally cooled to be not higher than 50 ℃, and when the concentration of nickel ions in the solution is reduced to 8g/L
After crystallization is finished, the nickel sulfate is dehydrated by a centrifugal machine and then packaged and weighed for sale, the centrifugate contains about 50 percent of sulfuric acid and can be used in the acid leaching stage of the electroplating sludge, the residual nickel can be treated in the acid leaching stage, and the acid can be recycled;
the specific processes of gold and silver separation by chlorination in the step (7) are as follows: the copper separating slag obtained in the step (4) enters a gold and silver separating tool for chlorination
And (4) sequencing.
2. The process of claim 1, wherein the waste recovery process is performed by a precious metal extraction process
Step (2) polymetallic sulfating roasting: the addition amount of the sodium sulfate is 3-6% of the dry ore weight.
3. The process of claim 1, wherein the copper is recovered from the waste produced by the precious metal extraction process
The mass ratio of the extracting agent to the sulfonated kerosene diluent is 1: 6-8.
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