CN115261635B - Comprehensive recycling method for high-grade multi-element gold concentrate - Google Patents
Comprehensive recycling method for high-grade multi-element gold concentrate Download PDFInfo
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- CN115261635B CN115261635B CN202210917275.6A CN202210917275A CN115261635B CN 115261635 B CN115261635 B CN 115261635B CN 202210917275 A CN202210917275 A CN 202210917275A CN 115261635 B CN115261635 B CN 115261635B
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- gold
- leaching
- silver
- tailings
- pulp
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- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 title claims abstract description 206
- 229910052737 gold Inorganic materials 0.000 title claims abstract description 186
- 239000010931 gold Substances 0.000 title claims abstract description 186
- 238000000034 method Methods 0.000 title claims abstract description 99
- 239000012141 concentrate Substances 0.000 title claims abstract description 67
- 238000004064 recycling Methods 0.000 title claims abstract description 48
- 238000002386 leaching Methods 0.000 claims abstract description 124
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims abstract description 92
- 229910052709 silver Inorganic materials 0.000 claims abstract description 81
- 239000004332 silver Substances 0.000 claims abstract description 81
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 41
- 230000008569 process Effects 0.000 claims abstract description 40
- 238000005188 flotation Methods 0.000 claims abstract description 36
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 28
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 28
- 239000011593 sulfur Substances 0.000 claims abstract description 28
- 239000002994 raw material Substances 0.000 claims abstract description 21
- 238000000227 grinding Methods 0.000 claims abstract description 14
- 238000007670 refining Methods 0.000 claims abstract description 12
- 239000007788 liquid Substances 0.000 claims description 74
- 238000006243 chemical reaction Methods 0.000 claims description 27
- 239000002002 slurry Substances 0.000 claims description 27
- 238000000967 suction filtration Methods 0.000 claims description 27
- 238000011084 recovery Methods 0.000 claims description 23
- 239000007787 solid Substances 0.000 claims description 22
- 239000012535 impurity Substances 0.000 claims description 20
- 238000006722 reduction reaction Methods 0.000 claims description 20
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 18
- 239000003112 inhibitor Substances 0.000 claims description 18
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 17
- 238000005406 washing Methods 0.000 claims description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 17
- 230000002000 scavenging effect Effects 0.000 claims description 16
- 238000000926 separation method Methods 0.000 claims description 15
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 14
- 239000004571 lime Substances 0.000 claims description 14
- 229910017604 nitric acid Inorganic materials 0.000 claims description 14
- 238000001556 precipitation Methods 0.000 claims description 14
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 13
- 235000008733 Citrus aurantifolia Nutrition 0.000 claims description 12
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 12
- 235000011941 Tilia x europaea Nutrition 0.000 claims description 12
- 239000004088 foaming agent Substances 0.000 claims description 12
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 claims description 11
- QZPSXPBJTPJTSZ-UHFFFAOYSA-N aqua regia Chemical compound Cl.O[N+]([O-])=O QZPSXPBJTPJTSZ-UHFFFAOYSA-N 0.000 claims description 10
- 230000035484 reaction time Effects 0.000 claims description 10
- 238000003756 stirring Methods 0.000 claims description 10
- 239000007789 gas Substances 0.000 claims description 9
- 230000001590 oxidative effect Effects 0.000 claims description 9
- 239000011780 sodium chloride Substances 0.000 claims description 9
- HRZFUMHJMZEROT-UHFFFAOYSA-L sodium disulfite Chemical compound [Na+].[Na+].[O-]S(=O)S([O-])(=O)=O HRZFUMHJMZEROT-UHFFFAOYSA-L 0.000 claims description 9
- 229940001584 sodium metabisulfite Drugs 0.000 claims description 9
- 235000010262 sodium metabisulphite Nutrition 0.000 claims description 9
- 238000003723 Smelting Methods 0.000 claims description 8
- 239000003599 detergent Substances 0.000 claims description 8
- 239000002562 thickening agent Substances 0.000 claims description 8
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 7
- 239000011449 brick Substances 0.000 claims description 6
- TUZCOAQWCRRVIP-UHFFFAOYSA-N butoxymethanedithioic acid Chemical compound CCCCOC(S)=S TUZCOAQWCRRVIP-UHFFFAOYSA-N 0.000 claims description 6
- 239000004568 cement Substances 0.000 claims description 6
- 239000000463 material Substances 0.000 claims description 6
- 238000006864 oxidative decomposition reaction Methods 0.000 claims description 6
- 235000019353 potassium silicate Nutrition 0.000 claims description 6
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical group [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims description 6
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical group OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 5
- 239000002202 Polyethylene glycol Substances 0.000 claims description 5
- 229910052799 carbon Inorganic materials 0.000 claims description 5
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 claims description 5
- 238000001914 filtration Methods 0.000 claims description 5
- 229920003063 hydroxymethyl cellulose Polymers 0.000 claims description 5
- 229940031574 hydroxymethyl cellulose Drugs 0.000 claims description 5
- 239000007791 liquid phase Substances 0.000 claims description 5
- QUBQYFYWUJJAAK-UHFFFAOYSA-N oxymethurea Chemical compound OCNC(=O)NCO QUBQYFYWUJJAAK-UHFFFAOYSA-N 0.000 claims description 5
- 229950005308 oxymethurea Drugs 0.000 claims description 5
- 229920001223 polyethylene glycol Polymers 0.000 claims description 5
- NJRXVEJTAYWCQJ-UHFFFAOYSA-N thiomalic acid Chemical compound OC(=O)CC(S)C(O)=O NJRXVEJTAYWCQJ-UHFFFAOYSA-N 0.000 claims description 5
- WVYWICLMDOOCFB-UHFFFAOYSA-N 4-methyl-2-pentanol Chemical compound CC(C)CC(C)O WVYWICLMDOOCFB-UHFFFAOYSA-N 0.000 claims description 4
- 239000012752 auxiliary agent Substances 0.000 claims description 4
- 239000007795 chemical reaction product Substances 0.000 claims description 4
- 239000003814 drug Substances 0.000 claims description 4
- 229940079593 drug Drugs 0.000 claims description 4
- 239000012065 filter cake Substances 0.000 claims description 4
- 239000002245 particle Substances 0.000 claims description 4
- 238000003825 pressing Methods 0.000 claims description 4
- 229920002907 Guar gum Polymers 0.000 claims description 3
- 238000000354 decomposition reaction Methods 0.000 claims description 3
- 230000018044 dehydration Effects 0.000 claims description 3
- 238000006297 dehydration reaction Methods 0.000 claims description 3
- 239000000665 guar gum Substances 0.000 claims description 3
- 229960002154 guar gum Drugs 0.000 claims description 3
- 235000010417 guar gum Nutrition 0.000 claims description 3
- 230000003647 oxidation Effects 0.000 claims description 3
- 238000007254 oxidation reaction Methods 0.000 claims description 3
- 238000011085 pressure filtration Methods 0.000 claims description 3
- 241000254137 Cicadidae Species 0.000 claims description 2
- 229910052500 inorganic mineral Inorganic materials 0.000 abstract description 16
- 239000011707 mineral Substances 0.000 abstract description 16
- 238000000605 extraction Methods 0.000 abstract description 14
- 239000002184 metal Substances 0.000 abstract description 5
- 229910052751 metal Inorganic materials 0.000 abstract description 5
- 150000002739 metals Chemical class 0.000 abstract description 5
- -1 gold and silver Chemical class 0.000 abstract description 2
- 230000000052 comparative effect Effects 0.000 description 14
- 238000004090 dissolution Methods 0.000 description 14
- 238000004519 manufacturing process Methods 0.000 description 13
- 241000931705 Cicada Species 0.000 description 8
- 230000008901 benefit Effects 0.000 description 7
- 238000012546 transfer Methods 0.000 description 7
- XFXPMWWXUTWYJX-UHFFFAOYSA-N Cyanide Chemical compound N#[C-] XFXPMWWXUTWYJX-UHFFFAOYSA-N 0.000 description 6
- 238000011161 development Methods 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- 238000006073 displacement reaction Methods 0.000 description 4
- 238000003912 environmental pollution Methods 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 description 4
- 230000000694 effects Effects 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 239000002440 industrial waste Substances 0.000 description 3
- 239000011148 porous material Substances 0.000 description 3
- 239000002699 waste material Substances 0.000 description 3
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- WQYVRQLZKVEZGA-UHFFFAOYSA-N hypochlorite Chemical compound Cl[O-] WQYVRQLZKVEZGA-UHFFFAOYSA-N 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 239000011268 mixed slurry Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 238000010008 shearing Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- PGWMQVQLSMAHHO-UHFFFAOYSA-N sulfanylidenesilver Chemical compound [Ag]=S PGWMQVQLSMAHHO-UHFFFAOYSA-N 0.000 description 2
- 231100000331 toxic Toxicity 0.000 description 2
- 230000002588 toxic effect Effects 0.000 description 2
- 208000004434 Calcinosis Diseases 0.000 description 1
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-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
- 206010028980 Neoplasm Diseases 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 239000010953 base metal Substances 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 229910001424 calcium ion Inorganic materials 0.000 description 1
- 159000000007 calcium salts Chemical class 0.000 description 1
- 201000011510 cancer Diseases 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 150000002366 halogen compounds Chemical class 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 239000011133 lead Substances 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000002366 mineral element Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 238000005456 ore beneficiation Methods 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 239000002910 solid waste Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- DHCDFWKWKRSZHF-UHFFFAOYSA-N sulfurothioic S-acid Chemical compound OS(O)(=O)=S DHCDFWKWKRSZHF-UHFFFAOYSA-N 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc 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
- C22B11/00—Obtaining noble metals
- C22B11/04—Obtaining noble metals by wet processes
-
- 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
- B03D—FLOTATION; DIFFERENTIAL SEDIMENTATION
- B03D1/00—Flotation
- B03D1/02—Froth-flotation processes
-
- 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
- B03D—FLOTATION; DIFFERENTIAL SEDIMENTATION
- B03D1/00—Flotation
- B03D1/14—Flotation machines
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B17/00—Sulfur; Compounds thereof
- C01B17/02—Preparation of sulfur; Purification
- C01B17/027—Recovery of sulfur from material containing elemental sulfur, e.g. luxmasses or sulfur containing ores; Purification of the recovered sulfur
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B33/00—Clay-wares
- C04B33/02—Preparing or treating the raw materials individually or as batches
- C04B33/13—Compounding ingredients
- C04B33/132—Waste materials; Refuse; Residues
- C04B33/138—Waste materials; Refuse; Residues from metallurgical processes, e.g. slag, furnace dust, galvanic waste
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B7/00—Hydraulic cements
- C04B7/14—Cements containing slag
- C04B7/147—Metallurgical slag
-
- 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
- C22B3/04—Extraction of metal compounds from ores or concentrates by wet processes by leaching
-
- 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
- C22B3/04—Extraction of metal compounds from ores or concentrates by wet processes by leaching
- C22B3/06—Extraction of metal compounds from ores or concentrates by wet processes by leaching in inorganic acid solutions, e.g. with acids generated in situ; in inorganic salt solutions other than ammonium salt solutions
- C22B3/065—Nitric 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
- C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
- C22B3/04—Extraction of metal compounds from ores or concentrates by wet processes by leaching
- C22B3/06—Extraction of metal compounds from ores or concentrates by wet processes by leaching in inorganic acid solutions, e.g. with acids generated in situ; in inorganic salt solutions other than ammonium salt solutions
- C22B3/10—Hydrochloric acid, other halogenated 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
- 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
- C22B3/44—Treatment or purification of solutions, e.g. obtained by leaching by chemical processes
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- 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
- C22B3/44—Treatment or purification of solutions, e.g. obtained by leaching by chemical processes
- C22B3/46—Treatment or purification of solutions, e.g. obtained by leaching by chemical processes by substitution, e.g. by cementation
-
- 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 provides a comprehensive recycling method of high-grade multi-element gold concentrate, which belongs to the technical field of comprehensive recycling of mineral resources and comprises the following steps: grinding and grading the raw materials to obtain ground pulp; leaching and replacing the ground pulp to obtain gold mud and leached tailings; a flotation process of carrying out flotation treatment on the leached tailings to obtain sulfur concentrate and flotation tailings; refining the gold mud to obtain gold ingots and silver ingots; and a harmless process for performing harmless treatment on the flotation tailings. The invention discloses a comprehensive recycling method of high-grade multi-element gold concentrate, which is used for solving the problems of low gold and silver extraction rate caused by unsuitable mineral dressing agent in the existing recycling of high-grade multi-element gold concentrate, difficult enrichment of unit element minerals caused by complex ore properties, low extraction rate of high-value metals such as gold and silver, overlong recycling process, difficult operation, and entrainment of high-value elements such as gold, silver and sulfur in tailings.
Description
Technical Field
The invention relates to the technical field of comprehensive recycling of mineral resources, in particular to a comprehensive recycling method of high-grade multi-element gold concentrate.
Background
Gold and silver are noble rare metals, are important resources indispensable in economic development and daily life, and play a very important role in international finance, so that the production and processing of gold and silver are very important to be seen in various countries of the world. Along with the rapid development of the economy in China, the living standard of people is continuously improved, the production and consumption of gold and silver are increasingly increased, the production value of gold and silver is urgently increased, and the requirements of the current society can be met only by continuously searching, developing and utilizing new mineral resources. The comprehensive recycling of high-grade multi-element gold concentrate is a great direction at present.
The high-grade multi-element gold concentrate is comprehensively recycled, so that the purposes of fully and efficiently utilizing effective mineral resources and reducing environmental pollution can be achieved. However, although China takes the energy chemical industry as a support in a quite long period, a large-scale centralized comprehensive resource recycling system is not completely established, and the contradiction between economic development and ecological environment protection is increasingly prominent. Therefore, when gold and silver are produced by utilizing high-grade multi-element gold concentrate, the comprehensive utilization of co-associated mineral resources and tailings is also required to be enhanced, so as to continuously promote the ideas of energy conservation, emission reduction and cyclic development.
The existing beneficiation methods of gold concentrate mainly comprise flotation, gravity separation, cyanidation and the like. Over 85% of gold in the world is extracted by cyanidation, which is a mature technology for extracting gold. The cyanidation method has the advantages of high gold recovery rate, strong adaptability to ores, low cost and the like. However, the disadvantages of the cyanidation process are also quite evident: cyanide is extremely toxic, has great potential safety hazards and environmental pollution risks in the transportation, storage and use processes, and moreover, the discharge of industrial cyanide-containing wastewater and solid wastes can seriously pollute water sources and soil environments, destroy ecological balance and influence the body health of surrounding residents.
In order to solve the problem of extremely toxic pollution of cyanide, a great deal of research work is developed on gold ore beneficiation agents at home and abroad in recent years, and efforts are made to find non-cyanide and non-toxic beneficiation agents such as thiourea methods, thiosulfate methods, hypochlorite methods, halogen compounds and the like. However, these beneficiation agents have problems of high production cost, poor stability, high consumption, poor adaptability to ores and the like, and these factors restrict the industrial popularization and application of these agents. And the raw materials such as high-grade multi-element gold concentrate and the like have complex ore properties and contain various useful mineral elements, single elements are difficult to extract or remove cleanly, so that the single element minerals are difficult to enrich, the extraction rate of high-value metals such as gold and silver is low, the recovery process is overlong and is difficult to operate, and a considerable part of elements such as gold, silver and sulfur are entrained in tailings, so that the comprehensive and efficient recovery of the elements such as gold, silver and sulfur is difficult.
Disclosure of Invention
The invention provides a comprehensive recycling method of high-grade multi-element gold concentrate, which is used for solving the problems of low gold and silver extraction rate caused by unsuitable mineral dressing agent in the existing high-grade multi-element gold concentrate recycling, difficult enrichment of unit element minerals caused by complex ore properties, low extraction rate of high-value metals such as gold and silver, overlong recycling process, difficult operation, and entrainment of high-value elements such as gold, silver and sulfur in tailings.
The invention provides a comprehensive recycling method of high-grade multi-element gold concentrate, which comprises the following steps: grinding and grading the raw materials to obtain ground pulp; leaching and replacing the ground pulp to obtain gold mud and leached tailings; a flotation process of carrying out flotation treatment on the leached tailings to obtain sulfur concentrate and flotation tailings; refining the gold mud to obtain gold ingots and silver ingots; and a harmless process for performing harmless treatment on the flotation tailings.
Further setting that the grain size of the ground pulp is-200 meshes not less than 80%; the leaching agent used in the leaching treatment is an environment-friendly gold extracting agent for golden cicadas; zinc powder is adopted for replacement in the replacement treatment; in the raw material, the content of gold is more than 200.00g/t, the content of silver is more than 10.00g/t, and the content of sulfur is more than 3%.
In the invention, the raw materials are high-grade multi-element gold concentrate mainly containing gold, silver, sulfur and the like, in the process of comprehensive recycling, the environment-friendly gold extracting agent is adopted to leach gold and silver, zinc powder is adopted to replace and refine, flotation is adopted to recover sulfur concentrate in tailings, innocent treatment of tailings is completed, gold and silver sulfur in the gold concentrate is comprehensively and integrally recovered through a multi-stage separation technology, and the comprehensive recovery rates of gold, silver and sulfur respectively reach more than 99%, 80% and 80%.
The method achieves the purposes of fully and efficiently utilizing effective mineral resources and reducing environmental pollution, and comprehensively recycles the co-associated mineral resources and tailings during gold and silver production, prolongs the chain for comprehensively utilizing gold concentrate resources, ensures that the mineral resources are maximally utilized, is energy-saving and environment-friendly, has high product quality, improves the resource recycling level, improves the resource utilization rate, and simultaneously does not use cyanide and other gold extracting agents which are easy to cause pollution, so that the green and environment-friendly production is realized.
The leaching process is further provided with the following steps: and (3) sending the ground pulp into a thickener for solid-liquid separation before leaching, adding a leaching agent and a pH value regulator into underflow pulp with the solid content of 65% obtained by the solid-liquid separation, leaching, washing and separating the leached pulp obtained by leaching for 4-5 times after leaching, sending the leached tailings obtained by washing and separating into a flotation process, merging the noble liquid obtained by washing and separating with the noble liquid obtained by solid-liquid separation in the thickener before leaching, adding zinc powder into the noble liquid for displacement treatment, displacing gold and silver from the noble liquid, and filtering by a plate frame to obtain gold mud.
The adding amount of the leaching agent is 300-1000g/t; the pH value regulator is lime, and the addition amount of the lime reaches 10-12 in terms of pH value; the leaching treatment time is 36h; the addition amount of zinc powder is 50-250g/t, and the particle size of zinc powder is-325 meshes not less than 95%.
The environment-friendly gold extraction agent for the golden cicada is an alkaline leaching agent, and the main components of the environment-friendly gold extraction agent comprise sodium carbo-cyanuric acid, alkaline thiourea, alkaline polymeric iron, alkali, carbonate and the like, and the components can be mutually matched, complex and dissolve gold in the ore and transfer the gold into a liquid phase, so that the leaching effect is achieved, and the environment-friendly gold extraction agent for the golden cicada has the advantages of safety, low toxicity, high gold recovery rate, stable property and simplicity and convenience in operation.
Further provided is that the flotation process comprises the following steps: adding 300-500g/t of active carbon into the leached tailings for removing the drugs, then adding sulfuric acid to adjust the pH value of the leached tailings to be 4.5-5.5, and then adding 400-500g/t of inhibitor, 200-300g/t of collector and 20-50g/t of foaming agent into the leached tailings to obtain rough concentrate and rough tailings through one-time roughing; then, scavenging the coarse tailings for three times, adding 100-150g/t of collector for each scavenging, and sending the scavenged tailings as flotation tailings to a harmless process; and (3) carrying out three times of concentration on the rough concentrate, wherein 150-300g/t of inhibitor is added in each concentration, and the concentration tailings are the sulfur concentrate.
The inhibitor is guar gum or hydroxymethyl cellulose, the collector is water glass, butyl xanthate and No. 2 oil in a weight ratio of 8-10:5-9:1, and the foaming agent is polyethylene glycol ether or methyl isobutyl carbinol; the rough concentration time is 5-30min, the single scavenging time is 20-60min, and the single concentration time is 20-60min.
The gold and silver-containing sulfur concentrate in the leached tailings is separated through floatation, the floatation process is stable, the grade of the sulfur concentrate is higher, the recovery of sulfur elements is realized, the entrainment of the sulfur concentrate to co-associated metals such as iron and the like is reduced, the comprehensive utilization value of the leached tailings is improved, and the comprehensive recovery utilization rate of the raw gold concentrate is further improved.
Further, the refining step comprises the steps of: adding nitric acid solution into gold mud to perform impurity removal operation, then adding water to perform suction filtration, wherein the solid obtained by suction filtration is crude gold powder, the liquid phase obtained by suction filtration is silver noble liquid, adding aqua regia into the crude gold powder to perform gold dissolving operation, then performing suction filtration, adding sodium metabisulfite into the obtained gold noble liquid to perform gold reduction reaction, performing suction filtration after the reaction, and smelting the obtained gold powder to obtain gold ingots; the silver noble liquid is subjected to precipitation reaction by sodium chloride and then suction filtration, iron powder is added into the obtained filter cake to perform silver reduction reaction, then coarse silver powder is obtained through suction filtration, and then the coarse silver powder is smelted to form silver ingots.
The method is further characterized in that in the impurity removal operation, the concentration of the nitric acid solution is 15-30%, the solid-to-liquid ratio of the gold mud to the nitric acid solution is 1:1-1.5, the impurity removal temperature is 60-90 ℃, and the impurity removal time is 60-200min; in the gold dissolving operation, the solid-to-liquid ratio of the crude gold powder to the aqua regia is 1:1-2, the temperature is 50-90 ℃ and the time is 1-12h; the addition amount of sodium metabisulfite is 0.5-1% of the weight of the gold noble liquid, and the gold reduction reaction time is 10-30min.
Further setting that in the precipitation reaction, the solid-liquid ratio of sodium chloride to silver noble liquid is 1:1.5-3, and the precipitation time is 40-90min; in the silver reduction reaction, the addition amount of iron powder is 100-300g/kg, the temperature is 20-40 ℃ and the time is 3-6h; the smelting temperature of the gold powder and the crude silver powder is 1000-1200 ℃. The gold mud is refined, so that base metals such as zinc, lead, copper and the like in the gold mud can be further removed, simple substances of gold and silver are separated from impurities, and the purity of gold ingots and silver ingots of products is improved.
The harmless treatment step is further provided as follows: the flotation tailings are sent to a filter press for pressure filtration and dehydration, backwater is sent to a flotation process for recycling, the obtained filter residues are sent to a stirring barrel, water is added to form filter residue slurry with the solid content of 25%, then a reagent-removing detergent is added to be mixed uniformly, the filter residue slurry is sent to a reaction tank, oxidizing gas is introduced into the reaction tank for oxidation and decomposition reaction, after the reaction is finished, reaction products are washed, water is obtained by washing for recycling, and the obtained filter residues are sold as light brick raw materials or cement auxiliary materials after filter pressing.
The detergent is hydrogen peroxide solution with concentration of 20-30%, and the adding amount is 50-300g/t; the oxidizing gas is ozone, and the ozone inlet amount is 5-20m 3 /h; the oxidative decomposition reaction time is 0.5-5h.
The tailings are subjected to innocent treatment to become recyclable general industrial waste, and the recycled general industrial waste is usually reused as light brick production raw materials or auxiliary materials in the cement industry, so that the pollution of the tailings to the surrounding environment can be avoided, the purposes of environmental protection and emission reduction are achieved, economic benefits can be created, and the recycling development space of waste resources can be expanded.
Further arranged that during leaching treatment, the underflow pulp is leached out in an ultrasonic environment; the above ultrasonic environment is provided by sinusoidal ultrasonic wave and variable frequency ultrasonic wave in alternating sequence of sine-variable frequency-sine-variable frequencyThe frequency of the power is 20-40KHz, and the power is 300mW/cm 2 The method comprises the steps of carrying out a first treatment on the surface of the The frequency of the variable frequency ultrasonic wave is 30-50KHz, and the power is 250mW/cm 2 。
Ultrasonic intervention is carried out during leaching, ultrasonic cavitation is utilized to promote gold and silver to be dissolved out, ultrasonic cavitation bubbles with different frequencies and powers are utilized to reduce dead angles caused by standing waves, the growth and collapse of the cavitation bubbles can generate shearing force in underflow slurry, different elements on the surface of the ore are dissociated to different degrees due to the difference of binding force, so that cracks or pores are generated on the surface of the ore more strongly, the surface of the ore is cracked earlier and faster, the mass transfer speed between the leaching agent and the ore is increased, the mass transfer surface area is increased, the leaching agent is assisted to improve the dissolution speed, the extraction rate and the yield of gold and silver, the leaching treatment time is shortened, and the time cost is saved.
The high-grade multi-element gold concentrate comprehensive recycling method provided by the invention realizes the following beneficial effects by recycling gold, silver and sulfur and performing innocent treatment on tailings:
1) In the invention, the raw materials are high-grade multi-element gold concentrate mainly containing gold, silver, sulfur and the like, in the process of comprehensive recycling, the environment-friendly gold extracting agent is adopted to leach gold and silver, zinc powder is adopted to replace and refine, the sulfur concentrate in tailings is recovered by floatation, the gold and silver sulfur in the gold concentrate is comprehensively and integrally recovered by a multi-stage separation technology, the comprehensive recovery rate of gold, silver and sulfur respectively reaches more than 99%, 80% and 80%, the' clean squeezing is realized, mineral resources are maximally utilized, the resource utilization rate is improved, and meanwhile, cyanide and other gold extracting agents which are easy to cause pollution are not used, so that the environment-friendly and environment-friendly production is realized.
2) The method of the invention realizes the purposes of precious metal purification and multi-element comprehensive recovery of gold concentrate, completes the harmless treatment of tailings, recycles the harmless tailings as light brick production raw materials or auxiliary materials in the cement industry, avoids the pollution of the tailings to the surrounding environment, has low energy consumption and low pollution in the recovery process, and has positive and obvious economic benefit, environmental benefit and social benefit.
3) The main products of the method are gold ingots, silver ingots and sulfur concentrates containing gold and silver, and the harmless tailings are recyclable general industrial wastes, so that the method achieves the purposes of fully and efficiently utilizing effective mineral resources and reducing environmental pollution, and comprehensively recycles the co-associated mineral resources and tailings during gold and silver production, prolongs the chain for comprehensively utilizing the gold concentrate resources, saves energy, protects the environment, has high product quality, improves the resource recycling level, and is beneficial to actively promoting the industrial development of comprehensive utilization, waste resource recycling and the like.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions of the prior art, the following description will briefly explain the drawings used in the embodiments or the description of the prior art, and it is obvious that the drawings in the following description are some embodiments of the present invention, and other drawings can be obtained according to these drawings without inventive effort for a person skilled in the art.
Fig. 1 is a schematic diagram showing the dissolution rate of gold on a circuit board under different conditions.
Detailed Description
For the purpose of making the objects, technical solutions and advantages of the embodiments of the present invention more clear, the technical solutions in the embodiments of the present invention will be clearly and completely described below, and it is apparent that the described embodiments are some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are also within the scope of the invention.
The comprehensive recovery and utilization method of the high-grade multi-element gold concentrate comprises the following steps:
1) Grinding: adding water into the raw materials, stirring to form primary pulp with the solid content of 20-40%, adding lime and noble liquid recycled from the leaching process, stirring to form pulp with the solid content of 20-25% and the pH value of more than 9, then sending the pulp into a ball mill for grinding, sending the pulp into a cyclone for classification, and sending the pulp into the leaching process after the pulp obtained by grinding reaches the condition that the mesh size of-200 is more than or equal to 80%.
2) Leaching: and (3) sending the ground pulp into a thickener for solid-liquid separation before leaching, adding a leaching agent and a pH value regulator into underflow pulp with the solid content of 65% obtained by the solid-liquid separation, leaching, washing and separating the leached pulp obtained by leaching for 4-5 times after leaching, sending the leached tailings obtained by washing and separating into a flotation process, merging the noble liquid obtained by washing and separating with the noble liquid obtained by solid-liquid separation in the thickener before leaching, adding zinc powder into the noble liquid for displacement treatment, displacing gold and silver from the noble liquid, and filtering by a plate frame to obtain gold mud.
In a specific embodiment, the leaching agent adopts an environment-friendly gold extracting agent of golden cicada, and the adding amount of the gold extracting agent is 300-1000g/t. The pH regulator is lime and is added in an amount to reach pH value of 10-12. The leaching treatment time was 36h.
In the replacement treatment, the addition amount of zinc powder is 50-250g/t, and the particle size of the zinc powder is-325 meshes not less than 95%.
3) Flotation procedure: adding 300-500g/t of active carbon into the leached tailings for removing the drugs, then adding sulfuric acid to adjust the pH value of the leached tailings to be 4.5-5.5, and then adding 400-500g/t of inhibitor, 200-300g/t of collector and 20-50g/t of foaming agent into the leached tailings to obtain rough concentrate and rough tailings through one-time roughing; then, scavenging the coarse tailings for three times, adding 100-150g/t of collector for each scavenging, and sending the scavenged tailings as flotation tailings to a harmless process; and (3) carrying out three times of concentration on the rough concentrate, wherein 150-300g/t of inhibitor is added in each concentration, and the concentration tailings are the sulfur concentrate.
In a specific embodiment, the inhibitor is guar gum or hydroxymethyl cellulose, the collector is water glass, butyl xanthate and No. 2 oil in a weight ratio of 8-10:5-9:1, and the foaming agent is polyethylene glycol ether or methyl isobutyl carbinol.
The roughing time is 5-30min, the single scavenging time is 20-60min, and the single refining time is 20-60min.
4) Refining: adding nitric acid solution into gold mud to perform impurity removal operation, then adding water to perform suction filtration, wherein the solid obtained by suction filtration is crude gold powder, the liquid phase obtained by suction filtration is silver noble liquid, adding aqua regia into the crude gold powder to perform gold dissolving operation, then performing suction filtration, adding sodium metabisulfite into the obtained gold noble liquid to perform gold reduction reaction, performing suction filtration after the reaction, and smelting the obtained gold powder to obtain gold ingots; the silver noble liquid is subjected to precipitation reaction by sodium chloride and then suction filtration, iron powder is added into the obtained filter cake to perform silver reduction reaction, then coarse silver powder is obtained through suction filtration, and then the coarse silver powder is smelted to form silver ingots.
In a specific embodiment, in the impurity removal operation, the concentration of the nitric acid solution is 15-30%, the solid-to-liquid ratio of the gold mud to the nitric acid solution is 1:1-1.5, the impurity removal temperature is 60-90 ℃, and the impurity removal time is 60-200min.
In the gold dissolving operation, the solid-liquid ratio of the crude gold powder to the aqua regia is 1:1-2, the temperature is 50-90 ℃ and the time is 1-12h.
The addition amount of the sodium metabisulfite is 0.5-1% of the weight of the gold noble liquid, and the gold reduction reaction time is 10-30min.
In the precipitation reaction, the solid-liquid ratio of the sodium chloride to the silver noble liquid is 1:1.5-3, and the precipitation time is 40-90min.
In the silver reduction reaction, the addition amount of iron powder is 100-300g/kg, the temperature is 20-40 ℃ and the time is 3-6h.
The smelting temperature of the gold powder and the crude silver powder is 1000-1200 ℃.
5) Harmless working procedure: the flotation tailings are sent to a filter press for pressure filtration and dehydration, backwater is sent to a flotation process for recycling, the obtained filter residues are sent to a stirring barrel, water is added to form filter residue slurry with the solid content of 25%, then a reagent-removing detergent is added to be mixed uniformly, the filter residue slurry is sent to a reaction tank, oxidizing gas is introduced into the reaction tank for oxidation and decomposition reaction, after the reaction is finished, reaction products are washed, water is obtained by washing for recycling, and the obtained filter residues are sold as light brick raw materials or cement auxiliary materials after filter pressing.
In a specific embodiment, the detergent is a hydrogen peroxide solution with the concentration of 20-30%, and the adding amount is 50-300g/t. The oxidizing gas is ozone, and the ozone inlet amount is 5-20m 3 And/h. The oxidative decomposition reaction time is 0.5-5h.
As an improvement to the previous implementation, the underflow slurry is leached in an ultrasonic environment during the leaching treatment; the ultrasonic environment is provided by sinusoidal ultrasonic wave and variable frequency ultrasonic wave in alternating sequence of sine-variable frequency-sine-variable frequency, the frequency of the sinusoidal ultrasonic wave is 20-40KHz, and the power is 300mW/cm 2 The method comprises the steps of carrying out a first treatment on the surface of the The frequency of the variable frequency ultrasonic wave is 30-50KHz, and the power is 250mW/cm 2 。
Ultrasonic intervention is carried out during leaching, ultrasonic cavitation is utilized to promote gold and silver to be dissolved out, ultrasonic cavitation bubbles with different frequencies and powers are utilized to reduce dead angles caused by standing waves, the growth and collapse of the cavitation bubbles can generate shearing force in underflow slurry, different elements on the surface of the ore are dissociated to different degrees due to the difference of binding force, so that cracks or pores are generated on the surface of the ore more strongly, the surface of the ore is cracked earlier and faster, the mass transfer speed between the leaching agent and the ore is increased, the mass transfer surface area is increased, the leaching agent is assisted to improve the dissolution speed, the extraction rate and the yield of gold and silver, the leaching treatment time is shortened, and the time cost is saved.
As a further improvement to the previous implementation, 50-200g/t of leaching aid is also added into the underflow slurry during leaching treatment, and the leaching aid comprises mercaptosuccinic acid and dimethylolurea in a weight ratio of 1:1-2.
The addition of the leaching auxiliary agent can link with elements with higher activity on the surface of the ore by virtue of active groups of the leaching auxiliary agent, so that the hydrophilicity of the ore is increased, the dispersibility of the ore in the underflow slurry is better, the contact and collision opportunities of the ore and the leaching agent are increased, gold elements in the underflow slurry are fully complexed, the dissolution speed of gold and silver is increased, the leaching rate of gold and silver is promoted, the leaching time is shortened, and the extraction rate, the recovery rate and the production efficiency of gold and silver are improved. Meanwhile, the leaching aid can increase connectivity of gaps between insoluble calcium salt and ore by utilizing hydrophilicity, so that gold and silver leaching efficiency in the later stage of leaching treatment is reduced due to the fact that calcium ions deposit calcium carbonate or calcium sulfate precipitate on the surface of the ore in an alkaline environment, and a higher gold and silver leaching rate can be maintained in the later stage of leaching treatment.
The present invention will be described in further detail with reference to examples.
Example 1:
in this example, the main components and contents of the gold concentrate raw material are shown in Table 1 below.
TABLE 1 Main Components and content (%) (Au, ag units: g/t) of gold concentrate
In the embodiment, the comprehensive recycling method of the high-grade multi-element gold concentrate comprises the following steps:
1) Grinding: adding water into the raw materials, stirring to form primary pulp with the solid content of 20%, adding lime and noble liquid recycled from the leaching process, stirring to form pulp with the solid content of 20% and the pH value of more than 9, then sending the pulp into a ball mill for grinding, sending the pulp into a cyclone for classification, and sending the pulp into the leaching process after the pulp obtained by grinding reaches the condition that the pulp size is more than or equal to 80% of minus 200 meshes.
2) Leaching: the method comprises the steps of feeding ground pulp into a thickener for solid-liquid separation before leaching, adding 300g/t of leaching agent, namely environment-friendly gold extraction agent for golden cicada and pH value regulator, namely lime into underflow pulp with the solid content of 65% obtained by solid-liquid separation, adjusting the pH value of the underflow pulp to 10 by lime, leaching for 36 hours, washing and separating leached pulp obtained by leaching for 4 times, feeding leached tailings obtained by washing and separating into a flotation process, mixing the precious liquid obtained by washing and separating with the precious liquid obtained by solid-liquid separation in the thickener before leaching, adding 50g/t of zinc powder with the particle size of-325 meshes of more than or equal to 95% into the precious liquid for replacement treatment, replacing gold and silver from the precious liquid, and filtering by a plate frame to obtain gold mud.
3) Flotation procedure: adding 300g/t of activated carbon into leached tailings for removing drugs, then adding sulfuric acid to adjust the pH value of the leached tailings to be 4.5, adding 400g/t of inhibitor, 200g/t of collector and 20g/t of foaming agent, and performing primary roughing to obtain rough concentrate and rough tailings; then, scavenging the coarse tailings for three times, adding 100g/t of collector for each scavenging, and sending the scavenged tailings serving as flotation tailings to a harmless process; and (3) carrying out three times of concentration on the rough concentrate, wherein 150g/t inhibitor is added for each concentration, and the concentration tailings are the sulfur concentrate.
The inhibitor is Gul gum, the collector is water glass, butyl xanthate and No. 2 oil in a weight ratio of 8:5:1, and the foaming agent is polyethylene glycol ether.
The roughing time is 10min, the single scavenging time is 20min, and the single refining time is 20min.
4) Refining: adding a nitric acid solution with the concentration of 15% into gold mud according to the solid-to-liquid ratio of 1:1, performing impurity removal operation at the temperature of 60 ℃ for 60min, then adding water for suction filtration, obtaining solid which is coarse gold powder through suction filtration, obtaining liquid phase which is silver noble liquid, adding aqua regia into the coarse gold powder for gold dissolving operation, then performing suction filtration, adding sodium metabisulfite accounting for 0.5% of the weight of the gold noble liquid into the obtained gold noble liquid for gold reduction reaction for 10min, performing suction filtration after the reaction, and smelting the obtained gold powder at the temperature of 1000-1200 ℃ to obtain gold ingots. In the gold dissolving operation, the solid-liquid ratio of the crude gold powder to the aqua regia is 1:1, the temperature is 50 ℃, and the time is 2 hours.
Adding sodium chloride into the silver noble liquid in a solid-to-liquid ratio of 1:1.5 for precipitation reaction for 40min, performing suction filtration, adding 100g/kg of iron powder into the obtained filter cake, performing silver reduction reaction for 3h at the temperature of 20 ℃, performing suction filtration to obtain crude silver powder, and smelting the crude silver powder at the temperature of 1000-1200 ℃ to form silver ingots.
5) Harmless working procedure: filtering the flotation tailings in a filter press to dewater, returning water to a flotation process for recycling, feeding the obtained filter residues into a stirring barrel, adding water to form filter residue slurry with the solid content of 25%, adding 50g/t of a reagent-removing detergent-hydrogen peroxide solution with the concentration of 20%, uniformly mixing, feeding the filter residue slurry into a reaction tank, and introducing 5m of the filter residue slurry into the reaction tank 3 And (3) carrying out oxidative decomposition reaction on the oxidizing gas and ozone for 5 hours, washing reaction products after the reaction is finished, recycling washing water, and taking the obtained tailings as light brick raw materials or cement auxiliary materials for sale after filter pressing.
Example 2:
in this embodiment, the method for comprehensively recycling high-grade multi-element gold concentrate is different from embodiment 1 only in that:
1) Grinding: the solid content of the primary pulp is 40%, lime and the noble liquid recycled from the leaching process are added into the primary pulp, and the primary pulp is stirred to form the pulp with the solid content of 25% and the pH value of more than 9.
2) Leaching: the leaching agent-golden cicada environment-friendly gold extracting agent is added into the underflow slurry, the amount of the leaching agent-golden cicada environment-friendly gold extracting agent is 1000g/t, and the pH value of the underflow slurry is adjusted to 12 by the pH value regulator-lime; in the displacement treatment, 250g/t zinc powder was added to the pregnant solution.
3) Flotation procedure: the addition amount of the active carbon is 500g/, and the pH value of the tailings is adjusted to 5.5 by sulfuric acid; during roughing, 500g/t of inhibitor, 300g/t of collector and 50g/t of foaming agent are added, and the roughing time is 30min; 150g/t collector is added for each scavenging, and the single scavenging time is 60min; 300g/t inhibitor was added for each beneficiation, with a single beneficiation time of 60 minutes.
The inhibitor is hydroxymethyl cellulose, the collector is water glass, butyl xanthate and No. 2 oil in a weight ratio of 10:9:1, and the foaming agent is methyl isobutyl carbinol.
4) Refining: in the impurity removal operation, the concentration of the nitric acid solution is 30%, the solid-to-liquid ratio of the gold mud to the nitric acid solution is 1:1.5, the impurity removal temperature is 90 ℃, and the impurity removal time is 200min. In the gold dissolving operation, the solid-to-liquid ratio of the crude gold powder to the aqua regia is 1:2, the temperature is 90 ℃, and the time is 12 hours. The addition amount of sodium metabisulfite is 1% of the weight of the gold noble liquid, and the gold reduction reaction time is 30min. In the precipitation reaction, the solid-to-liquid ratio of sodium chloride to silver noble liquid is 1:3, and the precipitation time is 90min. In the silver reduction reaction, the addition amount of iron powder is 300g/kg, the temperature is 40 ℃ and the time is 6h.
5) Harmless working procedure: the detergent is 30% hydrogen peroxide solution with the addition amount of 300g/t. The oxidizing gas is ozone, and the ozone inlet amount is 20m 3 And/h. The oxidative decomposition reaction time was 0.5h.
Example 3:
in this embodiment, the method for comprehensively recycling high-grade multi-element gold concentrate is different from embodiment 1 only in that:
1) Grinding: the solid content of the primary pulp is 30%, lime and the noble liquid recycled from the leaching process are added into the primary pulp, and the primary pulp is stirred to form the pulp with the solid content of 23% and the pH value of more than 9.
2) Leaching: the leaching agent-golden cicada environment-friendly gold extracting agent is added into the underflow slurry, the amount of the leaching agent-golden cicada environment-friendly gold extracting agent is 850g/t, and the pH value of the underflow slurry is adjusted to 11 by the pH value regulator-lime; in the displacement treatment, 200g/t zinc powder was added to the pregnant solution.
3) Flotation procedure: the addition amount of the active carbon is 450g/, and the pH value of the tailings is adjusted to 5 by sulfuric acid; during roughing, 450g/t of inhibitor, 230g/t of collector and 25g/t of foaming agent are added, and the roughing time is 20min; 140g/t collector is added for each scavenging, and the single scavenging time is 40min; 200g/t inhibitor was added for each beneficiation, with a single beneficiation time of 40min.
The inhibitor is hydroxymethyl cellulose, the collector is water glass, butyl xanthate and No. 2 oil in a weight ratio of 8.5:6:1, and the foaming agent is polyethylene glycol ether.
4) Refining: in the impurity removal operation, the concentration of the nitric acid solution is 20%, the solid-to-liquid ratio of the gold mud to the nitric acid solution is 1:1.5, the impurity removal temperature is 70 ℃, and the impurity removal time is 100min. In the gold dissolving operation, the solid-to-liquid ratio of the crude gold powder to the aqua regia is 1:1.5, the temperature is 90 ℃, and the time is 6 hours. The addition amount of sodium metabisulfite is 0.8% of the weight of the gold noble liquid, and the gold reduction reaction time is 30min. In the precipitation reaction, the solid-to-liquid ratio of sodium chloride to silver noble liquid is 1:2.5, and the precipitation time is 60min. In the silver reduction reaction, the addition amount of iron powder is 180g/kg, the temperature is 35 ℃ and the time is 4.5h.
5) Harmless working procedure: the detergent is 25% hydrogen peroxide solution with an addition amount of 200g/t. The oxidizing gas is ozone, and the ozone inlet amount is 15m 3 And/h. The oxidative decomposition reaction time was 2.5 hours.
Example 4:
in this embodiment, the high-grade multi-element gold concentrate comprehensive recycling method is different from embodiment 3 only in that:
2) Leaching: during leaching treatment, the underflow slurry is leached out in an ultrasonic environmentIs a kind of device for the treatment of a cancer; the ultrasonic environment is provided by sine state ultrasonic wave with frequency of 30KHz and power of 300mW/cm and frequency-variable ultrasonic wave with alternating sequence of sine-variable frequency-sine-variable frequency 2 The method comprises the steps of carrying out a first treatment on the surface of the The frequency of the variable frequency ultrasonic wave is 45KHz, and the power is 250mW/cm 2 。
Example 5:
in this embodiment, the high-grade multi-element gold concentrate comprehensive recycling method is different from embodiment 3 only in that:
2) Leaching: during leaching treatment, 120g/t of leaching aid is also added into the underflow slurry, and the leaching aid comprises mercaptosuccinic acid and dimethylolurea in a weight ratio of 1:1.5.
Example 6:
in this embodiment, the high-grade multi-element gold concentrate comprehensive recycling method is different from embodiment 4 only in that:
2) Leaching: during leaching treatment, 120g/t of leaching aid is also added into the underflow slurry, and the leaching aid comprises mercaptosuccinic acid and dimethylolurea in a weight ratio of 1:1.5.
Comparative example 1:
in this embodiment, the high-grade multi-element gold concentrate comprehensive recycling method is different from embodiment 3 only in that:
2) Leaching: during leaching treatment, the underflow slurry is leached out in an ultrasonic environment; the ultrasonic environment is provided by sinusoidal ultrasonic wave with frequency of 30KHz and power of 300mW/cm 2 。
Comparative example 2:
in this embodiment, the high-grade multi-element gold concentrate comprehensive recycling method is different from embodiment 4 only in that:
2) Leaching: during leaching treatment, 120g/t of leaching aid is also added into the underflow slurry, and the leaching aid is mercaptosuccinic acid.
Comparative example 3:
in this embodiment, the high-grade multi-element gold concentrate comprehensive recycling method is different from embodiment 4 only in that:
2) Leaching: during leaching treatment, 120g/t of leaching aid is also added into the underflow slurry, and the leaching aid is dimethylol urea.
Test example 1:
and (3) production index evaluation: comprehensive recovery of gold concentrate was performed according to the methods of example 3-example 6 and comparative example 1-comparative example 3, respectively, and recovery rates of the finally obtained products (gold ingot, silver ingot, sulfur concentrate) were uniformly measured and calculated using the raw materials of example 1 as uniform raw materials, and the results are shown in table 2. Each example and comparative example was provided with 3 sets of replicates and averaged.
TABLE 2 quality index of products of different methods
From comparison of the results, the recovery rates of gold, silver and sulfur show significant differences according to the different methods, wherein the recovery rate of example 4 and example 5 are better than that of example 3 to different degrees, and the recovery rate of example 6 is optimal; the results of comparative example 1 are better than those of example 3, but worse than those of example 4; the results of comparative example 2 and comparative example 3 are better than those of example 4, but worse than those of example 6. It is explained that, on the basis of example 3, optimizing the recovery method can improve the recovery rate of the main element (gold and silver), and the recovery rate of sulfur element is not greatly affected, and the effect of using ultrasonic waves of different frequencies and powers in example 4 is superior to that of the single ultrasonic wave in comparative example 1; example 5 also improved gold and silver recovery using a leaching aid, but in comparison with example 6 it was found that the combination of ultrasonic leaching and a leaching aid in example 6 was most effective.
Test example 2:
leaching Rate test
The test method comprises the following steps: leaching tests are carried out according to the parameters related to the leaching procedures in the methods of the examples 3-6 and the comparative examples 1-3 respectively, mixed slurry of the leaching agent and the pH value regulator is prepared, waste circuit boards containing gold are taken as raw materials, the circuit boards are respectively put into each group of mixed slurry, leaching operation is carried out according to the parameters of leaching treatment in the methods of each group, the circuit boards are taken out and weighed at intervals, the weight difference is taken as a measurement value of the dissolution rate, meanwhile, the dissolution condition of gold on the circuit boards is observed, and the dissolution rate of the whole leaching treatment process is compared. Each example and comparative example was provided with 3 sets of replicates and averaged. The results are shown in FIG. 1.
It was observed that example 6 started to dissolve first, 10min later, example 4 started to dissolve, 17min later, comparative examples 2 and 3, and 13min later, example 5 and comparative example 1 started to dissolve, example 3 finally started to dissolve, and for a total of 6.5h, all the gold on the circuit boards was not dissolved.
Fig. 1 is a schematic diagram showing the dissolution rate of gold on a circuit board under different conditions. From the results of fig. 1 and observations, it is found that the dissolution rate of example 6 is the fastest, the dissolution rate of example 3 is the slowest, and comparative examples 3, 4, and 6 find that the dissolution rate of example 6 is still fast in the later stage of the leaching process, and that the dissolution rates of examples 3 and 4 have a significant tendency to decrease in the later stage.
Comprehensive description shows that ultrasonic intervention is performed by adopting ultrasonic waves with different frequencies and powers during leaching treatment, so that cracks or pores can appear on the surface of the ore earlier and faster, the mass transfer speed between the leaching agent and the ore is increased, the mass transfer surface area is increased, the leaching agent is assisted to improve the dissolution speed, the extraction rate and the yield of gold and silver, and meanwhile, the time of leaching treatment can be shortened. Meanwhile, the leaching aid is added to increase the contact and collision opportunities of the ore and the leaching agent, so that the dissolution speed of gold and silver is increased, the leaching rate of gold and silver is promoted, the leaching time is shortened, and in the later stage of leaching treatment, the leaching aid can enable the ore to keep higher leaching rate of gold and silver, so that the extraction rate, the recovery rate and the production efficiency of gold and silver are improved.
In the present invention, the concentration, the proportion, etc. which are not specifically described are weight concentration, weight ratio, etc. which are common writing habits of those skilled in the art, and therefore are not described in detail in the present invention.
It should be noted that, in the present invention, specific details of some operations are not described in detail, but are known in the prior art by those skilled in the art, so they are not described herein.
Finally, it should be noted that the above embodiments are merely illustrative of the technical solution of the present invention, and not limiting thereof; although the invention has been described in detail with reference to the foregoing embodiments, those of ordinary skill in the art will appreciate that; the technical scheme described in the foregoing embodiments can be modified or some or all of the technical features thereof can be replaced by equivalents; such modifications and substitutions do not depart from the spirit of the invention.
Claims (9)
1. The comprehensive recovery and utilization method for the high-grade multi-element gold concentrate is characterized by comprising the following steps of: grinding and grading the raw materials to obtain ground pulp; leaching and replacing the ground pulp to obtain gold mud and leached tailings; a flotation process of carrying out flotation treatment on the leached tailings to obtain sulfur concentrate and flotation tailings; refining the gold mud to obtain gold ingots and silver ingots; and a harmless treatment step of performing a harmless treatment on the flotation tailings;
the grain size of the ground pulp is-200 meshes and is more than or equal to 80 percent;
the leaching process comprises the following steps: sending ground pulp into a thickener for solid-liquid separation before leaching, adding a leaching agent and a pH value regulator into underflow pulp with the solid content of 65% obtained by the solid-liquid separation, leaching, washing and separating leached pulp for 4-5 times after leaching, sending leached tailings obtained by washing and separating into a flotation process, merging noble liquid obtained by washing and separating with noble liquid obtained by solid-liquid separation in the thickener before leaching, adding zinc powder into the noble liquid for replacement treatment, replacing gold and silver from the noble liquid, and filtering by a plate frame to obtain gold mud;
the leaching agent used in the leaching treatment is an environment-friendly gold extracting agent for golden cicadas; the replacement treatment adopts zinc powder for replacement; the leaching positionWhen the method is used, the underflow slurry is leached out in an ultrasonic environment; the ultrasonic environment is provided by sine state ultrasonic wave and frequency conversion ultrasonic wave in alternating sequence of sine-frequency conversion-sine-frequency conversion, the frequency of the sine state ultrasonic wave is 20-40KHz, and the power is 300mW/cm 2 The method comprises the steps of carrying out a first treatment on the surface of the The frequency of the variable frequency ultrasonic wave is 30-50KHz, and the power is 250mW/cm 2 ；
During the leaching treatment, 50-200g/t of leaching auxiliary agent is also added into the underflow slurry, and the leaching auxiliary agent comprises mercaptosuccinic acid and dimethylolurea in a weight ratio of 1:1-2;
in the raw material, the content of gold is more than 200.00g/t, the content of silver is more than 10.00g/t, and the content of sulfur is more than 3%.
2. The method for comprehensively recycling high-grade multi-element gold concentrate according to claim 1, which is characterized in that: the adding amount of the leaching agent is 300-1000g/t; the pH value regulator is lime, and the addition amount of the lime reaches 10-12 in terms of pH value; the leaching treatment time is 36 hours; the addition amount of the zinc powder is 50-250g/t, and the particle size of the zinc powder is-325 meshes not less than 95%.
3. The method for comprehensively recycling high-grade multi-element gold concentrate according to claim 1, which is characterized in that: the ore grinding process comprises the following steps: adding water into the raw materials, stirring to form primary pulp with the solid content of 20-40%, adding lime and noble liquid recycled from the leaching process, stirring to form pulp with the solid content of 20-25% and the pH value of more than 9, then sending the pulp into a ball mill for grinding, sending the pulp into a cyclone for classification, and sending the pulp into the leaching process after the pulp obtained by grinding reaches the condition that the mesh size of-200 is more than or equal to 80%.
4. The method for comprehensively recycling high-grade multi-element gold concentrate according to claim 1, which is characterized in that: the flotation process comprises the following steps: adding 300-500g/t of active carbon into the leached tailings for removing the drugs, then adding sulfuric acid to adjust the pH value of the leached tailings to be 4.5-5.5, and then adding 400-500g/t of inhibitor, 200-300g/t of collector and 20-50g/t of foaming agent into the leached tailings to obtain rough concentrate and rough tailings through one-time roughing; then, scavenging the coarse tailings for three times, adding 100-150g/t of collector for each scavenging, and sending the scavenged tailings as flotation tailings to a harmless process; and (3) carrying out three times of concentration on the rough concentrate, wherein 150-300g/t of inhibitor is added in each concentration, and the concentration tailings are the sulfur concentrate.
5. The method for comprehensively recycling the high-grade multi-element gold concentrate according to claim 4, which is characterized in that: the inhibitor is guar gum or hydroxymethyl cellulose, the collector is water glass, butyl xanthate and No. 2 oil in a weight ratio of 8-10:5-9:1, and the foaming agent is polyethylene glycol ether or methyl isobutyl carbinol;
the roughing time is 5-30min, the single scavenging time is 20-60min, and the single refining time is 20-60min.
6. The method for comprehensively recycling high-grade multi-element gold concentrate according to claim 1, which is characterized in that: the refining process comprises the following steps: adding nitric acid solution into gold mud to perform impurity removal operation, then adding water to perform suction filtration, wherein the solid obtained by suction filtration is crude gold powder, the liquid phase obtained by suction filtration is silver noble liquid, adding aqua regia into the crude gold powder to perform gold dissolving operation, then performing suction filtration, adding sodium metabisulfite into the obtained gold noble liquid to perform gold reduction reaction, performing suction filtration after the reaction, and smelting the obtained gold powder to obtain gold ingots;
the silver noble liquid is subjected to precipitation reaction by sodium chloride and then suction filtration, iron powder is added into the obtained filter cake to perform silver reduction reaction, then coarse silver powder is obtained through suction filtration, and then the coarse silver powder is smelted to form silver ingots.
7. The method for comprehensively recycling the high-grade multi-element gold concentrate according to claim 6, which is characterized in that: in the impurity removal operation, the concentration of the nitric acid solution is 15-30%, the solid-liquid ratio of the gold mud to the nitric acid solution is 1:1-1.5, the impurity removal temperature is 60-90 ℃, and the impurity removal time is 60-200min;
in the gold dissolving operation, the solid-to-liquid ratio of the crude gold powder to the aqua regia is 1:1-2, the temperature is 50-90 ℃ and the time is 1-12h;
the addition amount of the sodium metabisulfite is 0.5-1% of the weight of the gold noble liquid, and the gold reduction reaction time is 10-30min;
in the precipitation reaction, the solid-to-liquid ratio of sodium chloride to silver noble liquid is 1:1.5-3, and the precipitation time is 40-90min;
in the silver reduction reaction, the addition amount of iron powder is 100-300g/kg, the temperature is 20-40 ℃ and the time is 3-6h;
the smelting temperature of the gold powder and the crude silver powder is 1000-1200 ℃.
8. The method for comprehensively recycling high-grade multi-element gold concentrate according to claim 1, which is characterized in that: the harmless procedure comprises the following steps: the flotation tailings are sent to a filter press for pressure filtration and dehydration, backwater is sent to a flotation process for recycling, the obtained filter residues are sent to a stirring barrel, water is added to form filter residue slurry with the solid content of 25%, then a reagent-removing detergent is added to be mixed uniformly, the filter residue slurry is sent to a reaction tank, oxidizing gas is introduced into the reaction tank for oxidation and decomposition reaction, after the reaction is finished, reaction products are washed, water is obtained by washing for recycling, and the obtained filter residues are sold as light brick raw materials or cement auxiliary materials after filter pressing.
9. The method for comprehensively recycling the high-grade multi-element gold concentrate according to claim 8, which is characterized in that: the medicine-removing detergent is hydrogen peroxide solution with the concentration of 20-30%, and the adding amount is 50-300g/t; the oxidizing gas is ozone, and the ozone inlet amount is 5-20m 3 /h; the oxidative decomposition reaction time is 0.5-5h.
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| CN1361295A (en) * | 2000-12-27 | 2002-07-31 | 中国科学院化工冶金研究所 | Direct zinc sulfide concentrate leaching-out process with coupled synergic leaching-out and solvent extraction and separation |
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| AU2021104912A4 (en) * | 2021-08-04 | 2021-09-30 | Dawei Feng | Method for Recovering Gold from Auriferous Tailings |
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| CN1361295A (en) * | 2000-12-27 | 2002-07-31 | 中国科学院化工冶金研究所 | Direct zinc sulfide concentrate leaching-out process with coupled synergic leaching-out and solvent extraction and separation |
| CN101451192A (en) * | 2007-11-28 | 2009-06-10 | 灵宝市金源矿业有限责任公司 | Comprehensive recovery method for directly cyanating and intensified leaching multi-metal gold ore concentrate |
| AU2021104912A4 (en) * | 2021-08-04 | 2021-09-30 | Dawei Feng | Method for Recovering Gold from Auriferous Tailings |
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