CN115572835B - Water chlorination gold extraction method for micro-fine particle gold-containing material - Google Patents
Water chlorination gold extraction method for micro-fine particle gold-containing material Download PDFInfo
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- CN115572835B CN115572835B CN202211193079.5A CN202211193079A CN115572835B CN 115572835 B CN115572835 B CN 115572835B CN 202211193079 A CN202211193079 A CN 202211193079A CN 115572835 B CN115572835 B CN 115572835B
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- 239000010931 gold Substances 0.000 title claims abstract description 241
- 229910052737 gold Inorganic materials 0.000 title claims abstract description 217
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 title claims abstract description 216
- 239000000463 material Substances 0.000 title claims abstract description 112
- 238000005660 chlorination reaction Methods 0.000 title claims abstract description 56
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 33
- 238000000605 extraction Methods 0.000 title abstract description 42
- 239000010419 fine particle Substances 0.000 title description 7
- 239000000460 chlorine Substances 0.000 claims abstract description 81
- 238000002386 leaching Methods 0.000 claims abstract description 81
- 238000000034 method Methods 0.000 claims abstract description 60
- 229910052500 inorganic mineral Inorganic materials 0.000 claims abstract description 55
- 239000011707 mineral Substances 0.000 claims abstract description 55
- 238000006243 chemical reaction Methods 0.000 claims abstract description 35
- AMWRITDGCCNYAT-UHFFFAOYSA-L manganese oxide Inorganic materials [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 claims abstract description 34
- 229910001385 heavy metal Inorganic materials 0.000 claims abstract description 30
- 238000005204 segregation Methods 0.000 claims abstract description 28
- 230000008569 process Effects 0.000 claims abstract description 27
- 229910052801 chlorine Inorganic materials 0.000 claims abstract description 24
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims abstract description 23
- 238000004090 dissolution Methods 0.000 claims abstract description 21
- 238000005859 coupling reaction Methods 0.000 claims abstract description 17
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 16
- 229910052751 metal Inorganic materials 0.000 claims abstract description 14
- 239000002184 metal Substances 0.000 claims abstract description 14
- 238000000926 separation method Methods 0.000 claims abstract description 14
- 239000010949 copper Substances 0.000 claims abstract description 12
- 239000011859 microparticle Substances 0.000 claims abstract description 9
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 6
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 6
- 239000011593 sulfur Substances 0.000 claims abstract description 6
- 239000011572 manganese Substances 0.000 claims description 74
- 150000002500 ions Chemical class 0.000 claims description 38
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 33
- 229910052748 manganese Inorganic materials 0.000 claims description 25
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 24
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 23
- 238000007254 oxidation reaction Methods 0.000 claims description 23
- 230000003647 oxidation Effects 0.000 claims description 22
- 239000002002 slurry Substances 0.000 claims description 22
- 229910052569 sulfide mineral Inorganic materials 0.000 claims description 20
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 claims description 18
- 238000010494 dissociation reaction Methods 0.000 claims description 16
- 230000005593 dissociations Effects 0.000 claims description 16
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 claims description 15
- 238000000227 grinding Methods 0.000 claims description 14
- 239000007788 liquid Substances 0.000 claims description 13
- 230000001590 oxidative effect Effects 0.000 claims description 13
- NIFIFKQPDTWWGU-UHFFFAOYSA-N pyrite Chemical compound [Fe+2].[S-][S-] NIFIFKQPDTWWGU-UHFFFAOYSA-N 0.000 claims description 13
- 229910052683 pyrite Inorganic materials 0.000 claims description 13
- 239000011028 pyrite Substances 0.000 claims description 13
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 12
- 238000003723 Smelting Methods 0.000 claims description 12
- 230000002378 acidificating effect Effects 0.000 claims description 12
- 238000002156 mixing Methods 0.000 claims description 11
- 230000033116 oxidation-reduction process Effects 0.000 claims description 11
- 230000001105 regulatory effect Effects 0.000 claims description 10
- 238000001179 sorption measurement Methods 0.000 claims description 10
- 230000003197 catalytic effect Effects 0.000 claims description 9
- 239000002245 particle Substances 0.000 claims description 9
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 8
- 239000007787 solid Substances 0.000 claims description 8
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 7
- 229910052799 carbon Inorganic materials 0.000 claims description 7
- 238000006056 electrooxidation reaction Methods 0.000 claims description 7
- 229910001437 manganese ion Inorganic materials 0.000 claims description 7
- 238000003756 stirring Methods 0.000 claims description 7
- 125000001309 chloro group Chemical group Cl* 0.000 claims description 6
- 239000013081 microcrystal Substances 0.000 claims description 6
- 229910052759 nickel Inorganic materials 0.000 claims description 6
- 239000002893 slag Substances 0.000 claims description 6
- 229910052964 arsenopyrite Inorganic materials 0.000 claims description 5
- MJLGNAGLHAQFHV-UHFFFAOYSA-N arsenopyrite Chemical compound [S-2].[Fe+3].[As-] MJLGNAGLHAQFHV-UHFFFAOYSA-N 0.000 claims description 5
- 239000006229 carbon black Substances 0.000 claims description 5
- 229910052951 chalcopyrite Inorganic materials 0.000 claims description 5
- DVRDHUBQLOKMHZ-UHFFFAOYSA-N chalcopyrite Chemical compound [S-2].[S-2].[Fe+2].[Cu+2] DVRDHUBQLOKMHZ-UHFFFAOYSA-N 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 5
- 230000035484 reaction time Effects 0.000 claims description 5
- 239000004566 building material Substances 0.000 claims description 4
- 238000006555 catalytic reaction Methods 0.000 claims description 4
- 238000002360 preparation method Methods 0.000 claims description 4
- 229910052952 pyrrhotite Inorganic materials 0.000 claims description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 3
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 3
- 239000000919 ceramic Substances 0.000 claims description 3
- 150000001804 chlorine Chemical class 0.000 claims description 3
- -1 chlorine ions Chemical class 0.000 claims description 3
- NEHMKBQYUWJMIP-UHFFFAOYSA-N chloromethane Chemical compound ClC NEHMKBQYUWJMIP-UHFFFAOYSA-N 0.000 claims description 3
- 229910017604 nitric acid Inorganic materials 0.000 claims description 3
- 238000010979 pH adjustment Methods 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims description 2
- 230000000087 stabilizing effect Effects 0.000 claims description 2
- VRRFSFYSLSPWQY-UHFFFAOYSA-N sulfanylidenecobalt Chemical compound [Co]=S VRRFSFYSLSPWQY-UHFFFAOYSA-N 0.000 claims description 2
- 239000003795 chemical substances by application Substances 0.000 abstract description 12
- 229910052785 arsenic Inorganic materials 0.000 abstract description 10
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 abstract description 10
- XFXPMWWXUTWYJX-UHFFFAOYSA-N Cyanide Chemical compound N#[C-] XFXPMWWXUTWYJX-UHFFFAOYSA-N 0.000 abstract description 8
- 229910052787 antimony Inorganic materials 0.000 abstract description 8
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 abstract description 8
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 abstract description 7
- 229910052802 copper Inorganic materials 0.000 abstract description 7
- 229910052742 iron Inorganic materials 0.000 abstract description 7
- 239000002253 acid Substances 0.000 abstract description 5
- 230000008878 coupling Effects 0.000 abstract description 5
- 238000010168 coupling process Methods 0.000 abstract description 5
- 230000010718 Oxidation Activity Effects 0.000 abstract description 4
- 238000004064 recycling Methods 0.000 abstract description 4
- 230000006641 stabilisation Effects 0.000 abstract description 4
- 238000011105 stabilization Methods 0.000 abstract description 4
- 230000006378 damage Effects 0.000 abstract description 3
- 238000003912 environmental pollution Methods 0.000 abstract description 2
- 238000005272 metallurgy Methods 0.000 abstract description 2
- 229920006395 saturated elastomer Polymers 0.000 description 12
- 239000012141 concentrate Substances 0.000 description 9
- FDWREHZXQUYJFJ-UHFFFAOYSA-M gold monochloride Chemical compound [Cl-].[Au+] FDWREHZXQUYJFJ-UHFFFAOYSA-M 0.000 description 9
- 239000002994 raw material Substances 0.000 description 9
- 229910052736 halogen Inorganic materials 0.000 description 7
- 150000002367 halogens Chemical class 0.000 description 7
- 229910003771 Gold(I) chloride Inorganic materials 0.000 description 6
- 150000002739 metals Chemical class 0.000 description 5
- 238000011084 recovery Methods 0.000 description 5
- 239000002351 wastewater Substances 0.000 description 5
- 230000009286 beneficial effect Effects 0.000 description 4
- 230000033228 biological regulation Effects 0.000 description 4
- 230000001276 controlling effect Effects 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- WQYVRQLZKVEZGA-UHFFFAOYSA-N hypochlorite Chemical compound Cl[O-] WQYVRQLZKVEZGA-UHFFFAOYSA-N 0.000 description 4
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 4
- 229910052976 metal sulfide Inorganic materials 0.000 description 4
- 238000001556 precipitation Methods 0.000 description 4
- 230000001603 reducing effect Effects 0.000 description 4
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 3
- 239000003814 drug Substances 0.000 description 3
- MXZVHYUSLJAVOE-UHFFFAOYSA-N gold(3+);tricyanide Chemical compound [Au+3].N#[C-].N#[C-].N#[C-] MXZVHYUSLJAVOE-UHFFFAOYSA-N 0.000 description 3
- 239000011268 mixed slurry Substances 0.000 description 3
- 239000012071 phase Substances 0.000 description 3
- 238000005728 strengthening Methods 0.000 description 3
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 2
- 239000012298 atmosphere Substances 0.000 description 2
- 239000000969 carrier Substances 0.000 description 2
- 229910017052 cobalt Inorganic materials 0.000 description 2
- 239000010941 cobalt Substances 0.000 description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 2
- INPLXZPZQSLHBR-UHFFFAOYSA-N cobalt(2+);sulfide Chemical compound [S-2].[Co+2] INPLXZPZQSLHBR-UHFFFAOYSA-N 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000005538 encapsulation Methods 0.000 description 2
- 229910003439 heavy metal oxide Inorganic materials 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- 239000007800 oxidant agent Substances 0.000 description 2
- 238000004886 process control Methods 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 239000011343 solid material Substances 0.000 description 2
- 239000007790 solid phase Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 230000009466 transformation Effects 0.000 description 2
- 238000009279 wet oxidation reaction Methods 0.000 description 2
- NMKSBNZBSLHAKW-UHFFFAOYSA-N Cl.ClO Chemical compound Cl.ClO NMKSBNZBSLHAKW-UHFFFAOYSA-N 0.000 description 1
- DKNPRRRKHAEUMW-UHFFFAOYSA-N Iodine aqueous Chemical compound [K+].I[I-]I DKNPRRRKHAEUMW-UHFFFAOYSA-N 0.000 description 1
- WAEMQWOKJMHJLA-UHFFFAOYSA-N Manganese(2+) Chemical compound [Mn+2] WAEMQWOKJMHJLA-UHFFFAOYSA-N 0.000 description 1
- ZMZDMBWJUHKJPS-UHFFFAOYSA-M Thiocyanate anion Chemical compound [S-]C#N ZMZDMBWJUHKJPS-UHFFFAOYSA-M 0.000 description 1
- PFRUBEOIWWEFOL-UHFFFAOYSA-N [N].[S] Chemical compound [N].[S] PFRUBEOIWWEFOL-UHFFFAOYSA-N 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- KXZJHVJKXJLBKO-UHFFFAOYSA-N chembl1408157 Chemical compound N=1C2=CC=CC=C2C(C(=O)O)=CC=1C1=CC=C(O)C=C1 KXZJHVJKXJLBKO-UHFFFAOYSA-N 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- JFBJUMZWZDHTIF-UHFFFAOYSA-N chlorine chlorite Inorganic materials ClOCl=O JFBJUMZWZDHTIF-UHFFFAOYSA-N 0.000 description 1
- 238000010668 complexation reaction Methods 0.000 description 1
- 239000008139 complexing agent Substances 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- XLJMAIOERFSOGZ-UHFFFAOYSA-M cyanate Chemical compound [O-]C#N XLJMAIOERFSOGZ-UHFFFAOYSA-M 0.000 description 1
- 150000007973 cyanuric acids Chemical class 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000005188 flotation Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- QIYFTTFTJMLKAQ-UHFFFAOYSA-N gold manganese Chemical compound [Mn].[Au] QIYFTTFTJMLKAQ-UHFFFAOYSA-N 0.000 description 1
- ZMZDMBWJUHKJPS-UHFFFAOYSA-N hydrogen thiocyanate Natural products SC#N ZMZDMBWJUHKJPS-UHFFFAOYSA-N 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000010842 industrial wastewater Substances 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 230000036284 oxygen consumption Effects 0.000 description 1
- 238000006213 oxygenation reaction Methods 0.000 description 1
- 229920001021 polysulfide Polymers 0.000 description 1
- 239000005077 polysulfide Substances 0.000 description 1
- 150000008117 polysulfides Polymers 0.000 description 1
- 238000002203 pretreatment Methods 0.000 description 1
- 238000011112 process operation Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000012429 reaction media Substances 0.000 description 1
- 239000012066 reaction slurry Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000001226 reprecipitation Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000013535 sea water Substances 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 239000002210 silicon-based material Substances 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
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
- C22B11/06—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
- 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
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
Abstract
The invention belongs to the technical field of metallurgy, and particularly relates to a water chlorination gold extraction method of a micro-particle gold-containing material, which solves the coupling problem of inclusion mineral pretreatment and gold extraction technology by controlling the leaching system condition of gold material-manganese oxide mineral-acid chlorine solution, realizes one-step non-cyanide water chlorination extraction of the micro-particle gold material, realizes the processes of rapid dissolution and destruction of the inclusion gold mineral, high-efficiency output of Jin Lvhua agents, high oxidation activity voltage stabilization chlorination gold dissolution, heavy metal strong chlorination segregation extraction and the like in the same step, and has high metal segregation separation efficiency in the short-process material. And the refractory micro-particle package Jin Wuliao is treated by adopting a full wet process, the granularity of the reaction materials can be the granularity of a vulcanized mineral aggregate, the application range of the granularity is greatly widened, the adaptability to gold materials is strong, the high utilization rate of heavy metals such as iron, copper, arsenic, antimony and sulfur is realized, the produced gold-dissolving solution is convenient for separating and recovering gold and heavy metals, and the recycling of the materials and the process environmental pollution are small.
Description
Technical Field
The invention belongs to the technical field of metallurgy, and particularly relates to a water chlorination gold extraction method for a micro-fine particle gold-containing material.
Background
Gold is in the form of micro-particles or microcrystal precipitation and is a typical refractory gold ore, and particularly the effective dissociation granularity of gold is below 0.010 mm. Gold in the refractory gold-containing material is separated out in a microscopic particle or microcrystal way, is tightly wrapped in gold-carrying sulfide minerals, and is necessarily subjected to splitting or reconstruction of an outer wrapping structure of Jin Liuhua-carrying minerals such as pyrite, chalcopyrite, arsenopyrite, stibium and the like before gold extraction. Because gold is in an occurrence state in the form of extremely fine particles or microcrystal precipitation, a pretreatment method is needed before gold extraction, so that gold is fully exposed and then extracted, the gold leaching efficiency is obviously affected by pretreatment, the treatment flow is complex, and the multi-process regulation and control difficulty is high.
At present, in the aspect of pretreatment, pretreatment processes such as superfine grinding, fire roasting, wet oxidation and the like are often adopted to realize the exposure of gold in the gold-carrying material. In terms of superfine grinding and strengthening gold extraction (granularity is less than 0.01 mm), the defects are that: the material fine grinding is required to be high, the slurry regulation and control operation is relatively difficult, the carriers such as vulcanized minerals after fine grinding are mechanically reinforced and activated, the leaching oxidation activity is inappropriately enhanced, so that the leaching competition with gold becomes severe in the gold leaching operation, the gold leaching agent and the solution oxygen consumption are increased, and the gold extraction efficiency is lowered. When gold is extracted by fire roasting pretreatment, although mineral lattice damage or reconstruction can be promoted, gold-carrying materials are fully oxidized to expose microcrystalline gold, the method has the problems of high energy consumption, high emission, high pollution and the like, and the emission control difficulty of process gas is high. The existing wet oxidation pretreatment technology has relatively good active oxygen effect, but the required oxidant is large in dosage and high in cost, and the oxidation efficiency of refractory sulfide carriers difficult to oxidize is relatively low.
On the other hand, the existing gold leaching systems mainly comprise cyanide gold extraction, halogen and derivatives thereof gold extraction, sulfur nitrogen organic solvent gold extraction, polysulfide gold extraction and other systems. These systems have more or less limitations in terms of efficient extraction of the fine-grained gold. For example, sodium cyanide, thiocyanate, low-toxicity cyanate, etc., containing uncontrolled CN - . Gold extraction with thiourea in acid environment, thiourea is easy to oxidize and consume, and its concentration is equal to Fe 3+ The balance of the concentration of the oxidant needs to be strictly regulated, and the process stability is weak. For multiple casesThe sulfide gold extraction system has very complex process control, obvious and prominent solution ion influencing factors, such as Cu 2+ -ammine complex ion, cu 2+ Thiosulfate complex ions, the complex composition of materials is poorly adaptable. Halogen gold leaching systems, such as hypochlorous acid-hydrochloric acid, iodine-potassium iodide and the like, have the advantages of high gold extraction efficiency, strong adaptability, simple process control and the like, are widely reported, but the application of the halogen gold leaching agent is often limited by the cost of the halogen gold leaching agent, the recycling of halogen and the like due to the strong reactivity of the halogen gold leaching agent and the Jin Liuhua-loaded mineral.
Currently, in order to adapt to the influence of impurities such as copper, antimony, arsenic and the like on gold leaching process, halogen and derivatives thereof can be adopted to leach gold in alkaline or acid environments, and the application prospect of adopting chlorine and derivatives thereof is high and the cost is low. An efficient gold extraction process using chlorine and hypochlorite which are cheaper than cyanide by adjusting Cl 2 /Cl - 、ClO - /Cl - Complexation with Au to extract gold from the material can be expressed as:
2Au+2Cl 2 +2HCl＝2HAuCl 4 (1)
2Au+3Cl 2 +2NaCl＝2NaAuCl 4 (2)
2Au+3ClO - +6H + +5Cl - ＝2AuCl 4 - +3H 2 O (3)
2Au+ClO - +2H + +3Cl - ＝2AuCl 2 - +H 2 O (4)
the premise of effective gold leaching is by adding Cl 2 、ClO - Isogold agents, but due to AuCl 4 Au has a high redox potential, there is a potential for reprecipitation of Au, as shown in equation (5),
AuCl 4 - +3e＝Au+Cl - E 0 ＝1.0V(vs.NHE) (5)
when the system contains high-content Jin Liuhua mineral with reducing activity, the secondary precipitation trend of Au is more prominent, namely how to stabilize gold chloride complex ions is the technological applicationOne of the difficulties in promotion. In order to optimize the chloridizing gold leaching process, the system is controlled to contain saturated Cl 2 Or in high concentration of ClO - The strong oxidizing substances are easy to react with gold-loaded sulfide minerals in the materials, so that the consumption of the gold-loaded sulfide minerals in the chloridizing and gold-extracting process is greatly increased, and the leaching rate of the gold-loaded sulfide minerals is relatively slow. Or, manganese oxide active minerals are utilized to pretreat refractory gold materials to improve gold extraction efficiency, such as a method for leaching arsenic-containing carbonaceous gold ores from pyrolusite under high pressure and non-cyanide and a method for treating arsenic-containing antimony-containing gold materials from CN111154975A, wherein pyrolusite is used to oxidize arsenic-containing sulfide minerals, carbon or arsenic-containing antimony-containing materials and the like under high-temperature and high-pressure acidic systems, pretreated oxidation residues are repeatedly washed, then low-toxic cyanuric acid salt or hydrochloric acid and hypochlorite are added to extract gold, and the processes adopt a step treatment mode of material pre-oxidation and gold extraction, and the processes need to properly size mixing and adding gold dissolving agents, so that the processing flow is long and the regulation and control processes are complex.
In the current non-cyanide gold extraction process, the water chlorination method is effective in treating refractory gold ores or concentrates, gao Dijin, and research tends to be active. For conventional aqueous chlorination processes, aqueous chlorination process gold extraction is limited to higher levels of gold material that are difficult to oxidatively decompose sulfidic minerals: 1) The rate of chloridizing, oxidizing and decomposing sulfide inclusion is slower, and the consumption of the medicament is large; 2) The gold extraction process by chlorination is relatively difficult to form stable gold chloride complex ions, and is obviously influenced by reduction active reaction particles in the solution; 3) The equilibrium reaction of gold dissolution is limited by the redox state of the system, and the Cl required by the gold dissolution is chlorinated by water 2 /ClO - The saturation state is difficult to maintain stable. The disadvantage of this method is that: 1) Gold is in a solution phase in which complex ions of chloridizing leaching enter, and is influenced by oxidation-reduction states in the system, the stability of the complex ions of Jin Lvhua is relatively poor, and the gold extraction efficiency of chloridizing leaching is influenced easily due to secondary precipitation; by saturated Cl 2 High concentration ClO - In the case of equi-control, the influence of the reducing active sulfide mineral contained in the drug consumption receptor system is remarkable, and general drugsThe dosage consumption is quite large. 2) Gold precipitated in the sulphide minerals as micro-particles/crystallites, which has a relatively slow rate of oxidative leaching of sulphide minerals, especially FeS, which is relatively oxidation-inert 2 、Sb 2 S 3 And the like, the rate of chloridizing, oxidizing and dissolving to destroy the sulfide minerals is slow, so that the gold extraction rate is slow and the efficiency is low. 3) The chloridized gold extracting agent is added in a supplementary way, which is mostly represented by a chloridized gold complexing agent, an ionic solution or salt thereof, etc., for example, the initial gold leaching solution is added with a sufficient amount of Cl 2 /ClO - And the cost of the isogold medicament is high. 4) The comprehensive utilization rate of metal of gold-containing materials is low, and the problems of heavy metal ion recovery, gold-leaching tailing recycling and the like in the precious liquid obtained by gold leaching are easily ignored. Therefore, a new method needs to be developed to strengthen the stability of gold chloride complex ions, effectively avoid the influence of material reducing minerals, reduce the consumption of gold extraction agents by chlorination and improve the efficiency of the water chlorination process.
Disclosure of Invention
Aiming at the problems, the invention aims to provide a water chlorination gold extraction method of a micro-fine particle gold material, which is used for optimizing saturated Cl 2 The formation and stability of the chloridized gold-extracting derivative, the stability of the complex ion of the strengthening system Jin Lvhua, the rapid dissolution of the gold-coated sulfide mineral by catalysis, the reduction of the consumption of chloridized gold-extracting agent, and the like. In one aspect, the invention discloses a method for extracting gold from a fine-particle gold-containing material by water chlorination, which comprises the following steps:
crushing and grinding the fine gold ores to an effective dissociation granularity or below the effective dissociation granularity to obtain gold-containing materials;
mixing the gold-containing material and crushed and ground manganese oxide active mineral in proportion based on oxidation-reduction charge balance, and adding the mixture into a chlorine-containing system to obtain a mixture containing free H + Mixed acidic mineral slurries of Au-S (-II) -Mn (VI) -Cl (-I) ions;
carrying out coupling reaction leaching on the mixed acidic ore pulp of Au-S (-II) -Mn (VI) -Cl (-I), and dynamically regulating the oxidation-reduction state in a leaching system to obtain leaching slurry;
and carrying out solid-liquid separation on the leaching slurry to obtain gold-containing water chlorination extract Jin Guiye and chlorination segregation tailings.
Further, the coupling reaction comprises the oxidation catalysis of high-valence manganese to produce chlorine and derivatives thereof, the stable dissolution of gold by chlorination and high-valence manganese ion Mn 4+ And the derivative thereof carries out electrochemical oxidation catalytic dissolution and heavy metal chloridization segregation leaching on sulfide inclusion in the gold-containing material.
Further, the high-valence manganese oxidation catalysis chlorine production and the derivative thereof comprise the following reaction formula:
MnO 2 +4H + +4Cl - →MnCl 2 +Cl 2 +2H 2 O；
2Au+2Cl 2 +2HCl→2HAuCl 4 ；
2Au+3Cl 2 +2NaCl→2NaAuCl 4 ；
the chloridized stable gold dissolution comprises the following reaction formula:
2Au+3ClO - +6H + +5Cl - →2AuCl 4 - +3H 2 O；
2Au+ClO - +2H + +3Cl - →2AuCl 2 - +H 2 O；
the high valence Mn ion Mn 4+ The electrochemical oxidation catalytic dissolution of sulfide inclusion in gold-containing materials by the derivatives thereof comprises the following reaction formula:
MnO 2 +MeS+4H + →Mn 2+ +S 0 +Me x+ (aq)+2H 2 O；
4MnO 2 +MeS+8H + →Mn 2+ +SO 4 2- +Me x+ (aq)+4H 2 O；
the heavy metal chloridizing segregation leaching comprises the following reaction formula:
MeO x +Cl 2 +2H + →MeCl x +Cl - +H 2 O。
further, the micro-fine gold ore is a gold material taking a pyrite mineral as a carrier, and the pyrite mineral comprises: pyrite, chalcopyrite, pyrrhotite, nickel/cobalt sulphide ore, arsenopyrite and stibium ore;
the Au content in the micro-fine gold ore is 0.1-300 g/t, and the sulfur content is 5-40%;
the Au is in micro-particles or microcrystals to be separated out and wrapped by sulfide minerals;
the effective dissociation particle size is less than 0.01mm; the prepared grinding fineness of the gold-containing material is less than 0.074mm and is more than or equal to 60 percent.
Further, the effective dissociation particle size is an effective dissociation particle size of the sulfide mineral encapsulation aggregate.
Further, the gold-containing material and the crushed and ground manganese oxide active mineral are configured according to the mass molar ratio of S to Mn in the material of 1:4-1:6.
Further, the manganese oxidation active mineral is a material containing high-valence manganese oxide, and comprises one or more of manganese dioxide, pyrolusite, manganese nodule, hydromanganese ore and manganese oxide smelting slag;
wherein, mn in the manganese oxidation active mineral 4+ /Mn 3+ The content is 10-63%.
Further, the chlorine-containing system is a chlorine-containing system - The solution system H is regulated by adding hydrochloric acid + With Cl - Effective ion concentration.
Further, when free Cl in the chlorine-containing system - /H + When the concentration is insufficient, hydrochloric acid, sulfuric acid and nitric acid are adopted for blending;
wherein, the addition amount of the hydrochloric acid and the Mn of high valence manganese ions in the free chlorine ions and the manganese oxidation active minerals 4+ In terms of mass molar ratio Cl - (H + ):Mn 4+ Is configured in a ratio of 1:2 to 1:6.
Further, during the coupling reaction: the temperature is 120-250 ℃ and the pressure is 0.2-4.0 MPa; high valence manganese ions and Cl in the leaching system - Produced Cl 2 In a saturated chlorine state.
Further, the liquid-solid ratio in the leaching slurry is 2:1-10:1, and free H + The concentration is 0.5-5 mol/L, the reaction time is 0.5-6 h, and the stirring speed is 100-600 r/min.
Further, the gold-containing water chloridizing gold-extracting noble liquid is adsorbed by active carbon, and the active carbon with high Au chloridizing complex ion content and heavy metal ion-containing solution are obtained through adsorption separation;
the active carbon with high Au chloride complex ion content is used for smelting gold;
the solution containing heavy metal ions adopts a pH adjustment mode to recycle metal in a gradient way, wherein the metal comprises Mn 2+ 、Fe 3+ And Cu 2+ 。
On the other hand, the water chlorination extract Jin Guiye containing gold obtained by the method can be used for gold smelting, and the obtained chlorination segregation tailings can be applied to the preparation of white carbon black, ceramics and building materials.
The invention has the beneficial effects that:
the invention overcomes the coupling problem of inclusion mineral pretreatment and gold extraction process by controlling the leaching system condition of gold material-manganese oxide mineral-acid chlorine solution, so as to contain Mn 4+ Cl in the material catalytic solution medium - Cl produced by oxidation 2 The gold dissolving agent is not needed to be added in the process, and the system is caused to be in Cl by controlling the reaction atmosphere such as the slurry temperature, the slurry pressure and the like 2 Saturated state of gold-dissolving water chloridizing to stabilize AuCl 4、 AuCl 2 - Waiting for the output of chlorinated complex ions; in the same step by Mn 4+ (MnO 2 /Mn 2+ Pair, oxidation-reduction potential E 0 =1.23V (vs. nhe)) and strong oxidative activity mno·oh (mno·oh/Mn) produced during dissolution 2+ Pair, oxidation-reduction potential E 0 Intermediate active derivatives such as =1.53V) to promote Cl 2 To ClO - The trend of equilibrium transformation is enhanced, and ClO in the gold dissolving process of chlorination is further enhanced and cooperated - To stabilize the formation of Jin Lvhua complex ions; in the same step, mn 4+ The sulfide inclusion is subjected to electrochemical oxidation catalytic dissolution by the derivative thereof, so that the mineral crystal lattice is destroyed; in the same step, saturated, high-permeability Cl 2 The heavy metal minerals of the materials are chloridized and separated, so that the heavy metal oxides and the sulphide minerals enter the solution after being chloridized and separated and dissolved, the extraction of the heavy metals in the materials is realized, the intensified chloridization and separation of the heavy metal ions of the materials are synchronously realized,gold in the micro-fine gold material is efficiently recovered, heavy metal elements such as manganese, copper, iron, arsenic, antimony and the like are synchronously and comprehensively utilized, the recycling utilization rate is high, the recovery rate of gold and heavy metal reaches more than 98%, and the solid tailings after segregation and leaching can be used as raw materials of high-purity silicon materials, so that tailless emission of the materials is realized. The steps realize one-step non-cyanide water chlorination extraction of the micro-fine gold material, the same step realizes rapid dissolution and destruction of the coated gold mineral, high-efficiency output of Jin Lvhua agents, high oxidation activity pressure stabilization chlorination gold dissolution, heavy metal strong chlorination segregation extraction and the like, the process treatment flow is short, and the segregation and separation efficiency of the metals in the material is high.
The invention adopts the full wet process to treat refractory micro-particle package Jin Wuliao, the granularity of the reaction material can adopt the granularity of the sulfide mineral aggregate, the application range of granularity is greatly widened, the adaptability to gold materials is strong, the high utilization rate of heavy metals such as iron, copper, arsenic, antimony, sulfur and the like is realized, the produced gold-dissolving solution is convenient for separating and recovering gold and heavy metals, and the process environmental pollution is small. The method uses the water chlorination system to treat the gold-containing material and the manganese-containing material, has wide adaptability to the gold material, is simple in process operation and maintenance, realizes the simultaneous extraction of valuable metals in the gold-carrying material and the manganese-carrying material, and achieves the aims of high-efficiency comprehensive utilization and tailless emission of the materials by chloridizing and segregating the materials to obtain the high-quality silicon-based raw material.
Additional features and advantages of the invention will be set forth in the description which follows, and in part will be obvious from the description, or may be learned by practice of the invention. The objectives and other advantages of the invention may be realized and attained by the structure particularly pointed out in the written description and claims hereof as well as the appended drawings.
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 shows a flow chart of a method of aqueous chloridizing gold extraction of a fine-grained gold-containing material of the invention;
fig. 2 shows a schematic diagram of a water chlorination process for fine-grained sulphide mineral encapsulation Jin Wuliao in an embodiment of the invention.
Detailed Description
For the purpose of making the objects, technical solutions and advantages of the embodiments of the present invention more apparent, the technical solutions of the embodiments of the present invention will be clearly and completely described below with reference to the accompanying drawings in the embodiments of the present invention, and it is apparent that the described embodiments are some embodiments of the present invention, but not all embodiments of the present invention. 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 intended to be within the scope of the invention.
The invention provides a method for extracting gold from a fine-particle gold-containing material by water chlorination; the method adopts a coupling leaching reaction system of the micro-fine gold-containing material, the acidic chlorine-containing leaching solution and the manganese-containing oxidation active mineral, and realizes stable chlorination leaching of micro-fine gold, corrosion dissociation of sulfide mineral inclusion and chlorination segregation leaching of multiple metals in the same step, thus having wider adaptability to gold-containing materials, good technical index, non-cyanide gold extraction, environmental protection and high-efficiency comprehensive utilization of resources in the coupling material. The reaction process and mechanism include:
MnO 2 +4H + +4Cl - →MnCl 2 +Cl 2 +2H 2 O (1)
to contain Mn 4+ Cl in the material catalytic solution medium - Cl produced by oxidation 2 Controlling the reaction atmosphere such as the slurry temperature, the slurry pressure and the like to promote the reaction to be in Cl 2 Saturated state of gold dissolved by water chlorination to maintain AuCl 4、 AuCl 2 - Stabilization of isochoric complex ions, the equation is expressed as:
2Au+2Cl 2 +2HCl→2HAuCl 4 (2)
2Au+3Cl 2 +2NaCl→2NaAuCl 4 (3)
in the same step by Mn 4+ (MnO 2 /Mn 2+ Pair, oxidation-reduction potential E 0 =1.23V (vs. nhe)) and strong oxidative activity mno·oh (mno·oh/Mn) produced during dissolution 2+ Pair, oxidation-reduction potential E 0 Intermediate active derivatives such as =1.53V) to promote Cl 2 To ClO - The trend of equilibrium transformation is enhanced, and ClO in the gold dissolving process of chlorination is further enhanced and cooperated - To stabilize the formation of Jin Lvhua complex ions, the reaction formula is expressed as:
2Au+3ClO - +6H + +5Cl - →2AuCl 4 - +3H 2 O (4)
2Au+ClO - +2H + +3Cl - →2AuCl 2 - +H 2 O (5)
in addition, mn 4+ And the derivative thereof maintains the high oxidation activity state of the system, which is beneficial to the stabilization of Au chloridized complex ions.
In the same step, mn 4+ And the derivative thereof carries out electrochemical oxidation catalytic dissolution on sulfide inclusion to destroy mineral crystal lattice, and the reaction comprises:
MnO 2 +MeS+4H + →Mn 2+ +S 0 +Me x+ (aq)+2H 2 O (6)
4MnO 2 +MeS+8H + →Mn 2+ +SO 4 2- +Me x+ (aq)+4H 2 O (7)
wherein, meS is a gold-loaded sulfide mineral and comprises Me (Fe, cu, ni, co, as, sb and the like) S.
In the same step, saturated, high-permeability Cl 2 The method comprises the steps of carrying out chloridizing segregation on heavy metal minerals in materials, so that heavy metal oxides and sulfide minerals enter a solution after chloridizing segregation and dissolution, and extracting heavy metals in the materials is realized, wherein the reaction comprises the following steps:
MeO x +Cl 2 +2H + →MeCl x +Cl - +H 2 O (8)
as shown in fig. 1, the above mechanism is specifically implemented by the following execution steps:
s1: crushing and grinding gold-containing materials, namely crushing and grinding fine gold ores to proper granularity; the breaking and grinding dissociation granularity selects the effective dissociation granularity of inclusion sulphide minerals or sulphide mineral aggregate, and can also be broken and ground to finer granularity to obtain gold-containing materials.
In step S1, the fine gold ore is gold material supported on pyrite minerals including, but not limited to, pyrite, chalcopyrite, pyrrhotite, nickel/cobalt sulfide ore, arsenopyrite, and stibium ore. The Au content in the micro-fine gold ore is 0.1-300 g/t, and the sulfur content is 5-40%; the Au is in micro-particles or microcrystals separated out and tightly wrapped by sulfide minerals, and the effective dissociation granularity is smaller than 0.01mm; the prepared broken fineness of the gold-containing material is more than or equal to 60 percent below 0.074mm, namely the gold-containing material with the fineness of less than 0.074mm accounts for more than 60 percent of the whole gold-containing material, and is preferably the effective dissociation granularity of the sulfide mineral inclusion aggregate.
S2: preparing gold-dissolving reaction slurry, crushing and grinding a material containing high-valence manganese oxide to obtain manganese oxide active mineral, mixing the manganese oxide active mineral and the gold-containing material in proportion based on oxidation-reduction charge balance to obtain a mixed material, and adding the mixed material into an acidic chlorine-containing system to obtain a catalyst containing a certain free H + Mixed acidic mineral slurry of Au-S (-II) -Mn (VI) -Cl (-I) with ion concentration; preferably, dilute hydrochloric acid with a certain molar concentration is selected as a leaching reaction medium.
In the step S2, the manganese oxidation active mineral is a material containing high-valence manganese oxide, and comprises one or more of manganese dioxide, pyrolusite, manganese nodule, hydromanganese ore, manganese oxide smelting slag and the like, wherein the manganese oxidation active mineral contains Mn 4+ /Mn 3+ The content is 10-63%.
Preferably, the acidic chlorine-containing system in step S2 is: containing Cl - The solution system H is regulated by adding hydrochloric acid + With Cl - The effective ion concentration comprises hydrochloric acid, chlorine-containing metallurgical wastewater, acidified seawater and the like, and hydrochloric acid is preferred; when the system is free of Cl - /H + When the concentration is insufficient, hydrochloric acid, sulfuric acid and nitric acid are adopted for blending. Hydrochloric acid addition amount and free chlorine ion and manganese oxidation active oreMn in the material 4+ In terms of mass molar ratio Cl - (H + ):Mn 4+ Is configured in a ratio of 1:2-1:6, and meanwhile, in a system to be regulated, the mass ratio of the manganese oxidation active mineral to the gold-containing material in the step S1 is configured according to the mass molar ratio of S to Mn in the material of 1:4-1:6.
S3: and (3) chloridizing gold leaching reaction and process regulation, namely placing mixed acidic ore pulp of Au-S (-II) -Mn (VI) -Cl (-I) into a pressurized stirring reaction kettle, heating, pressurizing, coupling, reacting and leaching, regulating the oxidation-reduction state of a system according to the addition amounts of different materials, and regulating the reaction temperature to accelerate the reaction and chloridizing, isolating and leaching of metals to obtain leaching slurry. The coupling reaction comprises the steps of oxidizing and catalyzing high-valence manganese to produce chlorine and derivatives thereof, and chloridizing and stabilizing gold dissolving and high-valence manganese ions Mn 4+ And the derivative thereof carries out electrochemical oxidation catalytic dissolution and heavy metal chloridization segregation leaching on sulfide inclusion in the gold-containing material. On the one hand, the coupling reaction promotes Mn in the acidic medium 4+ With Cl - The pre-oxidation reaction produces Cl 2 And heating to regulate and control Cl 2 In a saturated concentration state, the leaching system is in a high Cl state 2 Oxidizing the active state to strengthen gold to form stable chloridized complex ions to be leached into the liquid phase; on the other hand, the temperature control accelerates the sulphide mineral in the gold material and other reducing substances and Mn contained in the sulphide mineral 4+ The reaction of the inclusion mineral is accelerated to quickly erode and destroy the inclusion mineral to expose the gold surface; in addition saturated Cl 2 The water leaching system carries out rapid chloridizing segregation leaching on heavy metals in the added solid phase materials, and the heavy metals in the system are in an ionic state (Mn 2+ 、Fe 3+ 、Cu 2+ Etc.) into solution, the residual solid phase is high-purity silicate tailing treated by chloridizing and segregation, and after the reaction is completed, gold-containing chloridizing complex ions and leaching Mn 2+ And other metal ions enter the solution phase, and the tailings are chloridized and isolated tailings.
In the step S3, in the coupling reaction chlorination gold dissolution reaction, the reaction temperature is 120-250 ℃ and the pressure is 0.2-4.0 MPa so as to strengthen Mn 4+ With Cl - Produced Cl 2 In saturated chlorine state, the reinforced Jin Lvhua is leached into ions and keeps stable, and the high temperature is beneficial to Mn 4+ The rapid leaching of the structure of the coated Au mineral is destroyed to destroy the surface of the exposed Au, which is also beneficial to the chloridizing segregation leaching process of the solid heavy metal in the system.
Preferably, the liquid-solid ratio of the leaching slurry of the coupling reaction in the step S3 is 2:1-10:1, and free H + The concentration is 0.5-5 mol/L, the reaction time is 0.5-6 h, and the stirring speed is 100-600 r/min.
S4: step recovery of leaching solution metal and tail-free utilization of tailings, and carrying out solid-liquid separation on leaching slurry reacted in the step S3 to obtain gold-containing water chlorination extract Jin Guiye and chlorination segregation tailings; wherein, the gold-extracting noble liquid of the water chlorination containing gold adopts activated carbon adsorption, the adsorption separation obtains the activated carbon with high Au chloridized complex ion content, the activated carbon is used for subsequent gold smelting, the solution containing heavy metal ions after the activated carbon adsorption is adopted, and the Mn is recovered in a gradient way by adopting a pH adjusting mode 2+ \Fe 3+ \Cu 2+ Waiting for metal; the chloridized and separated tailing is used for preparing raw materials such as white carbon black, ceramics, building materials and the like, and realizes the comprehensive utilization of water chloridizing method separation and purification of gold-containing materials and manganese-containing materials.
In the step S4, solid-liquid separation is carried out on the slurry, the activated carbon of the leaching solution for extracting gold by water chlorination adsorbs Jin Huishou gold, and the solution after gold adsorption adopts a pH adjustment method to recycle metal salts such as manganese, iron, copper and the like in steps; the separated chloridized segregation tailings can be used as raw materials of high-purity silicate, silicon dioxide, white carbon black, building materials and the like for comprehensive utilization.
The micro-fine gold material is gold material with pyrite as carrier, and the carrier sulfide mineral includes pyrite, chalcopyrite, pyrrhotite, nickel/cobalt sulfide mineral, arsenopyrite, stibium ore, etc.
The above method is described in detail with reference to specific examples.
Example 1
The gold concentrate containing 50.0g/t of Au and 32.0% of S is obtained after flotation and enrichment of the gold concentrate taking pyrite as a main carrier is ground to-0.074 mm and accounting for 60%; wherein, more than 20% of Au in the gold concentrate is tightly wrapped by-0.005 mm of pyrite, cyanide leaching is adopted, superfine grinding is carried out until-0.009 mm, and then leaching is carried out, the oxygenation strengthening leaching is carried out in the gold leaching process, the Au leaching rate is not high, the Au leaching rate is lower than 80%, and the consumption of the reagent of cyanide and oxidation leaching accelerator is large.
Treating the gold concentrate with the treatment method of the invention as shown in figure 2;
step 1), preparing gold-containing materials, wherein the gold-containing materials adopt gold concentrate enriched by floatation and are not subjected to regrinding, and the fineness of the materials is-0.074 mm and accounts for 65%;
step 2), performing size mixing preparation of water chlorination gold extraction reaction, wherein the chlorine-containing acid solution is hydrochloric acid, the consumption of the hydrochloric acid is 4.0mol/L, the manganese oxidation active mineral is Guizhou high-grade pyrolusite, and MnO is obtained by 2 Grinding pyrolusite to-0.074 mm 80% before slurry preparation, mixing pyrolusite and gold concentrate according to a Mn to S mass ratio of 3:1 to obtain a mixed material, and mixing hydrochloric acid with a liquid-solid ratio (wherein the liquid is hydrochloric acid, the solid is the mixed material of pyrolusite and gold concentrate) of 3:1 and 4.0mol/L to obtain mixed slurry;
step 3), introducing the mixed slurry obtained in the step 2) into a chlorination extraction Jin Jiawen stirring reactor, heating, stirring, catalyzing, oxidizing, dissolving, wrapping, catalyzing, oxidizing, producing saturated leaching chlorine and derivatives thereof, chloridizing, high-stability gold dissolving and heavy metal ion chloridizing, separating and leaching by a strong oxidation system, controlling the gold dissolving reaction temperature to be 150 ℃, regulating chlorine output reaction and keeping saturated water Cl 2 The pressure is 0.8MPa, the chlorination reaction time is 1h, the leaching speed is 400r/min, after the reaction is finished, the filtration is carried out, and the solid-liquid separation is carried out to obtain gold-containing water chlorination extract Jin Guiye and chlorination segregation tailings;
step 4), adsorbing Au by using activated carbon to the water chloridizing gold-extracting noble liquid separated in the step 3) to obtain Au-enriched activated carbon particles, extracting gold for subsequent smelting, and sequentially separating valuable metals such as Fe, cu, mn and the like in the leaching solution by adjusting pH of the solution after gold adsorption; the chloridized segregation tailings obtained by solid-liquid separation are used as raw materials for preparing white carbon black and can also be used as high-purity silicon-based raw materials; the gold leaching rate is calculated to reach 97% by extracting Jin Guiye. Wherein, the Au extraction rate of the activated carbon obtained by adsorption is 98.7 percent relative to the original gold concentrate, and the recovery rate of Fe, cu and Mn is more than 98.5 percent according to the content of the raw materials.
The method improves the extraction rate of gold, adopts the full wet method to efficiently extract gold, and greatly shortens the extraction flow of gold.
Example 2
The main flow is shown in figure 2, the gold-containing material is obtained from a cyanide smelting plant in Fujian, the ore contains 2.13% arsenic, 0.56% antimony, 29.2% sulfur and 4.2g/t gold, the recovery rate of gold from cyanide leaching after leaching slag roasting is 43%, and the manganese oxide is manganese oxide slag produced by a smelting plant and contains 20.7% manganese, 1.7% nickel, 0.2% cobalt and 1.3% copper.
1) The gold-containing materials are prepared before leaching, the two types of solid materials are ground until the diameter of the solid materials is-0.074 mm accounting for 90 percent,
2) The industrial wastewater produced by a certain smelting plant is adopted, and the wastewater contains Cl - High-salt wastewater of (1) Cl - 13% by mass, adjusted to acidic Cl-containing by adding 2.0mol/L sulfuric acid - Preparing a gold-containing material and a manganese-containing material mixed material according to the mass ratio of Mn to S in the material of 6:1, and mixing slurry according to the liquid-solid ratio of 10:1 by using acidified high-salt wastewater to the gold-manganese mixed material;
3) Placing the mixed slurry in a heating reaction kettle, carrying out constant-temperature stirring oxidation-reduction-chlorination extraction and segregation coupling reaction, leaching at 200r/min, leaching at 230 ℃ and enriching Cl 2 The pressure of a saturated material reaction system is 2.7MPa, so as to strengthen the oxidation-chlorination reaction process, the multi-mineral phase coupling reaction time is 2 hours, and leaching slurry is obtained after the reaction is finished and cooled;
4) And (3) carrying out solid-liquid separation on the leaching slurry to obtain gold-containing water chlorination extract Jin Guiye and chlorination segregation tailings, wherein the gold is recovered by adsorption relative to the raw materials by 98.5%, and the leaching rates of arsenic, antimony, manganese, nickel, cobalt and copper are calculated to be 96.5%, 98.2%, 99.5%, 99.7% and 98.6% respectively in the heavy metal solution after adsorption relative to the raw materials.
The method realizes the cooperative treatment and utilization of the gold leaching tailings, the manganese smelting slag and the high-salt wastewater in one step, and the gold and heavy metals in the materials reach more than 96 percent.
Although the invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical scheme described in the foregoing embodiments can be modified or some technical features thereof can be replaced by equivalents; such modifications and substitutions do not depart from the spirit and scope of the technical solutions of the embodiments of the present invention.
Claims (11)
1. A method for extracting gold from a fine-grained gold-containing material by water chlorination, which is characterized by comprising the following steps:
crushing and grinding the fine gold ores to an effective dissociation granularity or below the effective dissociation granularity to obtain gold-containing materials;
mixing the gold-containing material and crushed and ground manganese oxide active mineral in proportion based on oxidation-reduction charge balance, and adding the mixture into a chlorine-containing system to obtain a mixture containing free H + Mixed acidic mineral slurries of Au-S (-II) -Mn (VI) -Cl (-I) ions; the manganese oxidation active mineral is a material containing high-valence manganese oxide, and comprises one or more of manganese dioxide, pyrolusite, manganese nodule, hydromanganese mineral and manganese oxide smelting slag; wherein, mn in the manganese oxidation active mineral 4+ /Mn 3+ The content is 10-63%;
carrying out coupling reaction leaching on the mixed acidic ore pulp of Au-S (-II) -Mn (VI) -Cl (-I), and dynamically regulating the oxidation-reduction state in a leaching system to obtain leaching slurry; the coupling reaction comprises the steps of oxidizing and catalyzing high-valence manganese to produce chlorine and derivatives thereof, and chloridizing and stabilizing gold dissolving and high-valence manganese ions Mn 4+ And its derivative is used in electrochemical oxidation catalytic dissolution and heavy metal chloridizing segregation leaching of sulfide inclusion in gold-containing material; the high-valence manganese oxidation catalysis chlorine production and the derivative thereof comprise the following reaction formula:
MnO 2 +4H + +4Cl - →MnCl 2 +Cl 2 +2H 2 O；
2Au+2Cl 2 +2HCl→2HAuCl 4 ；
2Au+3Cl 2 +2NaCl→2NaAuCl 4 ；
the chloridized stable gold dissolution comprises the following reaction formula:
2Au+3ClO - +6H + +5Cl - →2AuCl 4 - +3H 2 O；
2Au+ClO - +2H + +3Cl - →2AuCl 2 - +H 2 O；
the high valence Mn ion Mn 4+ The electrochemical oxidation catalytic dissolution of sulfide inclusion in gold-containing materials by the derivatives thereof comprises the following reaction formula:
MnO 2 +MeS+4H + →Mn 2+ +S 0 +Me x+ (aq)+2H 2 O；
4MnO 2 +MeS+8H + →Mn 2+ +SO 4 2- +Me x+ (aq)+4H 2 O；
the heavy metal chloridizing segregation leaching comprises the following reaction formula:
MeO x +Cl 2 +2H + →MeCl x +Cl - +H 2 O；
and carrying out solid-liquid separation on the leaching slurry to obtain gold-containing water chlorination extract Jin Guiye and chlorination segregation tailings.
2. The method for extracting gold from a fine gold-containing material by aqueous chlorination according to claim 1, wherein,
the micro-fine gold ore is a gold material taking a pyrite mineral as a carrier, and the pyrite mineral comprises: pyrite, chalcopyrite, pyrrhotite, nickel/cobalt sulphide ore, arsenopyrite and stibium ore;
the Au content in the micro-fine gold ore is 0.1-300 g/t, and the sulfur content is 5-40%;
the Au is in micro-particles or microcrystals to be separated out and wrapped by sulfide minerals;
the effective dissociation particle size is less than 0.01mm; the prepared grinding fineness of the gold-containing material is less than 0.074mm and is more than or equal to 60 percent.
3. The method for extracting gold from a fine-grained gold-containing material by aqueous chlorination according to claim 1 or 2, characterized in that,
the effective dissociation particle size is the effective dissociation particle size of the sulfide mineral package aggregate.
4. The method for extracting gold from the micro-fine gold-containing material by water chlorination according to claim 3, wherein,
the molar ratio of the gold-containing material to the crushed and ground manganese oxide active mineral is 1:4-1:6.
5. The method for extracting gold from a fine gold-containing material by aqueous chlorination according to claim 1, wherein,
the chlorine-containing system is Cl-containing - The solution system H is regulated by adding hydrochloric acid + With Cl - Effective ion concentration.
6. The method for extracting gold from a fine-grained gold-containing material by aqueous chlorination according to claim 1 or 5, characterized in that,
when free Cl in the chlorine-containing system - /H + When the concentration is insufficient, hydrochloric acid, sulfuric acid and nitric acid are adopted for blending;
wherein, the addition amount of the hydrochloric acid and the Mn of high valence manganese ions in the free chlorine ions and the manganese oxidation active minerals 4+ In terms of mass molar ratio Cl - (H + ):Mn 4+ Is configured in a ratio of 1:2 to 1:6.
7. The method for extracting gold from a fine gold-containing material by aqueous chlorination according to claim 1, wherein,
during the coupling reaction process: the temperature is 120-250 ℃ and the pressure is 0.2-4.0 MPa; high valence manganese ions and Cl in the leaching system - Produced Cl 2 In a saturated chlorine state.
8. The method for extracting gold from a fine gold-containing material by aqueous chlorination according to claim 1, wherein,
the liquid-solid ratio of the leaching slurry is 2:1-10:1, and free H + The concentration is 0.5-5 mol/L, the reaction time is 0.5-6 h, and the stirring speed is 100-600 r/min.
9. The method for extracting gold from a fine gold-containing material by aqueous chlorination according to claim 1, wherein,
the gold-containing water chloridizing gold-extracting noble liquid is adsorbed by active carbon, and the active carbon with high Au chloridizing complex ion content and heavy metal ion-containing solution are obtained through adsorption separation;
the active carbon with high Au chloride complex ion content is used for smelting gold;
the solution containing heavy metal ions adopts a pH adjustment mode to recycle metal in a gradient way, wherein the metal comprises Mn 2+ 、Fe 3+ And Cu 2+ 。
10. A gold-containing aqueous chloridizing extract Jin Guiye, characterized in that the gold-containing aqueous chloridizing extract is obtained by the method of any one of claims 1-9.
11. A chlorinated segregation tail, characterized in that the chlorinated segregation tail is obtained by the method of any one of claims 1-9, and the chlorinated segregation tail can be applied to the preparation of white carbon black, ceramics and building materials.
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| US3992507A (en) * | 1973-02-28 | 1976-11-16 | Deepsea Ventures, Inc. | Halidation of manganiferous ore to obtain metal values and recovery and recycle of halide values |
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| CN104694764A (en) * | 2015-03-09 | 2015-06-10 | 中南大学 | Reinforced leaching method of fine-grained encapsulated gold |
| CN111154975A (en) * | 2020-02-14 | 2020-05-15 | 中国恩菲工程技术有限公司 | Method for treating arsenic-antimony-containing gold-carrying material |
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| US3992507A (en) * | 1973-02-28 | 1976-11-16 | Deepsea Ventures, Inc. | Halidation of manganiferous ore to obtain metal values and recovery and recycle of halide values |
| US5232490A (en) * | 1985-11-27 | 1993-08-03 | Leadville Silver And Gold | Oxidation/reduction process for recovery of precious metals from MnO2 ores, sulfidic ores and carbonaceous materials |
| US5169503A (en) * | 1988-06-24 | 1992-12-08 | Baughman David R | Process for extracting metal values from ores |
| CN104694764A (en) * | 2015-03-09 | 2015-06-10 | 中南大学 | Reinforced leaching method of fine-grained encapsulated gold |
| CN111154975A (en) * | 2020-02-14 | 2020-05-15 | 中国恩菲工程技术有限公司 | Method for treating arsenic-antimony-containing gold-carrying material |
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