CN114058867A - Chlorine dioxide gold leaching method for preparing leaching agent in ore pulp - Google Patents
Chlorine dioxide gold leaching method for preparing leaching agent in ore pulp Download PDFInfo
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- 238000002386 leaching Methods 0.000 title claims abstract description 112
- 238000000034 method Methods 0.000 title claims abstract description 61
- 239000003795 chemical substances by application Substances 0.000 title claims abstract description 44
- -1 Chlorine dioxide gold Chemical compound 0.000 title claims abstract description 19
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims abstract description 141
- 239000010931 gold Substances 0.000 claims abstract description 141
- 229910052737 gold Inorganic materials 0.000 claims abstract description 141
- OSVXSBDYLRYLIG-UHFFFAOYSA-N dioxidochlorine(.) Chemical compound O=Cl=O OSVXSBDYLRYLIG-UHFFFAOYSA-N 0.000 claims abstract description 118
- 239000004155 Chlorine dioxide Substances 0.000 claims abstract description 59
- 235000019398 chlorine dioxide Nutrition 0.000 claims abstract description 59
- 230000008569 process Effects 0.000 claims abstract description 20
- 229910052500 inorganic mineral Inorganic materials 0.000 claims abstract description 12
- 239000011707 mineral Substances 0.000 claims abstract description 12
- 239000007787 solid Substances 0.000 claims abstract description 11
- 230000003213 activating effect Effects 0.000 claims abstract description 9
- BRSVJNYNWNMJKC-UHFFFAOYSA-N [Cl].[Au] Chemical compound [Cl].[Au] BRSVJNYNWNMJKC-UHFFFAOYSA-N 0.000 claims abstract description 7
- 238000006243 chemical reaction Methods 0.000 claims abstract description 7
- 150000002500 ions Chemical class 0.000 claims abstract description 6
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 12
- 238000003756 stirring Methods 0.000 claims description 11
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 8
- 239000012190 activator Substances 0.000 claims description 8
- 229910052787 antimony Inorganic materials 0.000 claims description 7
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 claims description 7
- 239000002002 slurry Substances 0.000 claims description 7
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 6
- 229910052799 carbon Inorganic materials 0.000 claims description 6
- QBWCMBCROVPCKQ-UHFFFAOYSA-N chlorous acid Chemical group OCl=O QBWCMBCROVPCKQ-UHFFFAOYSA-N 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 6
- 239000002245 particle Substances 0.000 claims description 6
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 claims description 4
- 229910052785 arsenic Inorganic materials 0.000 claims description 4
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 claims description 4
- 238000000227 grinding Methods 0.000 claims description 4
- 238000002360 preparation method Methods 0.000 claims description 4
- 229910052959 stibnite Inorganic materials 0.000 claims description 4
- IHBMMJGTJFPEQY-UHFFFAOYSA-N sulfanylidene(sulfanylidenestibanylsulfanyl)stibane Chemical compound S=[Sb]S[Sb]=S IHBMMJGTJFPEQY-UHFFFAOYSA-N 0.000 claims description 4
- 239000011975 tartaric acid Substances 0.000 claims description 4
- 235000002906 tartaric acid Nutrition 0.000 claims description 4
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 3
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 claims description 3
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 3
- 239000007788 liquid Substances 0.000 claims description 3
- GPRLSGONYQIRFK-UHFFFAOYSA-N hydron Chemical compound [H+] GPRLSGONYQIRFK-UHFFFAOYSA-N 0.000 claims description 2
- 238000010907 mechanical stirring Methods 0.000 claims description 2
- 239000005864 Sulphur Substances 0.000 claims 1
- 238000007613 slurry method Methods 0.000 claims 1
- XFXPMWWXUTWYJX-UHFFFAOYSA-N Cyanide Chemical compound N#[C-] XFXPMWWXUTWYJX-UHFFFAOYSA-N 0.000 abstract description 9
- 239000007789 gas Substances 0.000 abstract description 8
- 231100000331 toxic Toxicity 0.000 abstract description 5
- 230000002588 toxic effect Effects 0.000 abstract description 5
- 239000003814 drug Substances 0.000 abstract description 4
- 239000006227 byproduct Substances 0.000 abstract description 3
- 239000002351 wastewater Substances 0.000 abstract description 3
- 239000010891 toxic waste Substances 0.000 abstract description 2
- 239000000047 product Substances 0.000 abstract 1
- 230000000694 effects Effects 0.000 description 8
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 230000008901 benefit Effects 0.000 description 5
- 230000035484 reaction time Effects 0.000 description 5
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 4
- 229910001919 chlorite Inorganic materials 0.000 description 4
- 229910052619 chlorite group Inorganic materials 0.000 description 4
- 238000000605 extraction Methods 0.000 description 4
- MXZVHYUSLJAVOE-UHFFFAOYSA-N gold(3+);tricyanide Chemical compound [Au+3].N#[C-].N#[C-].N#[C-] MXZVHYUSLJAVOE-UHFFFAOYSA-N 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 238000007254 oxidation reaction Methods 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 230000009286 beneficial effect Effects 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000011084 recovery Methods 0.000 description 3
- 239000011780 sodium chloride Substances 0.000 description 3
- 238000004659 sterilization and disinfection Methods 0.000 description 3
- 229910052569 sulfide mineral Inorganic materials 0.000 description 3
- 229910052717 sulfur Inorganic materials 0.000 description 3
- 239000011593 sulfur Substances 0.000 description 3
- KEQXNNJHMWSZHK-UHFFFAOYSA-L 1,3,2,4$l^{2}-dioxathiaplumbetane 2,2-dioxide Chemical compound [Pb+2].[O-]S([O-])(=O)=O KEQXNNJHMWSZHK-UHFFFAOYSA-L 0.000 description 2
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 229910052924 anglesite Inorganic materials 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 239000008139 complexing agent Substances 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- JJLJMEJHUUYSSY-UHFFFAOYSA-L copper(II) hydroxide Inorganic materials [OH-].[OH-].[Cu+2] JJLJMEJHUUYSSY-UHFFFAOYSA-L 0.000 description 2
- 238000005520 cutting process Methods 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 239000003651 drinking water Substances 0.000 description 2
- 235000020188 drinking water Nutrition 0.000 description 2
- 230000002401 inhibitory effect Effects 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 231100000252 nontoxic Toxicity 0.000 description 2
- 230000003000 nontoxic effect Effects 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 239000002893 slag Substances 0.000 description 2
- UKLNMMHNWFDKNT-UHFFFAOYSA-M sodium chlorite Chemical compound [Na+].[O-]Cl=O UKLNMMHNWFDKNT-UHFFFAOYSA-M 0.000 description 2
- 229960002218 sodium chlorite Drugs 0.000 description 2
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- 208000005623 Carcinogenesis Diseases 0.000 description 1
- KZBUYRJDOAKODT-UHFFFAOYSA-N Chlorine Chemical compound ClCl KZBUYRJDOAKODT-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 239000005708 Sodium hypochlorite Substances 0.000 description 1
- 208000031320 Teratogenesis Diseases 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- MJLGNAGLHAQFHV-UHFFFAOYSA-N arsenopyrite Chemical compound [S-2].[Fe+3].[As-] MJLGNAGLHAQFHV-UHFFFAOYSA-N 0.000 description 1
- 229910052964 arsenopyrite Inorganic materials 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000036952 cancer formation Effects 0.000 description 1
- 231100000504 carcinogenesis Toxicity 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 239000002781 deodorant agent Substances 0.000 description 1
- 238000004332 deodorization Methods 0.000 description 1
- 239000000645 desinfectant Substances 0.000 description 1
- 230000000249 desinfective effect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- 238000009920 food preservation Methods 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 description 1
- 231100000086 high toxicity Toxicity 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000011133 lead Substances 0.000 description 1
- 229910052976 metal sulfide Inorganic materials 0.000 description 1
- 238000005272 metallurgy Methods 0.000 description 1
- 238000002703 mutagenesis Methods 0.000 description 1
- 231100000350 mutagenesis Toxicity 0.000 description 1
- 230000008520 organization Effects 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 230000033116 oxidation-reduction process Effects 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- NIFIFKQPDTWWGU-UHFFFAOYSA-N pyrite Chemical compound [Fe+2].[S-][S-] NIFIFKQPDTWWGU-UHFFFAOYSA-N 0.000 description 1
- 229910052683 pyrite Inorganic materials 0.000 description 1
- 239000011028 pyrite Substances 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 230000001954 sterilising effect Effects 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
Images
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
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B11/00—Oxides or oxyacids of halogens; Salts thereof
- C01B11/02—Oxides of chlorine
- C01B11/022—Chlorine dioxide (ClO2)
- C01B11/023—Preparation from chlorites or chlorates
- C01B11/024—Preparation from chlorites or chlorates from chlorites
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Life Sciences & Earth Sciences (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Geology (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Inorganic Chemistry (AREA)
- Manufacture And Refinement Of Metals (AREA)
Abstract
The invention discloses a chlorine dioxide gold leaching method for preparing gold leaching agent in ore pulp, which comprises the following steps: respectively adding a generating agent and an activating agent for preparing chlorine dioxide into the gold ore pulp, and reacting to generate gold leaching agent chlorine dioxide; and dissolving the generated chlorine dioxide in the ore pulp, then carrying out chemical reaction with the gold mineral, dissolving the gold, generating stable gold-chlorine complex ions, putting the stable gold-chlorine complex ions into the solution to obtain a gold leaching solution, and recovering a target product, namely the gold. The invention prepares chlorine dioxide by directly reacting the chlorine dioxide generating agent and the activating agent in the ore pulp, completely replaces the traditional highly toxic cyanide with the chlorine dioxide, greatly simplifies the gold leaching operation process and simultaneously realizes the environment-friendly cyanide-free gold leaching, and the chlorine dioxide is prepared by reacting the solid medicament in the ore pulp, does not generate toxic waste gas, waste water and toxic byproducts in the leaching process, and has simple and environment-friendly method, easy control and industrialization.
Description
Technical Field
The invention belongs to the technical field of metallurgy, and particularly relates to a chlorine dioxide gold leaching method for preparing a leaching agent in ore pulp.
Background
Gold is usually extracted from ores or gold-containing waste materials in a hydrometallurgical manner, and a cyanide leaching method has the outstanding advantages of simple operation, high recovery rate, low production cost and the like, so that the cyanide leaching method is widely applied to gold production, but the cyanide leaching speed is low, the leaching effect on gold ores containing carbon, arsenic, antimony, copper and other elements is poor, and the cyanide leaching method has high toxicity and cannot meet the sustainable development requirement of the gold industry. In recent years, miners have conducted intensive research on non-cyanide gold leaching processes and leaching agents, and proposed a variety of new gold leaching methods, some of which have reached the industrial application level and achieved significant effects, wherein the non-cyanide gold leaching technology has become an important means for gold extraction.
Chlorine dioxide is a strong oxidant, the standard electrode potential of the chlorine dioxide is 1.511V, the chlorine dioxide can generate oxidation-reduction reaction with sulfide, cyanide and the like, and the chlorine dioxide can be used for oxidation pretreatment of refractory gold ore and treatment of cyanide-containing gold leaching wastewater. Chlorine dioxide has strong environmental protection advantages, does not generate harmful wastes and byproducts in the oxidation and disinfection process, has been widely applied as a safe, efficient and broad-spectrum sterilization, preservation and deodorant, and is the most ideal substitute of chlorine preparations. The World Health Organization (WHO) has also listed chlorine dioxide as a A1 grade safe and efficient disinfectant, and in order to control the generation of teratogenesis, carcinogenesis and mutagenesis in drinking water, European and American countries have widely popularized and applied chlorine dioxide to replace chlorine gas for disinfecting drinking water. Chlorine dioxide has been approved and recommended in the united states, canada, japan, western europe, etc. for disinfection, deodorization, mold prevention, food preservation, and the like in the fields of food, food processing industry, pharmaceutical industry, hospitals, public environments, and the like.
The oxidation-reduction potential of chlorine dioxide is higher than the dissolution potential of gold under the acidic condition, and gold can be leached by the chlorine dioxide and stably exists in the form of gold-chlorine complex, so that the chlorine dioxide is a potential, efficient, non-toxic and non-cyanide gold leaching agent. The existing gold leaching method of chlorine dioxide is realized by introducing high-purity chlorine dioxide gas into ore pulp or adding high-concentration chlorine dioxide solution, has the defects of low utilization efficiency of chlorine dioxide, difficult storage of gas and solution, explosion risk of high-purity gas and the like, and cannot realize large-scale industrial application. The solid medicament is added into the ore pulp at normal temperature and normal pressure to quantitatively and smoothly control the generation amount of the chlorine dioxide, and the direct leaching method of the actual ore is not reported in documents. Patent application CN95105351.5 discloses a gold extraction process from bromide leachate, which comprises the procedures of ore crushing, batching, roasting leaching, size mixing, solid-liquid separation, gold recovery and the like, and adopts a gold extraction system consisting of bromide-sulfuric acid-chlorine dioxide and a sectional leaching process to accelerate the gold extraction speed, reduce the reagent dosage and improve the leaching speed and the leaching rate, but the method has the defects of volatilization of toxic bromide, need of preparing chlorine dioxide gas and the like, and has great difficulty in industrial application; patent application CN201510027146.X discloses a method for leaching gold in refractory gold ore by ultrasonic-enhanced chlorination-oxidation synergy, mineral powder, sodium hydroxide, sodium hypochlorite and water are fully mixed to obtain ore pulp, air is introduced into the ore pulp, ultrasonic-enhanced leaching is carried out under the stirring condition, hydrogen peroxide is periodically added in the enhanced leaching process, and non-cyanide leaching is realized by utilizing ultrasonic enhancement and the synergistic action of hydrogen peroxide and sodium hydroxide, but the method has complex medicament system, the leaching process needs ultrasonic enhancement assistance, and the leaching cost is high.
Aiming at the current situation, the invention provides a non-cyanide gold ore leaching method for efficiently and conveniently preparing a chlorine dioxide leaching agent in ore pulp.
Disclosure of Invention
The invention aims to provide a safe, efficient, environment-friendly and feasible gold ore chlorine dioxide leaching method, so as to improve the operability of gold leaching and realize efficient cyanide-free leaching of gold.
In order to achieve the purpose, the invention adopts the following technical effects:
the invention provides a chlorine dioxide gold leaching method for preparing gold leaching agent in ore pulp, which comprises the following steps:
(1) respectively adding a generating agent and an activating agent for preparing gold leaching agent chlorine dioxide into the gold ore pulp, and reacting to generate chlorine dioxide;
(2) and after the generated chlorine dioxide is dissolved in the ore pulp, carrying out chemical reaction with gold minerals, dissolving gold, generating stable gold-chlorine complex ions, putting the stable gold-chlorine complex ions into the solution to obtain a gold leaching solution, and recovering the target gold to obtain the gold-leaching solution.
In the above method of the present invention, the generator is a chlorite, and the ratio of the chlorite to the amount of the hydrogen ion-ionizable substance by the activator is 5: 4.
in the method, the pulp liquid-solid ratio of the gold ore is based on the guarantee of the solubility of chlorine dioxide; according to the difference of the contents of sulfide minerals and gold in the gold ore, the liquid-solid ratio of the ore pulp can be correspondingly adjusted, and the preferable liquid-solid mass ratio is 4: 1.
in the method, when the gold ore contains harmful components of carbonate or sulfur, arsenic and antimony, sulfuric acid is used for adjusting the acidity of the ore pulp to pH 1-2, and the strong acidity of the solution is beneficial to inhibiting FeAsO4、PbSO4、Cu(OH)2And the generation of precipitates is helpful for improving the leaching effect.
In the method, when the gold ore contains stibnite, tartaric acid or citric acid is used as an activator for preparing chlorine dioxide, so that antimony stably exists in the ore pulp, and the coating effect on the gold ore is reduced.
According to the method, the gold leaching process can be carried out within 20-60 ℃ according to the content and the composition of gold in the gold ore; the gold leaching of gold in gold ore can be realized under the condition of room temperature, the reaction temperature is properly increased to help increase the gold leaching speed, however, the excessive ore pulp temperature can reduce the solubility of chlorine dioxide in the ore pulp.
In the method, mechanical stirring is adopted in the gold leaching process of chlorine dioxide, and the stirring speed is 400-1000 r/min.
In the method, the chlorine dioxide gold leaching period is not more than 5 hours, and the reaction time can be properly prolonged or shortened according to the content and the composition of gold in the gold ore and the temperature condition when leaching is carried out.
In the method, the gold ore pulp is obtained by crushing the gold ore raw ore to 5-15 mm and grinding the ore until the content of particles with the granularity of not more than 0.074mm accounts for more than 80%.
In the method, finely ground gold ore is pre-oxidized or directly transferred to a gold leaching tank according to the properties of the ore, a chlorine dioxide activator and sodium chloride are added to the gold ore to mix the gold ore, the stirring speed is adjusted and fixed, the acidity and the temperature of the ore pulp are adjusted at the same time, a chlorine dioxide generator is added to start timing after the gold ore is kept stable, the stirring is stopped after the preset leaching reaction time is reached, and the gold in the leaching solution is recovered by a carbon pulp method.
The reaction formula of the chlorine dioxide preparation and gold leaching generated in the ore pulp is as follows:
5ClO- 2+4H+＝4ClO2+Cl-+2H2O
compared with the prior art, the invention has the beneficial effects that:
(1) the invention prepares chlorine dioxide by direct reaction of the chlorine dioxide generating agent and the activating agent in the ore pulp, and the novel nontoxic leaching agent chlorine dioxide completely replaces the traditional highly toxic cyanide, thereby greatly simplifying the gold leaching operation process and realizing the environment-friendly cyanide-free gold leaching. In addition, the high-efficiency gold leaching agent chlorine dioxide is prepared by reacting a solid medicament in ore pulp, is not introduced in a gas form, does not generate toxic waste gas, waste water and toxic byproducts in the leaching process, generates remarkable economic benefit and eliminates the danger of using high-concentration chlorine dioxide gas and solution.
(2) The method does not need oxidation pretreatment when leaching the low-sulfur refractory gold ore, and can greatly improve the direct leaching rate.
(3) The invention can make the recovery valuable metals such as copper, lead, zinc, antimony and the like in the gold ore enter the solution by adding the complexing agent or adjusting the acidity value, and separate and recycle the metals from the gold ore, thereby realizing the comprehensive recycling of the minerals and furthest realizing the economic benefit.
(4) The method is carried out at low temperature and normal pressure, the acidity of the leaching process does not need to be controlled in the conventional gold ore, and the method is simple and easy to control and industrialize.
Drawings
FIG. 1 is a schematic flow chart of a chlorine dioxide gold leaching method for preparing gold leaching agent from ore pulp in the embodiment.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions of the embodiments of the present invention are clearly and completely described below with reference to the drawings of the embodiments of the present invention. It is to be understood that the embodiments described are only a few embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the described embodiments of the invention without any inventive step, are within the scope of protection of the invention.
The chlorine dioxide gold leaching method for preparing gold leaching agent from gold ore pulp in the following examples is as follows: chlorine dioxide generating agent and activating agent are respectively added into the ore pulp, and the chlorine dioxide generated by the chlorine dioxide generating agent and the activating agent is dissolved in the ore pulp and then chemically reacts with the gold mineral, so that gold is dissolved and stable gold-chlorine complex ions are generated and enter the solution, and the purpose of leaching gold is achieved.
When the generating agent is chlorite, the ratio of the chlorite to the amount of hydrogen ion substances ionized by the activator is 5: 4, the actual dosage can be properly adjusted according to the actual production.
According to the different contents of the sulfide minerals and gold in the gold ore, the liquid-solid ratio of the ore pulp can be correspondingly adjusted, and the liquid-solid ratio of the sulfide minerals and the gold ore with high gold content can ensure the solubility of the chlorine dioxide.
When the gold ore contains harmful components such as carbonate or sulfur, arsenic, antimony and the like, sulfuric acid is used for adjusting the acidity of the ore pulp to pH 1-2, and strong solution acidity is beneficial to inhibiting FeAsO4、PbSO4、Cu(OH)2The generation of precipitate is helpful for improving the leaching effect; when the gold ore contains stibnite, tartaric acid or citric acid is used as an activator for preparing chlorine dioxide, so that stibium stably exists in the ore pulp, and the coating effect on the gold ore is reduced.
The method can realize leaching of gold in the gold ore at room temperature, the reaction temperature is properly increased to help increase the gold leaching speed, the excessive ore pulp temperature can reduce the solubility of chlorine dioxide in the ore pulp, and the gold leaching process can be carried out within the range of 20-60 ℃ according to the content and the composition of gold in the gold ore.
The method can complete the leaching of gold within 5h, and can properly prolong and shorten the reaction time according to the content and the composition of the gold in the gold ore and the temperature condition when the leaching is carried out.
In some embodiments, the gold ore raw ore is crushed to 5-15 mm and reground to a particle size of no greater than 0.074mm with a particle content of greater than 80%. Pre-oxidizing the finely ground gold ore or directly transferring the gold ore into a gold leaching tank according to the properties of the ore, adding a chlorine dioxide activating agent and sodium chloride, then mixing the slurry, and adjusting and fixing the stirring speed. Adjusting the acidity and temperature of the ore pulp, adding a chlorine dioxide generating agent after the ore pulp is kept stable, starting timing, stopping stirring after the preset leaching reaction time is reached, and recovering gold in the leaching solution by using a carbon pulp method.
The present invention will be further described with reference to the following specific examples.
Example 1
The sample used in this example was gold ore of karlin type, gansu. The gold ore of the type is dipped in the ore in a star-dispersed state by using metal sulfides mainly comprising pyrite, stibnite and arsenopyrite, gold is usually wrapped in the sulfide ore in fine grains or sub-microscopic grains, the leaching rate of direct cyanidation of gold is 39%, and the gold belongs to refractory ore, and the chemical components of the gold ore are shown in table 1.
Table 1: the results of multielement analysis of raw ore (%,*g/t)
the gold ore is finely ground until the particle size of the gold ore is not more than 0.074mm accounts for 90 percent, sulfuric acid with the concentration of 0.625mol/L, tartaric acid with the concentration of 0.20mol/L, sodium chloride with the concentration of 0.05mol/L, sodium chlorite with the concentration of 0.30mol/L and the liquid-solid mass ratio of 4:1 are added, and the gold ore is mechanically stirred and leached for 5 hours under the conditions of the stirring speed of 900r/min and the leaching temperature of 30 ℃, wherein the leaching rate of gold can reach 91.02 percent.
Example 2
The type of sample used in this example was a carbonaceous refractory gold ore, the chemical composition of which is shown in table 2. Due to the gold cutting effect of the organic carbon, the direct cyanidation leaching rate of the ore is only 9.29 percent, and the ore belongs to refractory gold ore.
Table 2: the results of multi-element analysis of a certain carbonaceous gold ore (%,*g/t)
roasting the ore to be leached for 1h at 700 ℃ in an oxygen-rich environment to remove the gold-cutting carbon. Finely grinding the roasting slag, then mixing the pulp, and respectively adding a chlorine dioxide generating agent (sodium chlorite NaClO) into the pulp2Concentration 0.12mol/L) and activator (citric acid C)6H8O7And the concentration is 0.10mol/L), and the generated chlorine dioxide is dissolved in the ore pulp and then immediately reacts with the gold mineral to realize gold leaching. The specific process is as follows: grinding 500g of roasting slag to make the granularity of below 0.074mm account for 90 wt%, adding a chlorine dioxide activating agent and a gold complexing agent, mixing according to the liquid-solid mass ratio of 4:1, and adjusting and fixing the stirring speed to 900 r/min. After stirring and stabilizing, adding a chlorine dioxide generating agent, timing, and leaching for 5 hours at the temperature of 30 ℃. Stopping stirring after the preset reaction time is reached, and extracting the gold in the leaching solution after solid-liquid separation. The gold leaching rate can reach more than 90% under the best test condition.
The above examples are only for illustrating the technical solutions of the present invention, and are not limited thereto.
Claims (10)
1. A chlorine dioxide gold leaching method for preparing gold leaching agent in ore pulp is characterized by comprising the following steps:
(1) respectively adding a generating agent and an activating agent for preparing chlorine dioxide into the gold ore pulp, and reacting to generate gold leaching agent chlorine dioxide;
(2) and (2) after the chlorine dioxide generated in the step (1) is dissolved in the ore pulp, carrying out chemical reaction with gold minerals, dissolving gold, generating stable gold-chlorine complex ions, entering the solution, obtaining a gold leaching solution, and recovering a target product gold.
2. The chlorine dioxide gold leaching process in pulp to produce a gold leaching agent according to claim 1, wherein the generator is a chlorite salt and the ratio of the amount of chlorite salt to the amount of hydrogen ion species ionizable by the activator is 5: 4.
3. the chlorine dioxide gold leaching process with in-pulp gold leaching agent preparation according to claim 1, characterized in that the gold ore pulp has a liquid to solid mass ratio of 4: 1.
4. the chlorine dioxide gold leaching method for preparing gold leaching agent in mineral slurry according to claim 1, characterized in that when said gold ore contains harmful components of carbonate or sulphur, arsenic and antimony, sulfuric acid is used to adjust the acidity of mineral slurry to pH 1-2.
5. The chlorine dioxide gold leaching process with preparation of gold leaching agent in pulp according to claim 1, characterized in that when the gold ore contains stibnite, tartaric acid or citric acid is used as activator for preparing chlorine dioxide to make antimony stably exist in pulp.
6. The chlorine dioxide gold leaching method for preparing gold leaching agent in mineral slurry according to claim 1, characterized in that the gold leaching temperature in step (2) is selected to be 20-60 ℃ according to the content and composition of gold in the gold ore.
7. The method for leaching gold with chlorine dioxide to produce a gold leaching agent in mineral slurry of claim 1, wherein the period of the chlorine dioxide leaching is not more than 5 hours.
8. The chlorine dioxide gold leaching method for preparing gold leaching agent in ore pulp as claimed in claim 1, characterized in that the chlorine dioxide gold leaching process adopts mechanical stirring, and the stirring speed is 400-1000 r/min.
9. The chlorine dioxide gold leaching process for producing gold leaching agent in mineral slurry according to claim 1, characterized in that the target product gold is extracted from the gold leaching solution by using a carbon slurry method.
10. A chlorine dioxide gold leaching process according to any one of claims 1 to 9 in which the gold ore slurry is obtained by crushing a gold ore raw ore to 5-15 mm and grinding the ore to a particle size of no more than 0.074mm with a particle content of 80% or more.
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| CN101054623A (en) * | 2007-02-09 | 2007-10-17 | 上海大学 | Method for leaching gold mine by electrochemistry oxidation method |
| CN107385208A (en) * | 2017-07-31 | 2017-11-24 | 中南大学 | A kind of microwave radiation technology, which is strengthened, soaks golden method |
| CN108103310A (en) * | 2018-01-22 | 2018-06-01 | 东北大学 | A kind of chlorine dioxide method for pre-oxidizing containing sulfur gold ore |
| 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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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101054623A (en) * | 2007-02-09 | 2007-10-17 | 上海大学 | Method for leaching gold mine by electrochemistry oxidation method |
| CN107385208A (en) * | 2017-07-31 | 2017-11-24 | 中南大学 | A kind of microwave radiation technology, which is strengthened, soaks golden method |
| CN108103310A (en) * | 2018-01-22 | 2018-06-01 | 东北大学 | A kind of chlorine dioxide method for pre-oxidizing containing sulfur gold ore |
| 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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