WO2023186027A1 - 一种含碳硫砷金矿的绿色浸金方法 - Google Patents

一种含碳硫砷金矿的绿色浸金方法 Download PDF

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Publication number
WO2023186027A1
WO2023186027A1 PCT/CN2023/085157 CN2023085157W WO2023186027A1 WO 2023186027 A1 WO2023186027 A1 WO 2023186027A1 CN 2023085157 W CN2023085157 W CN 2023085157W WO 2023186027 A1 WO2023186027 A1 WO 2023186027A1
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Prior art keywords
gold
arsenic
sulfur
ore
carbon
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PCT/CN2023/085157
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English (en)
French (fr)
Inventor
涂学炎
唐志宇
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云南大学
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Publication of WO2023186027A1 publication Critical patent/WO2023186027A1/zh
Priority to ZA2023/11027A priority Critical patent/ZA202311027B/en

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B11/00—Obtaining noble metals
    • C22B11/04—Obtaining noble metals by wet processes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B03—SEPARATION OF SOLID MATERIALS USING LIQUIDS OR USING PNEUMATIC TABLES OR JIGS; MAGNETIC OR ELECTROSTATIC SEPARATION OF SOLID MATERIALS FROM SOLID MATERIALS OR FLUIDS; SEPARATION BY HIGH-VOLTAGE ELECTRIC FIELDS
    • B03D—FLOTATION; DIFFERENTIAL SEDIMENTATION
    • B03D1/00—Flotation
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B1/00—Preliminary treatment of ores or scrap
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B1/00—Preliminary treatment of ores or scrap
    • C22B1/11—Removing sulfur, phosphorus or arsenic other than by roasting
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
    • C22B3/04—Extraction of metal compounds from ores or concentrates by wet processes by leaching
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25C—PROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
    • C25C1/00—Electrolytic production, recovery or refining of metals by electrolysis of solutions
    • C25C1/20—Electrolytic production, recovery or refining of metals by electrolysis of solutions of noble metals
    • 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

Definitions

  • the invention relates to the technical field of the metallurgical industry, and in particular to a green gold leaching method for carbon-, sulfur- and arsenic-containing gold ores.
  • gold ores are Carlin-type gold ores. This type of gold ore contains sulfur, arsenic, and carbon. The gold particles are extremely fine and are embedded in pyrite and arsenopyrite. Even if they are leached, the organic carbon inside will adsorb the gold again. (Gold robbery), it is difficult to recover gold efficiently.
  • Chinese patent CN103146920A discloses a pretreatment method for arsenic-containing sulfur-containing refractory gold ore. This method uses ozone + sodium hydroxide to treat the ore, and the gold leaching agent used is sodium cyanide.
  • Sodium cyanide is a highly toxic reagent. Contact with skin wounds, inhalation, and swallowing trace amounts can cause poisoning and death. It will also pollute the environment during the leaching process. Therefore, non-cyanide non-toxic leaching gold is the future development direction.
  • the object of the present invention is to provide a green gold leaching method for carbon-sulfur-arsenic gold ores.
  • the reagents used in the present invention are green and environmentally friendly reagents, do not contain toxic cyanide, and are environmentally friendly.
  • the invention provides a green gold leaching method for carbon-containing sulfur-arsenic gold ore, which includes the following steps:
  • the ore powder is subjected to jet pulse flotation to obtain gold fine powder
  • the preparation method of the non-cyanide gold leaching agent includes: mixing urea, sodium hydroxide and yellow blood salt, and calcining to obtain a calcined product; mixing the calcined product and additives to obtain a non-cyanide gold leaching agent;
  • the additive includes at least one of sodium bromate, sodium thiocyanide, polysulfide, halide, thiourea and thiosulfate.
  • the carbon-containing sulfur-arsenic gold ore includes carbon 0.1-5wt%, sulfur 0.1-15wt%, arsenic 0.1-10wt%, and gold 0.5-100g/t.
  • the fine grinding is performed in a triple vertical mill catalytic arsenic removal and gold leaching device;
  • the triple vertical mill catalytic arsenic removal and gold leaching device includes at least two series-connected mill bodies, ozone generators, A feed port, a catalyst feed port and a discharge port, the ozone generator is connected to the bottom of each of the mill bodies through a gas supply pipeline, and the feed port is provided at the head end of one of the mill bodies, The discharge port is provided at the tail end of a mill body, and the catalyst feeding port is provided on a feed pipeline connected to the feed port.
  • the powder with a fineness less than 44 microns in the mineral powder accounts for more than 85wt%.
  • the jet pulse flotation is carried out in a pulse jet cyclone flotation machine;
  • the pulse jet cyclone flotation machine includes a frame, a feeding mechanism, a mineralization transport mechanism and a flotation mechanism.
  • the frame The flotation mechanism is provided on the upper end of the flotation mechanism.
  • the feeding mechanism is provided on the upper end of the flotation mechanism.
  • the feeding mechanism is connected to the mineralization transportation mechanism.
  • the mineralization transportation mechanism is connected to the flotation mechanism.
  • the flotation mechanism is provided with a concentrate discharge port, a tailings discharge port and a heavy ore discharge port.
  • the gold content in the gold fine powder is 20 to 801 g/t.
  • the base includes sodium carbonate, sodium hydroxide, calcium oxide or calcium hydroxide;
  • the oxidant includes air, oxygen, ozone or hydrogen peroxide;
  • the first catalyst includes manganese oxide, manganese dioxide, iron oxide or oxidized water. Cerium; the mass ratio of the total mass of the gold powder, alkali, oxidant and first catalyst to water is 1:2.5 ⁇ 5.
  • the oxidation reaction is carried out under grinding conditions.
  • the iron salt includes one or more of ferric chloride, ferrous chloride, ferric sulfate and ferrous sulfate.
  • the second catalyst includes ferric chloride or manganite.
  • the invention provides a green gold leaching method for carbon-containing sulfur-arsenic gold ore, which includes the following steps: finely grinding the carbon-containing sulfur-arsenic gold ore to obtain ore powder; subjecting the ore powder to jet pulse flotation to obtain gold Refined powder; mix the gold fine powder with alkali, oxidant, first catalyst and water to perform an oxidation reaction to obtain a carbon-containing sulfur arsenic salt solution; mix the carbon-containing sulfur arsenic salt solution with iron salt and lime to perform precipitation Reaction to obtain decarburized sulfur-arsenic gold ore; mix the decarburized sulfur-arsenic gold ore with a non-cyanide gold leaching agent and a second catalyst, grind and leach to recover gold.
  • the invention uses fine grinding to open the inclusions of carbon-sulfur-arsenic gold ore, which is beneficial to the leaching of gold; it enriches gold through jet pulse flotation and reduces the amount of ore processed; and then converts arsenic into arsenate through oxidation reaction. , sulfur is converted into sulfate, the carbon is passivated, and fine gold is exposed; the precipitation reaction is then used to convert arsenic into stable scorodite, arsenic is no longer dissolved, and sulfate and carbonate are converted into calcium sulfate and calcium carbonate.
  • the present invention uses a non-cyanide gold leaching agent to leach gold from decarburized sulfur and arsenic gold mines. It uses a green and environmentally friendly agent that does not contain toxic cyanide and is environmentally friendly.
  • the green gold immersion method of the present invention is carried out under normal temperature and pressure, near neutral (pH value of 6 to 8) conditions, and is suitable for popularization and application.
  • Figure 1 is a schematic structural diagram of a three-piece vertical mill catalytic arsenic removal and gold leaching device; in Figure 1: 1-1 is the mill body, 1-2 is the ozone generator, 1-3 is the feed inlet, and 1-4 is Catalyst feeding port, 1-5 is the outlet, 1-6 is the feed pipeline, 1-7 is the silo, 1-8 is the main gas pipeline, and 1-9 is the branch pipeline;
  • FIG. 2 is a schematic structural diagram of the pulse jet cyclone flotation machine; in Figure 2: 1 is the pulse jet cyclone flotation machine, 2 is the frame, 3 is the mortar pump, 4 is the feeding pipe, and 5 is the mortar distribution tank. 6 is the branch pipe, 7 is the mixing tank, 8 is the air inlet valve, 9 is the mineralization pipe, 10 is the rotating nozzle, 11 is the mineralization chamber, 12 is the overflow chamber, 13 is the concentrate tank, and 14 is the concentrate discharge 15 is the tailings outlet, and 16 is the heavy ore outlet.
  • 1 is the pulse jet cyclone flotation machine
  • 2 is the frame
  • 3 is the mortar pump
  • 4 is the feeding pipe
  • 5 is the mortar distribution tank.
  • 6 is the branch pipe
  • 7 is the mixing tank
  • 8 is the air inlet valve
  • 9 is the mineralization pipe
  • 10 is the rotating nozzle
  • 11 is the mineralization chamber
  • 12 is the overflow chamber
  • 13 is the concentrate tank
  • 14 is the concentrate discharge 15 is the tailing
  • the invention provides a green gold leaching method for carbon-containing sulfur-arsenic gold ore, which includes the following steps:
  • the ore powder is subjected to jet pulse flotation to obtain gold fine powder
  • the decarburized sulfur-arsenic gold ore is mixed with a non-cyanide gold leaching agent and a second catalyst, and is ground and leached to recover gold;
  • the preparation method of the non-cyanide gold leaching agent includes: combining urea, sodium hydroxide and yellow blood salt mix, Calcination is performed to obtain a calcined product; the calcined product is mixed with an additive to obtain a non-cyanide gold leaching agent; the additive includes sodium bromate, sodium thiocyanide, polysulfide, halide, thiourea and thiosulfate at least one of them.
  • the carbon-containing sulfur-arsenic gold ore is finely ground to obtain mineral powder.
  • the carbon-containing sulfur-arsenic gold ore preferably includes carbon 0.1-5wt%, sulfur 0.1-20wt%, arsenic 0.1-30wt%, and gold 0.5-100g/t.
  • the mass content of carbon in the carbon-containing sulfur-arsenic gold ore is more preferably 1 to 5 wt%; the mass content of sulfur is more preferably 5 to 15 wt%; the mass content of arsenic is more preferably 5 to 10 wt%;
  • the mass content of gold is more preferably 1 to 20 g/t.
  • the fine grinding is preferably performed in a triple vertical mill catalytic arsenic removal and gold leaching device.
  • the specific structure of the triple vertical mill catalytic arsenic removal and gold leaching device will be described in detail below.
  • the powder with a fineness of less than 44 microns in the mineral powder is preferably 85 wt% or more, and more preferably 85 to 90 wt%.
  • the present invention After obtaining the ore powder, the present invention performs jet pulse flotation on the ore powder to obtain gold fine powder.
  • the jet pulse flotation is preferably carried out in a pulse jet cyclone flotation machine.
  • the specific structure of the pulse jet cyclone flotation machine will be described in detail below.
  • this invention uses jet pulse flotation to increase the metal recovery rate by 8 to 10%; especially for the flotation of precious metal minerals and micro- or ultra-fine particles of gold, silver and rare earth minerals, it is more Conducive to improving its recovery rate.
  • the gold content in the gold fine powder is preferably 20 to 801 g/t, and more preferably 43.2 to 52.16 g/t.
  • the present invention mixes the gold fine powder with an alkali, an oxidant, a first catalyst and water, and performs an oxidation reaction to obtain a carbon-containing sulfur arsenic salt solution.
  • the base preferably includes sodium hydroxide or calcium hydroxide; in other embodiments, the base can be replaced by a strong base weak acid salt or an alkaline metal oxide; the strong base weak acid salt is preferably Sodium carbonate; the alkaline metal oxide is preferably calcium oxide; the mass ratio of the gold concentrate and alkali is preferably 1.2 times the theoretical amount.
  • the The oxidizing agent preferably includes air, oxygen, ozone or hydrogen peroxide; the mass ratio of the gold concentrate and the oxidizing agent is preferably 1:0.05-0.1, more preferably 1:0.05.
  • the first catalyst preferably includes manganese oxide, manganese dioxide, iron oxide or cerium oxide; the mass ratio of the gold concentrate and the first catalyst is preferably 1:0.01 ⁇ 0.05, more preferably 1: 0.01.
  • the mass ratio of the total mass of gold powder, alkali, oxidant and first catalyst to water is preferably 1:2.5-5, more preferably 1:2.5.
  • the oxidation reaction is preferably carried out under grinding conditions.
  • the grinding is preferably carried out in a triple vertical mill catalytic arsenic removal and gold leaching device.
  • the carbon, sulfur and arsenic salts in the carbon, sulfur and arsenic salt solution preferably include sodium carbonate, sodium sulfate and sodium arsenate.
  • the present invention mixes the carbon-containing sulfur-arsenic salt solution with iron salt and lime to perform a precipitation reaction to obtain decarburized sulfur-arsenic gold ore.
  • the iron salt preferably includes one or more of ferric chloride, ferrous chloride, ferric sulfate and ferrous sulfate; the carbon, sulfur arsenic salt and iron salt in the carbon-containing sulfur arsenic salt solution
  • the mass ratio is preferably 1:1 to 1.5, more preferably 1:1.5.
  • the mass ratio of carbon, sulfur and arsenic salt to lime in the carbon-sulfur-arsenic salt solution is preferably 1:0.5-1.5, and more preferably 1:0.8.
  • the gold content in the decarburized sulfur-arsenic gold ore is preferably 20 to 80 g/t, and more preferably 50 g/t.
  • the present invention mixes the decarburized sulfur-arsenic gold ore with a non-cyanide gold leaching agent and a second catalyst, and grinds and leaches the gold ore to recover gold.
  • the preparation method of the non-cyanide gold leaching agent includes: mixing urea, sodium hydroxide and yellow blood salt, and calcining to obtain a calcined product; mixing the calcined product and additives to obtain non-cyanide leaching gold. agent; the additive includes at least one of sodium bromate, sodium thiocyanide, polysulfide, halide, thiourea and thiosulfate.
  • the mass ratio of urea, sodium hydroxide and yellow blood salt is preferably 7:2:1.
  • the calcination temperature is preferably 1050°C; the calcination time is preferably 2 hours.
  • the particle size of the calcined powder is preferably 200 mesh.
  • the mass of the additive is preferably 1 to 5% of the mass of the calcined material.
  • the mass ratio of the decarburized sulfur-arsenic gold ore and the non-cyanide gold leaching agent is preferably 1:0.002-0.005, and more preferably 1:0.002.
  • the second catalyst preferably includes three Ferric chloride or gray manganese ore; the mass ratio of the decarburized sulfur-arsenic gold ore and the second catalyst is preferably 1:0.01 to 0.1, more preferably 1:0.01.
  • the grinding and leaching is preferably performed in a triple vertical mill catalytic arsenic removal and gold leaching device.
  • the pH value of the grinding and immersion is preferably 6 to 8.
  • the gold-containing solution it is preferable to obtain a gold-containing solution after grinding and leaching; the gold-containing solution is electrolyzed to recover gold.
  • the gold content in the gold-containing solution is preferably 1 to 20 g/t, and more preferably 10 g/t.
  • the purity of the recovered gold is preferably 99 to 99.99%, more preferably 99.99%.
  • the three-piece vertical mill catalytic arsenic removal and gold leaching device used in the present invention includes at least two series-connected mill bodies 1-1, ozone generators 1-2, feed ports 1-3, and catalysts.
  • the feeding port 1-4 and the discharging port 1-5, the ozone generator 1-2 are connected to the bottom of each mill body 1-1 through the air supply pipeline, and the feeding port 1-3 is provided at the first end of a mill body
  • the head end of 1-1, the discharge port 1-5 is set at the tail end of a mill body 1-1
  • the catalyst feeding port 1-4 is set at the inlet connected to the feed port 1-3.
  • three grinding mill bodies 1-1 are arranged in series, and the head and tail of the three grinding mill bodies 1-1 are connected in series, that is, the discharge port 1 of one mill body 1-1 at the head end -5 is connected to the feed port of the mill body 1-1 at the adjacent tail end.
  • the air outlet of the ozone generator 1-2 is connected to the main gas pipeline 1-8, and the main gas pipeline 1-8 is provided with three bottoms of the mill body 1-1 respectively.
  • the branch pipelines 1-9 provide ozone to the three mill bodies 1-1 respectively through the branch pipelines 1-9.
  • the first end of the feed pipeline 1-6 is connected to the silo 1-7 containing gold concentrate powder, and the discharge port 1-5 is connected to a diaphragm hydraulic press for subsequent processes.
  • the triple vertical mill catalytic arsenic removal and gold leaching device is provided with three mill bodies 1-1 connected in series, and additionally adds a catalyst inlet and an ozone inlet, so that catalyst can be added into the mill body 1-1 , introduce ozone, add chemical crushing on the basis of physical crushing, so that the refractory sulfide is coated with gold, and fine grinding in the three-piece ultra-fine vertical mill fully exposes the dissociation of the coated gold.
  • Electric power is more economical than conventional ball mills. Energy consumption; the new process of extracting gold by adding catalyst while grinding and leaching has the most significant advantage of strengthening the leaching function.
  • the leaching time of gold is shortened by 2/3 compared with conventional stirring leaching.
  • the fine gold particles themselves are also continuously ground, which increases the surface area for dissolution, thereby shortening the dissolution time of gold, greatly reducing energy consumption, and saving more than 50% energy than traditional methods.
  • the dissolution time of immersion gold saves about 4/5 of the energy consumption time compared with traditional gold immersion time.
  • the heat generated by intense grinding between the grinding medium and the ore material increases the temperature of the slurry, which is conducive to the leaching of gold and shortens the process.
  • the three-piece vertical ultra-fine grinding and leaching machine is more effective than the single tower mill while grinding and leaching. Unique efficiency. It replaces the long and cumbersome process of refractory gold ore that is difficult to treat and leaches with traditional technology, which requires two stages of roasting to remove arsenic, sulfur and impurities, water crushing, regrinding, stirring and leaching, zinc powder replacement, and smelting and casting of gold. At the same time, it causes two environmental problems. Secondary pollution pressure is a serious problem, which makes the atmosphere more purified and is conducive to environmental protection.
  • the mill body is a tower mill among existing ball mills, and its structure and working principle will not be described in detail.
  • the pulse jet cyclone flotation machine 1 includes a frame 2, a feeding mechanism, a mineralization transport mechanism and a flotation mechanism.
  • the frame 2 is provided with a flotation mechanism, and the upper end of the flotation mechanism is provided with a feeding mechanism.
  • the feeding mechanism is connected to the mineralization transportation mechanism, and the mineralization transportation mechanism is connected to the lower end of the flotation mechanism.
  • the flotation mechanism is provided with a concentrate discharge port 14, a tailings discharge port 15 and a heavy ore discharge port. Mine discharge port 16.
  • the feeding mechanism includes a mortar pump 3, a feeding pipe 4 and a mortar distribution tank 5.
  • the mortar distribution tank 5 is arranged on the top of the flotation mechanism.
  • the mortar pump 3 communicates with the mortar through the feeding pipe 4.
  • the bottom of the distribution tank 5 is connected, and the mortar distribution tank 5 is connected with the mineralization transport mechanism.
  • the mortar pump 3 is a variable frequency pump, which can appropriately adjust the power of the mortar pump 3 according to the size and dispersion of bubbles in the overflow chamber 12, and then adjust the rotation speed and spray pressure of the rotating nozzle 10 to make the bubbles meet the requirements of flotation. Require.
  • the feeding tube 4 is provided with rifling, which facilitates the uniform mixing of the mortar during transportation and also facilitates the uniform mixing of the mortar in the mortar distribution tank 5 .
  • the mineralization transportation mechanism includes a mixing tank 7, an air inlet valve 8, a mineralization pipe 9 and a rotating nozzle 10.
  • the four mixing tanks 7 are each connected to the mortar distribution tank 5 through a branch pipe 6.
  • An air inlet valve 8 is provided on the side wall of the mixing tank 7, and a mineralization pipe 9 is connected to the bottom.
  • the end of the mineralization pipe 9 extends into the flotation mechanism and is provided with a rotating nozzle 10.
  • the mineralization tube 9 is provided with rifling, which facilitates the mortar to carry air during transportation, enables the air and the mortar to be quickly and fully mixed, increases the swirl function, and improves the mineralization effect of the mortar;
  • the rotating nozzle 10 includes a throat tube and two nozzles.
  • the flotation mechanism includes a mineralization chamber 11, an overflow chamber 12 and a concentrate tank 13.
  • the concentrate tank 13 is provided in the middle of the mineralization chamber 11 through a hollow bracket, and the top is connected with a concentrate tank 13.
  • Overflow chamber 12 The top of the mineralization chamber 11 is connected to the concentrate tank 13 through the overflow chamber 12.
  • the concentrate tank 13 is provided with a concentrate discharge port 14 and a tailings discharge port 16.
  • the concentrate tank 13 is connected with the overflow chamber 12.
  • the concentrate outlet 14 and the tailings outlet 16 respectively penetrate the bottom of the mineralization chamber 11.
  • the tailings outlet 16 is used to collect tailings. .
  • a heavy ore discharge port 16 is provided at the bottom of the mineralization chamber 11 for collecting heavy ore.
  • the mineralization chamber 11 includes a cone, a straight cylinder and a cone bucket connected in sequence.
  • the cone is small at the top and large at the bottom, which is conducive to the separation of heavy ores.
  • the nozzles are evenly distributed on the wall of the straight cylinder, and the hollow bracket is arranged on the concentrate tank. Between the bottom of 13 and the conical bucket, heavy ore can fall into the heavy ore area through the hollow bracket.
  • the concentrate tank 13 is in the shape of a conical bucket, and the cone angle of the concentrate tank 13 is 25° to 40°, which facilitates the enrichment of tailings and concentrate.
  • the bottom of the concentrate tank 13 is connected to a tailings cone, the tailings cone is provided with a tailings discharge port 15, and the lower end of the concentrate tank 13 is provided with a concentrate discharge port 14.
  • the height of the concentrate discharge port 14 can be selected to be 5 to 50 cm from the bottom of the tailings cone, and the total height of the mineralization chamber 11 is 100 to 200 cm. , according to different mineral types, different enrichment heights can be set for collection to improve the recovery rate of concentrates.
  • the pulse jet cyclone flotation machine 1 transports the slurry upward through the slurry pump and feeding pipe 4 to the mortar distribution tank 5, and then branches to four mineralization pipes 9, and carries air into the mineralization In chamber 11, the slurry pressure drops suddenly and the volume increases instantaneously through the swirling pulse injection from the rotating nozzle 10.
  • Minerals and flotation agents are added to the mixing tank 7.
  • the mineralization reaction is completed, and bubbles are formed instantly when sprayed out, so that the light minerals It adheres to the uniform bubbles to form a bubble suspension layer.
  • the bubble suspension layer floats up. It enters the overflow chamber 12 in the flotation mineralization chamber, and then enters the concentrate tank to complete the flotation of the concentrate.
  • the heavier tailings It will be enriched at the bottom of the cone hopper, and the tailings can be discharged from the tailings discharge port 15, and the concentrate can be discharged from the concentrate discharge port 14. ore; and after the rotating nozzle 10 is ejected, the heaviest heavy ore will directly sink to the bottom of the mineralization chamber 11, and the heavy ore will be discharged from the heavy ore discharge port 16 for other by-product processing.
  • the slurry of the jet cyclone flotation machine used in the present invention is controlled by a pulsating self-priming valve added at the upper end of the feeding pipe, so that the slurry changes from a continuous jet state to a pulsating jet state.
  • the high-pressure subduction self-priming mineralization passes through the nozzle, and then recoils
  • the flotation is completed by floating, and the slurry is mixed with the air through the rifling action, which accelerates the suction capacity of the slurry and improves the mineralization mixing efficiency; the microbubbles of the mineralized slurry account for 30% of the total bubbles, and the flotation foam is more stable and high.
  • the single-tube or double-tube type is used as the discharge pipe for the injection of slurry.
  • the nozzle can use the existing funnel-shaped nozzle, which is beneficial to the flotation of ultra-fine ores and is the ideal method for regeneration and recovery of ultra-fine ores. The best choice, it solves the problem of low flotation recovery rate and efficiency of general flotation machines, and the inability to effectively flotate refractory ore slurries that are too fine and easy to muddy.
  • the pulse jet cyclone flotation machine 1 of the present invention can be used in the production of non-ferrous metal mines, rare earth mines, non-metallic ores and gold mines, and can also be used for the flotation of any valuable metal ores and non-metallic ores, with flotation characteristics.
  • Fast selection and collection speed (the collection and separation time of minerals in the mineralization chamber 11 is about 3 seconds, and the concentrate can be obtained 5 to 6 minutes after the foam layer floats to the liquid level), large rich ore ratio, and high flotation efficiency , simple operation process, easy control of flotation liquid level, slurry concentration, grinding particle size, wide application range, etc., energy consumption can be reduced by 40 to 60%, flotation slurry concentration can reach 30 to 38%, and the total equipment investment is reduced by 40 %, the plant area is reduced by 40-60%, and the concentrate recovery rate is increased by 8-10%; especially for flotation recovery of fine-grained gold or ultra-fine gold, silver and rare earth minerals in precious metal minerals and Carlin-type gold mines The rate increase has a more obvious effect.
  • the invention enables the development of flotation equipment from large-scale to high-efficiency miniaturization, and overcomes the disadvantages of conventional flotation machines that micro-fine minerals are easily lost with the slurry and are difficult to flotation and capture. It is aimed at flotation capture of micro-fine minerals of 325 to 800 mesh. It has special effects and effectively improves flotation efficiency.
  • the main equipment adopts a triple vertical mill catalytic arsenic removal and gold leaching device with a rotating speed set at 22-33r/min. Mechanical strong friction, using 0.5wt% ferric chloride catalyst at normal temperature and pressure, introducing air to remove arsenic, desulfurization and impurities, destroy its original mineral structure, and generate arsenic pyrite (arsenic sand) that is easily soluble in water.
  • the pulp concentration is 40-50%, the silica inhibitor water glass is 0.5kg/t, stir for 30 minutes, the concentration of non-cyanide gold leaching agent is 0.3wt%, the pH value of the pulp is 6-9 (lime adjustment), and the catalyst manganese dioxide is 0.1wt %, the closed-circuit circulation grinding and immersion time is 1 to 8 hours, the rotation speed is 22 to 32 r/min, and oxygen is supplied; secondly, during the grinding process of the slurry, the gold particles continue to expose new surfaces, which increases the reaction activity and is conducive to cyanide-free
  • the gold leaching agent reacts with gold to obtain a gold-containing solution; at the same time, the gold particles are continuously finely ground, increasing the dissolution surface area, speeding up the gold leaching speed, shortening the gold leaching time, and recovering gold after electrolysis.
  • the gold leaching rate reaches 85%.
  • the preparation method of the non-cyanide gold leaching agent used in this embodiment is as follows: mix urea, sodium hydroxide and yellow blood salt according to the mass ratio of 7:2:1, and calcine at 1050°C for 2 hours to obtain a calcined product; in the calcined Add 1wt% sodium bromate to the mixture to obtain a non-cyanide gold leaching agent.
  • the raw ore contains 3.21g/t gold, 2.42% organic carbon, 7.82% total carbon, 0.68% arsenic, 4.21% iron, and 3.2% sulfur.
  • the raw ore is ground to -325 mesh accounting for 90wt%, and flotation is performed using a pulse jet cyclone flotation machine to obtain gold fine powder.
  • the gold fine powder contains 52.16g/t gold; the solid-liquid ratio is selected to be 1:3.
  • the ore is grinded and leached at the same time.
  • the main equipment adopts the mechanical strong friction of the triple vertical mill catalytic arsenic removal and gold leaching device with the rotation speed set at 22-33r/min, and uses 0.5wt% ferric chloride catalyst at normal temperature and pressure. Ozone is introduced to remove arsenic, desulfurization and impurities, destroying its original mineral structure.
  • Arsenic pyrite (arsenic sand) generates sodium arsenate that is easily soluble in water. After solid-liquid separation, arsenic enters the solution and oxidizes with ferric chloride to form scorodite and is removed; under the action of the catalyst cerium oxide, organic carbon is oxidized into carbonate, and the "gold robbing" function fails; after arsenic removal, the solid is in Three-piece vertical mill catalytic arsenic removal gold leaching device tower mill, gold concentrate fully dissociates and exposes gold and sulfide, stirs with non-cyanide gold leaching agent, the solid-liquid ratio is 1:2, and water is added to adjust the slurry concentration to 40-50 %, silica inhibitor water glass 0.5kg/t, stir for 30 minutes, the concentration of non-cyanide gold leaching agent is 0.3wt%, the pH value of the slurry is 6 to 9 (lime adjustment), the catalyst manganese dioxide is 0.1wt%, closed circuit The cyclic grinding
  • the preparation method of the non-cyanide gold leaching agent used in this embodiment is as follows: mix urea, sodium hydroxide and yellow blood salt according to the mass ratio of 7:2:1, and calcine at 1050°C for 2 hours to obtain a calcined product; in the calcined Add 1wt% sodium thiocyanide into the mixture to obtain a non-cyanide gold leaching agent.
  • the raw ore contains 3.21g/t gold, 2.42% organic carbon, 7.82% total carbon, 0.68% arsenic, 4.21% iron, and 3.2% sulfur.
  • Gold is leached according to the method of Example 1, and the obtained gold-containing solution is purified, deoxidized, and replaced with fast lightning zinc powder to efficiently obtain gold smelted and cast from gold mud.
  • oxygen-rich air is introduced, and the catalyst is manganese oxide.
  • Ferrous sulfate and hydrogen peroxide are added to the solution after filtering.
  • the calcium oxide is stirred and converted to synthesize.
  • the scorodite is backfilled by filtering, and lime is added to the filtrate in the reaction tank. After causticization, it enters the buffer tank for storage and returns to slurry mixing; the solid-liquid separation gold-containing carrier mineral dry residue is sent to the gold leaching process.
  • Gold leaching is also done by grinding and leaching, adding non-cyanide gold leaching agent, stirring the gold leaching slurry and then solid-liquid separation.
  • the expensive liquid is sent to the top for purification, deoxidation and gold recovery; the lean liquid is returned to the slurry for leaching; lime is added to the tailings to precipitate to obtain gypsum slag.
  • calcium sulfate and other standard emissions, and gelling agents can also be added to solidify the backfill.
  • the gold recovery rate is 96%.
  • the preparation method of the non-cyanide gold leaching agent used in this embodiment is as follows: mix urea, sodium hydroxide and yellow blood salt according to the mass ratio of 7:2:1, and calcine at 1050°C for 2 hours to obtain a calcined product; in the calcined Add 0.5wt% sodium bromate and 0.5wt% sodium thiocyanide into the mixture to obtain a non-cyanide gold leaching agent.
  • the gold recovery rate can be guaranteed to be above 94%, which is much better than the 30-70% gold recovery rate of current general treatment methods.

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Abstract

本发明提供了一种含碳硫砷金矿的绿色浸金方法，涉及冶金工业技术领域。本发明利用细磨，打开含碳硫砷金矿的包裹体，有利于金的浸出；通过射流脉冲浮选使金富集，减少矿石处理量；然后通过氧化反应，使砷转化为砷酸盐，硫转化为硫酸盐，碳钝化，细金暴露出来；再利用沉淀反应，使砷转变为稳定的臭葱石，砷不再溶出，硫酸盐、碳酸盐转变成硫酸钙、碳酸钙，碳酸钙除去，烧碱再生，重复使用；本发明采用非氰浸金剂浸出脱碳硫砷的金矿中的金，采用的是绿色环保药剂，不含有毒的氰化物，环境友好。本发明的绿色浸金方法在常温常压下进行，近中性(pH值为6～8)，适宜推广应用。

Description

一种含碳硫砷金矿的绿色浸金方法
本申请要求于2022年03月30日提交中国专利局、申请号为CN202210327436.6、发明名称为“一种含碳硫砷金矿的绿色浸金方法”的中国专利申请的优先权，其全部内容通过引用结合在本申请中。
技术领域
本发明涉及冶金工业技术领域，具体涉及一种含碳硫砷金矿的绿色浸金方法。
背景技术
一般难选难浸金矿石为卡林型金矿，这类金矿含硫砷碳，黄金颗粒极细，镶嵌在黄铁矿、毒砂中，即使浸出，里面的有机碳又重新将金吸附(劫金)，难以高效回收金。
中国专利CN103146920A公开了一种含砷含硫难浸金矿石预处理方法，该方法用臭氧+氢氧化钠处理矿石，采用的浸金剂为氰化钠。氰化钠是剧毒试剂，皮肤伤口接触、吸入、吞食微量可中毒死亡，在浸出过程中也会污染环境，因此，非氰无毒浸出金是未来的发展方向。
发明内容
本发明的目的在于提供一种含碳硫砷金矿的绿色浸金方法，本发明采用的药剂为绿色环保药剂，不含有毒的氰化物，环境友好。
为了实现上述发明目的，本发明提供以下技术方案：
本发明提供了一种含碳硫砷金矿的绿色浸金方法，包括以下步骤：
将含碳硫砷金矿进行细磨，得到矿粉；
将所述矿粉进行射流脉冲浮选，得到金精粉；
将所述金精粉和碱、氧化剂、第一催化剂以及水混合，进行氧化反应，得到含碳硫砷盐溶液；
将所述含碳硫砷盐溶液和铁盐以及石灰混合，进行沉淀反应，得到脱碳硫砷的金矿；
将所述脱碳硫砷的金矿和非氰浸金剂以及第二催化剂混合，边磨边浸， 回收金；所述非氰浸金剂的制备方法包括：将尿素、氢氧化钠和黄血盐混合，进行煅烧，得到煅烧物；将所述煅烧物和添加剂混合，得到非氰浸金剂；所述添加剂包括溴酸钠、硫氰化钠、多硫化物、卤化物、硫脲和硫代硫酸盐中的至少一种。
优选地，所述含碳硫砷金矿包括碳0.1～5wt％，硫0.1～15wt％，砷0.1～10wt％，金0.5～100g/t。
优选地，所述细磨在三连体立磨催化脱砷浸金装置中进行；所述三连体立磨催化脱砷浸金装置，包括至少两个串联的磨机本体、臭氧发生器、进料口、催化剂加料口和出料口，所述臭氧发生器通过供气管路连接各个所述磨机本体的底部，所述进料口设置于首端的一个所述磨机本体的首端，所述出料口设置于尾端的一个磨机本体的尾端，所述催化剂加料口设置于与所述进料口连通的进料管路上。
优选地，所述矿粉中细度小于44微米的粉剂为85wt％以上。
优选地，所述射流脉冲浮选在脉冲射流旋流浮选机中进行；所述脉冲射流旋流浮选机包括机架、上料机构、矿化运输机构和浮选机构，所述机架上设置有所述浮选机构，所述浮选机构的上端设置有所述上料机构，所述上料机构连通所述矿化运输机构，所述矿化运输机构连通所述浮选机构的下端，所述浮选机构上设置有精矿出料口、尾矿出料口和重矿出料口。
优选地，所述金精粉中金的含量为20～801g/t。
优选地，所述碱包括碳酸钠、氢氧化钠、氧化钙或氢氧化钙；所述氧化剂包括空气、氧气、臭氧或双氧水；所述第一催化剂包括氧化锰、二氧化锰、氧化铁或氧化铈；所述金精粉、碱、氧化剂和第一催化剂的总质量与水的质量比为1:2.5～5。
优选地，所述氧化反应在磨矿条件下进行。
优选地，所述铁盐包括氯化铁、氯化亚铁、硫酸铁和硫酸亚铁中的一种或几种。
优选地，所述第二催化剂包括三氯化铁或灰锰矿。
本发明提供了一种含碳硫砷金矿的绿色浸金方法，包括以下步骤：将含碳硫砷金矿进行细磨，得到矿粉；将所述矿粉进行射流脉冲浮选，得到金精 粉；将所述金精粉和碱、氧化剂、第一催化剂以及水混合，进行氧化反应，得到含碳硫砷盐溶液；将所述含碳硫砷盐溶液和铁盐以及石灰混合，进行沉淀反应，得到脱碳硫砷的金矿；将所述脱碳硫砷的金矿和非氰浸金剂以及第二催化剂混合，边磨边浸，回收金。本发明利用细磨，打开含碳硫砷金矿的包裹体，有利于金的浸出；通过射流脉冲浮选使金富集，减少矿石处理量；然后通过氧化反应，使砷转化为砷酸盐，硫转化为硫酸盐，碳钝化，细金暴露出来；再利用沉淀反应，使砷转变为稳定的臭葱石，砷不再溶出，硫酸盐、碳酸盐转变成硫酸钙、碳酸钙，碳酸钙除去，烧碱再生，重复使用；本发明采用非氰浸金剂浸出脱碳硫砷的金矿中的金，采用的是绿色环保药剂，不含有毒的氰化物，环境友好。本发明的绿色浸金方法在常温常压、近中性(pH值为6～8)条件下进行，适宜推广应用。
附图说明
图1为三连体立磨催化脱砷浸金装置的结构示意图；图1中：1-1为磨机本体、1-2为臭氧发生器、1-3为进料口、1-4为催化剂加料口、1-5为出料口、1-6为进料管路、1-7为料仓、1-8为总输气管路、1-9为支管路；
图2为脉冲射流旋流浮选机的结构示意图；图2中：1为脉冲射流旋流浮选机，2为机架，3为砂浆泵，4为上料管，5为砂浆分配罐，6为支管，7为混合罐，8为进气阀，9为矿化管，10为旋转喷嘴，11为矿化室，12为溢流室，13为精矿罐，14为精矿出料口，15为尾矿出料口，16为重矿出料口。
具体实施方式
本发明提供了一种含碳硫砷金矿的绿色浸金方法，包括以下步骤：
将含碳硫砷金矿进行细磨，得到矿粉；
将所述矿粉进行射流脉冲浮选，得到金精粉；
将所述金精粉和碱、氧化剂、第一催化剂以及水混合，进行氧化反应，得到含碳硫砷盐溶液；
将所述含碳硫砷盐溶液和铁盐以及石灰混合，进行沉淀反应，得到脱碳硫砷的金矿；
将所述脱碳硫砷的金矿和非氰浸金剂以及第二催化剂混合，边磨边浸，回收金；所述非氰浸金剂的制备方法包括：将尿素、氢氧化钠和黄血盐混合， 进行煅烧，得到煅烧物；将所述煅烧物和添加剂混合，得到非氰浸金剂；所述添加剂包括溴酸钠、硫氰化钠、多硫化物、卤化物、硫脲和硫代硫酸盐中的至少一种。
本发明将含碳硫砷金矿进行细磨，得到矿粉。在本发明中，所述含碳硫砷金矿优选包括碳0.1～5wt％，硫0.1～20wt％，砷0.1～30wt％，金0.5～100g/t。在本发明中，所述含碳硫砷金矿中碳的质量含量更优选为1～5wt％；硫的质量含量更优选为5～15wt％；砷的质量含量更优选为5～10wt％；金的质量含量更优选为1～20g/t。
在本发明中，所述细磨优选在三连体立磨催化脱砷浸金装置中进行。在本发明中，所述三连体立磨催化脱砷浸金装置的具体结构在下文进行详细说明。
在本发明中，所述矿粉中细度小于44微米的粉剂优选为85wt％以上，更优选为85～90wt％。
得到矿粉后，本发明将所述矿粉进行射流脉冲浮选，得到金精粉。在本发明中，所述射流脉冲浮选优选在脉冲射流旋流浮选机中进行。在本发明中，所述脉冲射流旋流浮选机的具体结构在下文进行详细说明。本发明采用射流脉冲浮选相比于普通刮板浮选槽，金属回收率提高了8～10％；特别是对贵金属矿物及微细粒或超微细粒金、银和稀土矿物浮选，更有利于提高其回收率。相比而言，能耗降低40～60％，富矿比大、流程简单、设备总投资减少40％，厂房占地面积减少40～60％，具有工艺易于控制、矿浆浓度、磨矿粒度适用范围广等优点。克服了微细粒矿物易随矿浆流失泥化的弊端，针对微细粒325～600目矿物有特效。
在本发明中，所述金精粉中金的含量优选为20～801g/t，更优选为43.2～52.16g/t。
得到金精粉后，本发明将所述金精粉和碱、氧化剂、第一催化剂以及水混合，进行氧化反应，得到含碳硫砷盐溶液。在本发明中，所述碱优选包括氢氧化钠或氢氧化钙；在另外的实施例中，碱可以替换为强碱弱酸盐或碱性金属氧化物；所述强碱弱酸盐优选为碳酸钠；所述碱性金属氧化物优选为氧化钙；所述金精矿和碱的质量比优选为理论量的1.2倍。在本发明中，所述 氧化剂优选包括空气、氧气、臭氧或双氧水；所述金精矿和氧化剂的质量比优选为1:0.05～0.1，更优选为1:0.05。在本发明中，所述第一催化剂优选包括氧化锰、二氧化锰、氧化铁或氧化铈；所述金精矿和第一催化剂的质量比优选为1:0.01～0.05，更优选为1:0.01。在本发明中，所述金精粉、碱、氧化剂和第一催化剂的总质量与水的质量比优选为1:2.5～5，更优选为1:2.5。
在本发明中，所述氧化反应优选在磨矿条件下进行。在本发明中，所述磨矿优选在三连体立磨催化脱砷浸金装置中进行。
在本发明中，所述含碳硫砷盐溶液中的碳硫砷盐优选包括碳酸钠、硫酸钠和砷酸钠。
得到含碳硫砷盐溶液后，本发明将所述含碳硫砷盐溶液和铁盐以及石灰混合，进行沉淀反应，得到脱碳硫砷的金矿。在本发明中，所述铁盐优选包括氯化铁、氯化亚铁、硫酸铁和硫酸亚铁中的一种或几种；所述含碳硫砷盐溶液中碳硫砷盐与铁盐的质量比优选为1:1～1.5，更优选为1:1.5。在本发明中，所述含碳硫砷盐溶液中碳硫砷盐与石灰的质量比优选为1：0.5～1.5，更优选为1:0.8。
在本发明中，所述脱碳硫砷的金矿中金的含量优选为20～80g/t，更优选为50g/t。
得到脱碳硫砷的金矿后，本发明将所述脱碳硫砷的金矿和非氰浸金剂以及第二催化剂混合，边磨边浸，回收金。在本发明中，所述非氰浸金剂的制备方法包括：将尿素、氢氧化钠和黄血盐混合，进行煅烧，得到煅烧物；将所述煅烧物和添加剂混合，得到非氰浸金剂；所述添加剂包括溴酸钠、硫氰化钠、多硫化物、卤化物、硫脲和硫代硫酸盐中的至少一种。
在本发明中，所述尿素、氢氧化钠和黄血盐的质量比优选为7:2:1。在本发明中，所述煅烧的温度优选为1050℃；所述煅烧的时间优选为2h。本发明优选在所述煅烧后进行粉碎，然后将得到的煅烧粉末与添加剂混合。在本发明中，所述煅烧粉末的粒径优选为200目。
在本发明中，所述添加剂的质量优选为煅烧物质量的1～5％。
在本发明中，所述脱碳硫砷的金矿和非氰浸金剂的质量比优选为1:0.002～0.005，更优选为1:0.002。在本发明中，所述第二催化剂优选包括三 氯化铁或灰锰矿；所述脱碳硫砷的金矿和第二催化剂的质量比优选为1:0.01～0.1，更优选为1:0.01。
在本发明中，所述边磨边浸优选在三连体立磨催化脱砷浸金装置中进行。在本发明中，所述边磨边浸的pH值优选为6～8。
本发明优选在所述边磨边浸后得到含金溶液；将所述含金溶液进行电解，回收金。在本发明中，所述含金溶液中金的含量优选为1～20g/t，更优选为10g/t。
在本发明中，回收得到的金的纯度优选为99～99.99％，更优选为99.99％。
下面对所述三连体立磨催化脱砷浸金装置进行具体说明：
本发明采用的三连体立磨催化脱砷浸金装置，如图1所示，包括至少两个串联的磨机本体1-1、臭氧发生器1-2、进料口1-3、催化剂加料口1-4和出料口1-5，臭氧发生器1-2通过供气管路连接各个磨机本体1-1的底部，所述进料口1-3设置于首端的一个磨机本体1-1的首端，所述出料口1-5设置于尾端的一个磨机本体1-1的尾端，所述催化剂加料口1-4设置于与进料口1-3连通的进料管路1-6上。
作为本发明的一个实施例，所述磨机本体1-1串联设置有3个，3个磨机本体1-1的首尾串联连接，即首端的一个磨机本体1-1的出料口1-5连接与其相邻的尾端的磨机本体1-1的进料口。
作为本发明的一个实施例，所述臭氧发生器1-2的出气口连接总输气管路1-8，总输气管路1-8上设置有分别连接3个磨机本体1-1底部的支管路1-9，通过支管路1-9分别向3个磨机本体1-1提供臭氧。
作为本发明的一个实施例，所述进料管路1-6的首端连接装有金精矿粉的料仓1-7，出料口1-5连接隔膜压液机，进行后续工序。
在本发明中，所述三连体立磨催化脱砷浸金装置设置三个串联的磨机本体1-1，并且额外增加催化剂入口和臭氧入口，能够向磨机本体1-1内加入催化剂、通入臭氧，在物理破碎的基础上增加化学破碎，使难浸硫化物包裹金，在三连体超细立磨机细磨充分暴露包裹金的解离，电功比常规的球磨机更节省能耗；加入催化剂边磨边浸的提金新工艺，具有最大显著优点是强化浸出的功能，金的浸出比常规搅拌浸出缩短2/3时间。
所述三连体立磨催化脱砷浸金装置的原理如下：
(1)粗颗粒矿料在被三体立磨机细磨过程中不断暴露出新鲜的金微粒表面，该表面反应活性高，有利于络合反应的进行；
(2)磨矿介质与矿料、矿料与矿料之间强烈的碾磨搅拌作用，破坏或减薄了被浸金微粒表面的界面层，强化了无氰浸金剂碱金属离子分子和金络合离子的扩散，从而加快了金的氧化络合反应。
(3)微细粒金颗粒本身也不断被磨细，使溶解的表面积不断增加，从而缩短了金的溶解时间，大幅度降低能耗，比传统方法节能50％以上。浸金的溶解时间比传统浸金时间省4/5左右的能耗时间。
(4)磨矿介质和矿料之间强烈碾磨产生热量提高矿浆温度有利于金的浸出且流程缩短，三连体立式超细磨浸机比单体塔磨机边磨边浸更显独特的效率。解决替代了传统工艺难处理难浸金矿需要二段焙烧脱砷硫除杂、水碎、再磨矿、搅拌浸出，锌粉置换、冶炼铸金的慢长繁琐工序流程，同时对环保造成二次污染压力严肃问题，使大气更加得到净化，有利于环境保护。
需要说明的是，磨机本体为现有球磨机中的一种塔磨机，对其结构和工作原理不做赘述。
下面对所述脉冲射流旋流浮选机进行详细说明：
在本发明中，所述脉冲射流旋流浮选机的结构示意图如图2所示。脉冲射流旋流浮选机1包括机架2、上料机构、矿化运输机构和浮选机构，所述机架2上设置有浮选机构，浮选机构的上端设置有上料机构，所述上料机构连通所述矿化运输机构，所述矿化运输机构连通所述浮选机构的下端，所述浮选机构上设置有精矿出料口14、尾矿出料口15和重矿出料口16。
作为本发明的一个实施例，所述上料机构包括砂浆泵3、上料管4和砂浆分配罐5，砂浆分配罐5设置于浮选机构的顶部，砂浆泵3通过上料管4与砂浆分配罐5的底部连通，砂浆分配罐5与矿化运输机构连通。所述砂浆泵3为变频泵，可根据溢流室12内气泡的大小、分散情况，适当调节砂浆泵3的功率，进而调节旋转喷嘴10出的转速和喷浆压力，使气泡符合浮选的要求。所述上料管4内设置有膛线，便于砂浆在运输过程中混合均匀，也有利于砂浆在砂浆分配罐5中混合均匀。
作为本发明的一个实施例，所述矿化运输机构包括混合罐7、进气阀8、矿化管9和旋转喷嘴10，四个混合罐7分别通过一支管6与砂浆分配罐5连通，所述混合罐7的侧壁上设置有进气阀8、底部连通矿化管9，所述矿化管9的末端伸入浮选机构内部且设置有旋转喷嘴10。所述矿化管9内设置有膛线，便于砂浆在运输过程中携带空气，并使空气与砂浆能快速、充分混合，增加旋流功能，提高砂浆的矿化效果；所述旋转喷嘴10包括喉管和两个喷嘴。
作为本发明的一个实施例，所述浮选机构包括矿化室11、溢流室12和精矿罐13，所述矿化室11的中部通过镂空支架设置有精矿罐13、顶部连通有溢流室12，所述矿化室11的顶部通过溢流室12与精矿罐13连通，所述精矿罐13上设置有精矿出料口14和尾矿出料口16，所述精矿罐13与溢流室12相连通，所述精矿出料口14和尾矿出料口16分别穿出矿化室11的底部，所述尾矿出料口16用于收集尾矿。所述矿化室11的底部设置有重矿出料口16，用于收集重矿。所述矿化室11包括依次连通的锥筒、直筒和锥斗，锥筒上小下大，有利于重矿的分选，喷嘴均布于直筒的罐壁上，镂空支架设置于精矿罐13的底部与锥斗之间，重矿可通过镂空支架落入重矿区。所述精矿罐13呈锥斗状，精矿罐13的锥角为25°～40°，便于尾矿和精矿的富集。所述精矿罐13的底部连通有一尾矿锥斗，尾矿锥斗上设置有尾矿出料口15，所述精矿罐13的下端设置有精矿出料口14。根据矿石的种类、矿选常识和精矿回收率及品位，可将精矿出料口14选在距离尾矿锥斗底面的高度为5～50cm，矿化室11的总高度为100～200cm，可根据不同矿物种类，设置不同的富集高度，进行收集，以提高精矿的回收率。
在本发明中，所述脉冲射流旋流浮选机1从矿浆经矿浆泵和上料管4向上输送至砂浆分配罐5，在分流至四个矿化管9中，并携带空气进入矿化室11，经旋转喷嘴10旋流脉冲喷射，矿浆压力突降、体积瞬间增大，在混合罐7中添加矿物与浮选剂，矿化反应完成，喷出瞬间形成气泡，使轻细的矿物粘附在均匀的气泡上形成气泡悬浮层，气泡悬浮层富集后上浮，在浮选矿化室进入溢流室12，再进入精矿罐，完成精矿的浮选，较重的尾矿就会富集在锥斗底部，可由尾矿出料口15排出尾矿，精矿可由精矿出料口14排出精 矿；而旋转喷嘴10喷出后，最重的重矿将直接沉入矿化室11的底部，由重矿出料口16排出重矿，进行其他副产物加工。
本发明采用的射流旋流浮选机矿浆在下料管上端增加的脉动自吸气阀门控制下，使矿浆由连续射流状态转变为脉动射流状态，高压俯冲自吸气矿化经喷嘴，然后反冲上浮完成浮选，经膛线作用矿浆旋流与空气混合，加速矿浆的吸气能力，提高矿化混合效率；矿化后的矿浆微泡占气泡总量30％，浮选泡沫更稳定高，路经矿化室、喷射喉管，单管型或双管型作为喷射矿浆的下料管，喷嘴可采用现有的漏斗型状喷嘴，有利于超细矿的浮选，是超细矿再生回收最佳选择，解决了一般浮选机浮选回收率和效率不高、对过细易泥化的难选矿矿浆无法有效进行浮选的难题。
本发明的脉冲射流旋流浮选机1可应用于有色金属矿山、稀土矿山、非金属矿和黄金矿山的生产中，也可以用于任何有价金属矿及非金属矿的浮选，具有浮选速度快、捕收速度快(矿化室11内矿物的捕收分离时间约3秒钟，泡沫层上浮液面5～6分钟后即可获得精矿)、富矿比大、浮选效率高、操作流程简单、浮选液面易于控制、矿浆浓度、磨矿粒度、适用范围广等优点，能耗能够降低40～60％，浮选矿浆浓度可达到30～38％、设备总投资减少40％，厂房占地面积减少40～60％，精矿回收率提高8～10％；特别是对贵金属矿物及卡林型金矿中的微细粒金或超微细金、银和稀土矿物浮选回收率提高有更明显的效果。本发明使浮选设备由大型化转向高效小型化发展，克服了常规浮选机对微细粒矿物易随矿浆流失难以浮选捕收的弊端，针对微细粒325～800目矿物的浮选捕收具有特殊的效果，有效提高了浮选效率。
下面将结合本发明中的实施例，对本发明中的技术方案进行清楚、完整地描述。显然，所描述的实施例仅仅是本发明一部分实施例，而不是全部的实施例。基于本发明中的实施例，本领域普通技术人员在没有做出创造性劳动前提下所获得的所有其他实施例，都属于本发明保护的范围。
实施例1
将表1的原矿磨至-325目占85wt％，用脉冲射流旋流浮选机进行浮选，获得金精粉，所述金精粉中含金43.2g/t；固液比选择1：2.5进行边磨矿边浸，主体设备采用转速设定为22～33r/min三连体立磨催化脱砷浸金装置的机 械强烈磨擦，在常温、常压下利用氯化铁催化剂0.5wt％，通入空气，脱砷脱硫除杂、破坏其原生矿物质结构，砷黄铁矿(毒砂)生成易溶于水的砷酸钠，经固液分离后，砷进入溶液再与硫酸亚铁氧化反应生成臭葱石而除去；在催化剂二氧化锰作用下有机碳被氧化成碳酸盐，“劫金”功能失效；脱砷后固体在三连体立磨催化脱砷浸金装置塔磨，金精矿使金与硫化物充分解离暴露，与非氰浸金剂搅拌，固液比为1：2，加水调矿浆浓度40～50％，硅石抑制剂水玻璃0.5kg/t、搅拌30min，非氰浸金剂的浓度为0.3wt％，矿浆pH值为6～9(石灰调节)，催化剂二氧化锰0.1wt％作用下，闭路循环磨浸时间1～8小时，转速22～32r/min，通氧；其次矿浆在磨细过程中，金颗粒不断暴露出新的表面，使反应活性增加，有利于无氰浸金剂与金反应，得到含金溶液；同时金颗粒不断被细磨，溶解表面积增大，加快了浸金速度，缩短了浸金时间，电解后回收金，金的浸出率达85％。
本实施例采用的非氰浸金剂的制备方法为：将尿素、氢氧化钠和黄血盐按照7:2:1的质量比混合，在1050℃煅烧2h，得到煅烧物；在所述煅烧物中加入1wt％的溴酸钠，得到非氰浸金剂。
表1原矿品位，Au(g/t)，Ag(g/t)
实施例2
原矿含金3.21g/t，含有机碳2.42％，总碳7.82％，砷0.68％，铁4.21％，硫3.2％。
将所述原矿磨至-325目占90wt％，用脉冲射流旋流浮选机进行浮选，获得金精粉，所述金精粉中含金52.16g/t；固液比选择1：3进行边磨矿边浸，主体设备采用转速设定为22～33r/min三连体立磨催化脱砷浸金装置的机械强烈磨擦，在常温、常压下利用氯化铁催化剂0.5wt％，通入臭氧，脱砷脱硫除杂、破坏其原生矿物质结构，砷黄铁矿(毒砂)生成易溶于水的砷酸钠， 经固液分离后，砷进入溶液再与氯化铁氧化反应生成臭葱石而除去；在催化剂氧化铈作用下有机碳被氧化成碳酸盐，“劫金”功能失效；脱砷后固体在三连体立磨催化脱砷浸金装置塔磨，金精矿使金与硫化物充分解离暴露，与非氰浸金剂搅拌，固液比为1：2，加水调矿浆浓度40～50％，硅石抑制剂水玻璃0.5kg/t、搅拌30min，非氰浸金剂的浓度为0.3wt％，矿浆pH值为6～9(石灰调节)，催化剂二氧化锰0.1wt％作用下，闭路循环磨浸时间1～8小时，转速22～32r/min，通氧；其次矿浆在磨细过程中，金颗粒不断暴露出新的表面，使反应活性增加，有利于无氰浸金剂与金反应，得到含金溶液；同时金颗粒不断被细磨，溶解表面积增大，加快了浸金速度，缩短了浸金时间，电解后回收金，金的浸出率达95％。
本实施例采用的非氰浸金剂的制备方法为：将尿素、氢氧化钠和黄血盐按照7:2:1的质量比混合，在1050℃煅烧2h，得到煅烧物；在所述煅烧物中加入1wt％的硫氰化钠，得到非氰浸金剂。
实施例3
原矿含金3.21g/t，含有机碳2.42％，总碳7.82％，砷0.68％，铁4.21％，硫3.2％。
按照实施例1的方法浸出金，得到的含金溶液经净化脱氧快速闪电锌粉置换高效得到金泥冶炼铸造黄金。预处理浸出砷等杂质时，通入富氧空气，催化剂为氧化锰，经压滤溶液添加硫酸亚铁、双氧水，氧化钙搅拌转化合成，压滤得到臭葱石回填，滤液在反应槽加石灰苛化后进入缓冲池储存返回调浆；固液分离含金载体矿物质干渣料经送入浸金流程。浸金也是边磨边浸，加入非氰浸金剂，搅拌浸金矿浆再固液分离，贵液送净化脱氧置顶回收金；贫液进返回调浆浸出；尾渣料加入石灰沉淀得到石膏渣、硫酸钙等标准排放、同时也可以添加胶凝剂固化回填。金回收率96％。
本实施例采用的非氰浸金剂的制备方法为：将尿素、氢氧化钠和黄血盐按照7:2:1的质量比混合，在1050℃煅烧2h，得到煅烧物；在所述煅烧物中加入0.5wt％的溴酸钠和0.5wt％的硫氰化钠，得到非氰浸金剂。
测试例
在与实施例1基本工艺相同条件下，不同物料配比，总的实验浸金效果 如表2所示。
表2不同物料配比的浸金效果
由表2可以看出，金回收率可保证在94％以上，大大优于目前一般处理方法30～70％的金回收率。
以上所述仅是本发明的优选实施方式，应当指出，对于本技术领域的普通技术人员来说，在不脱离本发明原理的前提下，还可以做出若干改进和润饰，这些改进和润饰也应视为本发明的保护范围。

Claims (18)

  1. 一种含碳硫砷金矿的绿色浸金方法，包括以下步骤：
    将含碳硫砷金矿进行细磨，得到矿粉；
    将所述矿粉进行射流脉冲浮选，得到金精粉；
    将所述金精粉和碱、氧化剂、第一催化剂以及水混合，进行氧化反应，得到含碳硫砷盐溶液；
    将所述含碳硫砷盐溶液和铁盐以及石灰混合，进行沉淀反应，得到脱碳硫砷的金矿；
    将所述脱碳硫砷的金矿和非氰浸金剂以及第二催化剂混合，边磨边浸，回收金；所述非氰浸金剂的制备方法包括：将尿素、氢氧化钠和黄血盐混合，进行煅烧，得到煅烧物；将所述煅烧物和添加剂混合，得到非氰浸金剂；所述添加剂包括溴酸钠、硫氰化钠、多硫化物、卤化物、硫脲和硫代硫酸盐中的至少一种。
  2. 根据权利要求1所述的绿色浸金方法，其特征在于，所述含碳硫砷金矿包括碳0.1～5wt％，硫0.1～15wt％，砷0.1～10wt％，金0.5～100g/t。
  3. 根据权利要求1所述的绿色浸金方法，其特征在于，所述细磨在三连体立磨催化脱砷浸金装置中进行；所述三连体立磨催化脱砷浸金装置包括至少两个串联的磨机本体、臭氧发生器、进料口、催化剂加料口和出料口，所述臭氧发生器通过供气管路连接各个所述磨机本体的底部，所述进料口设置于首端的一个所述磨机本体的首端，所述出料口设置于尾端的一个磨机本体的尾端，所述催化剂加料口设置于与所述进料口连通的进料管路上。
  4. 根据权利要求1所述的绿色浸金方法，其特征在于，所述矿粉中细度小于44微米的粉剂为85wt％以上。
  5. 根据权利要求1所述的绿色浸金方法，其特征在于，所述射流脉冲浮选在脉冲射流旋流浮选机中进行；所述脉冲射流旋流浮选机包括机架、上料机构、矿化运输机构和浮选机构，所述机架上设置有所述浮选机构，所述浮选机构的上端设置有所述上料机构，所述上料机构连通所述矿化运输机构，所述矿化运输机构连通所述浮选机构的下端，所述浮选机构上设置有精矿出料口、尾矿出料口和重矿出料口。
  6. 根据权利要求1所述的绿色浸金方法，其特征在于，所述金精粉中 金的含量为20～801g/t。
  7. 根据权利要求1所述的绿色浸金方法，其特征在于，所述碱包括氢氧化钠或氢氧化钙；所述氧化剂包括空气、氧气、臭氧或双氧水；所述第一催化剂包括氧化锰、二氧化锰、氧化铁或氧化铈；所述金精粉、碱、氧化剂和第一催化剂的总质量与水的质量比为1:2.5～5。
  8. 根据权利要求1或7所述的绿色浸金方法，其特征在于，所述碱替换为强碱弱酸盐或碱性金属氧化物。
  9. 根据权利要求1或7所述的绿色浸金方法，其特征在于，所述氧化反应在磨矿条件下进行。
  10. 根据权利要求1所述的绿色浸金方法，其特征在于，所述铁盐包括氯化铁、氯化亚铁、硫酸铁和硫酸亚铁中的一种或几种。
  11. 根据权利要求1或10所述的绿色浸金方法，其特征在于，所述含碳硫砷盐溶液中碳硫砷盐与铁盐的质量比为1:1～1.5。
  12. 根据权利要求1所述的绿色浸金方法，其特征在于，所述含碳硫砷盐溶液中碳硫砷盐与石灰的质量比为1：0.5～1.5。
  13. 根据权利要求1所述的绿色浸金方法，其特征在于，所述第二催化剂包括三氯化铁或灰锰矿。
  14. 根据权利要求1所述的绿色浸金方法，其特征在于，所述尿素、氢氧化钠和黄血盐的质量比为7:2:1。
  15. 根据权利要求1或14所述的绿色浸金方法，其特征在于，所述煅烧的温度为1050℃；所述煅烧的时间为2h。
  16. 根据权利要求1所述的绿色浸金方法，其特征在于，所述添加剂的质量为煅烧物质量的1～5％。
  17. 根据权利要求1所述的绿色浸金方法，其特征在于，所述脱碳硫砷的金矿和非氰浸金剂的质量比为1:0.002～0.005。
  18. 根据权利要求1所述的绿色浸金方法，其特征在于，所述绿色浸金方法在pH值为6～8条件下进行。
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