Summary of the invention
The object of the invention provides a kind of technological operation is simply extracted platinum and palladium and weighed coloured valuable metal copper, nickel, cobalt from the sulphide ores of platinum group metal method.
The method of the extraction platinum from the sulphide ores of platinum group metal of foregoing invention purpose and palladium and heavy coloured valuable metal copper, nickel, cobalt comprises following several steps successively:
1. the digestion mineral aggregate pressurizes: mineral aggregate and digestion liquid were put into 50~250 ℃ of digestions of closed reactor 0.5~20 hour, and digestion liquid is selected from H
2SO
4, NaOH, water any, the weight ratio of this step mineral aggregate and this step digestion liquid is solid: liquid=1: 2~6 are filled with air, oxygen-rich air or pure oxygen gas in the reactor;
2. the solid slag that 1. obtains of 50~100 ℃ of digestion steps is 0.5~8 hour, and the digestion liquid that digestion is selected for use is HCl, H
2SO
4At least a, the weight ratio of the digestion liquid that the solid slag that 1. above-mentioned steps obtains and this step digestion are selected for use is solid: liquid=1: 2~6;
3. with the mixture solid slag that 2. the digestion step obtains under 40~100 ℃ of temperature of digestion liquid and oxygenant 0.5~8 hour, this step digestion liquid was selected from HCl, H
2SO
4, HCl and H
2SO
4Mixture, HCl and HNO
3Any of mixture, above-mentioned oxygenant is selected from H
2O
2, HClO
3, HClO, HNO
3, NaClO
3, NaClO, Na
2S
2O
8, chlorinated lime, Cl
2The solid-liquid weight ratio of the solid slag that 2. any of gas, above-mentioned steps obtain and this step digestion liquid is for solid: liquid=1: 2~6;
4. platinum, palladium during the leach liquor that 3. obtains with traditional enrichment, method of refining extraction step contains.
Behind each technical parameter, can further improve the productive rate of extract in the preferred technique scheme.
To step 1., its H
2SO
4, NaOH concentration be preferably 1wt%~40wt%, the gaseous tension in the reactor is preferably 1~5MPa.
To step 2., HCl, H
2SO
4Or the concentration of its mixture is preferably 5wt%~60wt%.
To step 3., digestion liquid HCl, H
2SO
4, HCl and H
2SO
4Mixture, HCl and HNO
3The concentration of mixture is preferably 5wt%~100wt%, oxygenant H
2O
2, HClO
3, HClO, HNO
3, NaClO
3, NaClO, Na
2S
2O
8, chlorinated lime, Cl
2The consumption of gas is preferably 0.5%~50% of solid slag weight that 2. step obtain.
To step oxygenant H 3.
2O
2, HClO
3, HClO, HNO
3, NaClO
3, NaClO, Na
2S
2O
8, in this step digestion liquid of the selected direct adding of chlorinated lime, oxygenant Cl
2In the digestion liquid of selected continuous this step of directly feeding of gas.
Further preferred steps consolidating in 1.: liquid=1: 3~5, step consolidating in 2.: liquid=1: 3~5, step consolidating in 3.: liquid=1: 3~5.
Can also preferred steps H in 1.
2SO
4Concentration is 15wt%~25wt%, and gaseous tension is 1~3MPa oxygen in the reactor, and digestion temperature is 180~200 ℃, and the digestion time is 8~15 hours.
Also can preferred steps H in 2.
2SO
4Concentration is 20wt%~50wt%, and digestion temperature is 80~100 ℃, 4~6 hours digestion time.
Can also preferred steps HCl concentration in 3. be 50wt%~100wt%, described digestion temperature is 80~100 ℃, 4~6 hours described digestion time.
Chlorinated lime in the technique scheme is meant Ca (ClO)
2CaCl
22H
2O.
In the technique scheme, step HCl and H 2.
2SO
4In the mixture, 0<HCl concentration<60wt%, 0<H
2SO
4Concentration<60wt%; Step HCl and H 3.
2SO
4In the mixture, 0<HCl concentration<100wt%, 0<H
2SO
4Concentration<100wt%; Step HCl and HNO 3.
3In the mixture, 0<HCl concentration<100wt%, 0<HNO
3Concentration<100wt%.
State on the implementation in the technical scheme process, because the oxygen in the step gas 1. participates in reaction process, so the gaseous tension in the reactor selects to remain a certain steady state value selected in appropriate technical solution gaseous tension parameter area.Help reaction like this and normally carry out, guarantee to obtain higher leaching yield, realize that simultaneously rapid extraction reclaims heavy non-ferrous metal copper, nickel, the cobalt in the mineral aggregate.
In the technique scheme, 1. step contains the leach liquor of copper, nickel, cobalt respective compound with the 2. equal output of step, available traditional method, and as solvent extraction, copper, nickel, cobalt in the difference Separation and Recovery digestion liquid.
In the technique scheme, step oxygenant 3. can with digestion liquid synchronized mixes, also can be in temperature-rise period substep add in the digestion liquid.
In the technique scheme, step traditional enrichment, method of refining 4. can be substitution method, ion exchange method, solvent extration or chromatograph absorption method.Substitution method can use metal replacements such as powdery, sheet or blocky Zn, Mg, Al, Fe or Cu to obtain platinum, palladium.Ion exchange method comprises various anionite-exchange resin absorption and obtains platinum, palladium.Solvent extration mainly is to obtain the platinum palladium with quaternary ammonium salt, tertiary amine, TRPO or TBP extraction.Use traditional method of refining output platinum metals product again through the platinum metals enriched substance that above-mentioned any enrichment obtains.
The present invention is to the pressure oxidation acidleach pre-treatment slag of platinum group metal sulfide, adopt atmospheric pressure oxidation acidleach platinum metals, saved the high-temperature cyanidation process, thereby the potential hazard of having avoided using huge malicious prussiate and environment and operator being existed, and shortened technical process, adopt normal pressure leaching-out technique means greatly to reduce and implement Financial cost of the present invention.Process program technology maturation of the present invention, simple to operate, the equipment used maintenance and management is easy.Adopt the present invention to handle the platinum group metal sulfide, platinum, palladium recovery rate can reach Pt>94%, Pd>96%, and copper, nickel, cobalt leaching yield reach more than 98%.Invention has the adaptable characteristics of material.
The present invention can be used for handling the Cu, Ni and Co sulfide content below 15%, the low-grade platinum metals sulphide ores of platinum metals content below 0.05%, be more suitable for handling its flotation concentrate, simultaneously also be suitable for handling other material of platinum group metal, for example platinum group burning ore deposit, the anode sludge, smelting intermediates etc.The present invention all has no special requirements to employed each chemical reagent of reactant gases that comprises, above commercial reagent of technical pure or gas can satisfy the technical scheme requirement.
Embodiment
Select for use the low-grade Pt-Pd sulphide ores through the flotation concentrate of floating and enriching as the technical solution of the present invention process object.This kind flotation concentrate sulfur-bearing is about 15%, belongs to sulphide ores, and the Pt+Pd grade can reach 70~100g/t, but Cu and Ni grade are respectively<5%, SiO
2Content is 26%, and MgO content is near 20%.The platinum palladium flotation concentrate material that experiment is handled is the toner powder darkly, and the sample quartering analytical results is listed in table 1.
Table 1 platinum palladium flotation concentrate multielement chemical analysis results (Pt, Pd:g/t, other element: wt%)
Element | ??Pt | ??Pd | ??Cu | ??Fe | ??Ni | ??Co | ???S | ??SiO
2 | ?CaO | ?MgO |
Content | ?32.14 | ?50.31 | ??3.77 | ?15.32 | ?3.55 | ?0.24 | ?14.15 | ?25.97 | ?2.89 | ?18.56 |
Embodiment 1
1. get mineral aggregate 500 grams in the table 1, with weight percent concentration 20%H
2SO
4Aqueous solution, the furnishing pulpous state is put into reactor.Mineral aggregate and H
2SO
4Aqueous solution solid-liquid weight ratio is 1: 4.Be heated to 200 ℃ of temperature, reacted 10 hours, gas is oxygen in the preceding reactor of heating, and the gaseous tension in the reaction process control reactor is constant to be 2.0MPa.
2. the acid leaching residue that 1. step is obtained under normal pressure with the H of weight percent concentration 20%
2SO
4Aqueous solution, solid-liquid weight ratio are 1: 4, and temperature of reaction is 90 ℃, 6 hours reaction times.
3. the acid leaching residue that 2. step is obtained is put into reactor, sizes mixing with weight percent concentration 50%HCl aqueous solution, and the solid-liquid weight ratio is 1: 5, is heated to 90 ℃ of temperature, adds weight and be the NaClO of the acid leaching residue 10% that 2. step obtain
3, normal pressure reacted 6 hours down.
4. the leach liquor zinc dust precipitation that 3. step is obtained obtains separating the purification platinum metals with traditional technology again behind the concentration of precious metal thing.
Platinum, palladium leaching yield are respectively: Pt97.07%, Pd98.90%.
Copper, nickel, cobalt leaching yield are respectively: Cu98.0%, Ni98.6%, Co98.5%.
Embodiment 2
1. get mineral aggregate 500 grams in the table 1, with weight percent concentration 15%H
2SO
4Aqueous solution, the furnishing pulpous state is put into reactor.Mineral aggregate and H
2SO
4Aqueous solution solid-liquid weight ratio is 1: 5.Be heated to 200 ℃ of temperature, reacted 15 hours, gas is oxygen in the preceding reactor of heating, and the constant system pressure of reaction process is 3.0MPa.
2. the acid leaching residue that 1. step is obtained under normal pressure with the HCl aqueous solution of concentration expressed in percentage by weight 20%, the solid-liquid weight ratio is 1: 4, temperature of reaction is 50 ℃, 4 hours reaction times;
3. the acid leaching residue that 2. step is obtained is put into reactor, mixes with weight percent concentration 100%HCl solution and sizes mixing, and the solid-liquid weight ratio is 1: 5, is heated to 40 ℃ of temperature, adds weight and be the H of the acid leaching residue 40% that 2. step obtain
2O
2, normal pressure reacted 4 hours down.
4. the leach liquor zinc dust precipitation that 3. step is obtained obtains separating the purification platinum metals with traditional technology again behind the concentration of precious metal thing.
Platinum, palladium leaching yield are respectively: Pt94.55%, Pd9730%.
Copper, nickel, cobalt leaching yield are respectively: Cu99.0%, Ni99.0%, Co98.5%.
Embodiment 3
1. get mineral aggregate 500 grams in the table 1, with weight percent concentration 25%H
2SO
4Aqueous solution, the furnishing pulpous state is put into reactor.Flotation concentrate and H
2SO
4Aqueous solution solid-liquid weight ratio is 1: 3.Be heated to 180 ℃ of temperature, reacted 8 hours, gas is oxygen in the preceding reactor of heating, and the constant system pressure of reaction process is 2.5MPa.
2. the acid leaching residue that 1. step is obtained under normal pressure is 20% HCl+H with concentration expressed in percentage by weight
2SO
4Aqueous solution, solid-liquid weight ratio are 1: 4, and temperature of reaction is 80 ℃, react 4 hours.
3. the acid leaching residue that 2. step is obtained is put into reactor, mixes with weight percent concentration 50%HCl solution and sizes mixing, and the solid-liquid weight ratio is 1: 4, is heated to 80 ℃ of temperature, adds weight percent concentration 15%NaClO, and normal pressure reacted 8 hours down.
4. the leach liquor zinc dust precipitation that 3. step is obtained obtains separating the purification platinum metals with traditional technology again behind the concentration of precious metal thing.
Platinum, palladium leaching yield are respectively: Pt94.0%, Pd96.5%.
Copper, nickel, cobalt leaching yield are respectively: Cu99.0%, Ni99.0%, Co98.5%.
Embodiment 4
1. get mineral aggregate 500 grams in the table 1, with weight percent concentration 15%NaOH aqueous solution, the furnishing pulpous state is put into reactor.Flotation concentrate and NaOH aqueous solution solid-liquid weight ratio are 1: 5.Be heated to 200 ℃ of temperature, reacted 20 hours, gas is oxygen in the preceding reactor of heating, and the constant system pressure of reaction process is 2.5MPa.
2. 1.) leached mud of Huo Deing under normal pressure is 50% H with concentration expressed in percentage by weight with step
2SO
4Aqueous solution, solid-liquid weight ratio are 1: 4, and temperature of reaction is 70 ℃, react 6 hours.
3. the leached mud that 2. step is obtained is put into reactor, with weight percent concentration 50%HCl+H
2SO
4Solution mixes sizes mixing, and the solid-liquid weight ratio is 1: 4, is heated to 80 ℃ of temperature, adds weight and be the HClO of the acid leaching residue 50% that 2. step obtain
3, normal pressure reacted 8 hours down.
4. the leach liquor zinc dust precipitation that 3. step is obtained obtains separating the purification platinum metals with traditional technology again behind the concentration of precious metal thing.
Platinum, palladium leaching yield are respectively: Pt95.7%, Pd96.0%.
Copper, nickel, cobalt leaching yield are respectively: Cu98.6%, Ni99.0%, Co99.2%.
Embodiment 5
1. get mineral aggregate 500 grams in the table 1, with weight percent concentration 20%H
2SO
4Aqueous solution, the furnishing pulpous state is put into reactor.Flotation concentrate and H
2SO
4Aqueous solution solid-liquid weight ratio is 1: 4.Be heated to 200 ℃ of temperature, reacted 10 hours, gas is oxygen in the preceding reactor of heating, and the constant system pressure of reaction process is 2.0MPa.
2. the acid leaching residue that 1. step is obtained under normal pressure with the H of weight percent concentration 30%
2SO
4Aqueous solution, solid-liquid weight ratio are 1: 4, and temperature of reaction is 90 ℃, 6 hours reaction times.
3. the acid leaching residue that 2. step is obtained is put into reactor, sizes mixing with weight percent concentration 100%HCl aqueous solution, and the solid-liquid weight ratio is 1: 5, is heated to 90 ℃ of temperature, feeds Cl in digestion liquid continuously
2, take out sample with sampler in the reaction process and send chemical analysis, with platinum metals leaching yield>90% as reaction end.
4. the leach liquor zinc dust precipitation that 3. step is obtained obtains separating the purification platinum metals with traditional technology again behind the concentration of precious metal thing.
Platinum, palladium leaching yield are respectively: Pt95.2%, Pd97.5%.
Copper, nickel, cobalt leaching yield are respectively: Cu98.0%, Ni98.6%, Co98.5%.
Embodiment 6
1. getting mineral aggregate 500 grams in the table 1, is that 2000 water that restrain mix with weight, and the furnishing pulpous state is put into reactor.Be heated to 200 ℃ of temperature, reacted 18 hours, gas is oxygen in the preceding reactor of heating, and the constant system pressure of reaction process is 3.0MPa.
2. the leached mud that 1. step is obtained under normal pressure is 20% HCl aqueous solution with concentration expressed in percentage by weight, and the solid-liquid weight ratio is 1: 4, and temperature of reaction is 100 ℃, reacts 4 hours.
3. the leached mud that 2. step is obtained is put into reactor, with weight percent concentration 50%HCl+HNO
3Solution mixes sizes mixing, and the solid-liquid weight ratio is 1: 4, is heated to 60 ℃ of temperature, and normal pressure reacted 4 hours down.
4. the leach liquor solvent extraction that 3. step is obtained obtains separating the purification platinum metals with traditional technology again behind the concentration of precious metal thing with zinc dust precipitation from strip liquor.
Platinum, palladium leaching yield are respectively: Pt95.4%, Pd96.2%.
Copper, nickel, cobalt leaching yield are respectively: Cu98.6%, Ni99.0%, Co99.2%.
Embodiment 7
1. get mineral aggregate 500 grams in the table 1, with weight percent concentration 20%H
2SO
4Aqueous solution, the furnishing pulpous state is put into reactor.Flotation concentrate and H
2SO
4Aqueous solution solid-liquid weight ratio is 1: 4.Be heated to 200 ℃ of temperature, reacted 10 hours, gas is oxygen in the preceding reactor of heating, and the constant system pressure of reaction process is 2.0MPa.
2. the acid leaching residue that 1. step is obtained under normal pressure with the H of weight percent concentration 30%
2SO
4Aqueous solution, solid-liquid weight ratio are 1: 4, and temperature of reaction is 90 ℃, 6 hours reaction times.
3. the leached mud that 2. step is obtained is put into reactor, with weight percent concentration 50%H
2SO
4Solution mixes sizes mixing, and the solid-liquid weight ratio is 1: 6, is heated to 100 ℃ of temperature, adds weight and be the NaClO of the acid leaching residue 10% that 2. step obtain
3, normal pressure reacted 8 hours down.
4. the leach liquor zinc dust precipitation that 3. step is obtained obtains separating the purification platinum metals with traditional technology again behind the concentration of precious metal thing.
Platinum, palladium leaching yield are respectively: Pt94.5%, Pd95.2%.
Copper, nickel, cobalt leaching yield are respectively: Cu98.6%, Ni99.0%, Co99.2%.
Embodiment 8
1. get mineral aggregate 500 grams in the table 1, with weight percent concentration 15%NaOH aqueous solution, the furnishing pulpous state is put into reactor.Flotation concentrate and NaOH aqueous solution solid-liquid weight ratio are 1: 5.Be heated to 200 ℃ of temperature, reacted 20 hours, gas is oxygen in the preceding reactor of heating, and the constant system pressure of reaction process is 2.5MPa.
2. the leached mud that 1. step is obtained under normal pressure is 50% HCl aqueous solution with concentration expressed in percentage by weight, and the solid-liquid weight ratio is 1: 4, and temperature of reaction is 70 ℃, reacts 6 hours.
3. the leached mud that 2. step is obtained is put into reactor, with weight percent concentration 95%HCl+HNO
3Solution mixes sizes mixing, and the solid-liquid weight ratio is 1: 4, is heated to 100 ℃ of temperature, and normal pressure reacted 2 hours down.
4. the leach liquor solvent extraction that 3. step is obtained obtains separating the purification platinum metals with traditional technology again behind the concentration of precious metal thing with zinc dust precipitation from strip liquor.
Platinum, palladium leaching yield are respectively: Pt96.4%, Pd97.0%.
Copper, nickel, cobalt leaching yield are respectively: Cu98.6%, Ni99.0%, Co99.2%.