CN102978400B - Method for recovering rare noble metal from waste water slag of process of producing silver and selenium - Google Patents

Method for recovering rare noble metal from waste water slag of process of producing silver and selenium Download PDF

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CN102978400B
CN102978400B CN201210385800.0A CN201210385800A CN102978400B CN 102978400 B CN102978400 B CN 102978400B CN 201210385800 A CN201210385800 A CN 201210385800A CN 102978400 B CN102978400 B CN 102978400B
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precious metal
slag
selenium
waste water
reaction
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CN102978400A (en
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王玉华
贺来荣
朱纪念
孙渊君
张立岩
王玉琴
张燕
赵静
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Jinchuan Group Co Ltd
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Jinchuan Group Co Ltd
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Abstract

The invention provides a method for recovering rare noble metal from waste water slag of a process of producing silver and selenium. The recovering steps are as follows: a. adding the waste water slag of the process of producing silver and selenium into a reaction kettle, adding a sulfuric acid solution to make a slag to liquid ration 5-5.5, reacting for 30-60 min at a room temperature with stirring, settling for 5-24 hours at the room temperature, and filtering after the settlement to obtain leaching slag enriched with selenium noble metal and a leaching solution with a small amount of residual noble metal, the leaching solution being for use in the next step; and b. putting the leaching solution with the small amount of the residual noble metal in the reaction kettle; heating to a temperature of 80-95 DEG C, adding discharge waste liquid produced by sodium sulfite desulfurization in the production process of the rare noble metal, wherein the adding amount of a precipitant is 1.1-1.3 times that of a theoretical usage amount of Cu2+ ions in the leaching solution with the small amount of the residual noble metal, reacting for 30-120 min at the temperature of 80-95 DEG C, and filtering to obtain cuprous sulfide slag and a solution after the reaction. The method is simple in process flow and circularly economic in waste utilization, and has low production cost and high metal recovery rate.

Description

The method of rare precious metal is reclaimed in a kind of waste water slag from producing silver-colored selenium process
Technical field
The invention belongs to the method and technology field of reclaiming rare precious metal from silver-colored selenium hydrometallurgy waste material, specifically in a kind of waste water slag from producing silver-colored selenium process, reclaiming the method for rare precious metal.
Background technology
Hydrometallurgy is produced in rare precious metal process, can produce a large amount of waste water in Wet-process metallurgy method purification refining rare precious metal flow process, these waste water contains the valuable metals such as some low-grade selenium, silver, platinum, palladium, gold, rhodium, iridium, copper in the precipitation slag of the processes such as neutralization.Wherein platinum metals grade is at a few to tens of gram of ton, but does not all well reclaim rare precious metal method all the time.Generally traditional recovery method is by after waste water slag drying treatment, be incorporated to reduction-sulfurization in firing method process to recycle with metal sulfonium, because this slag is moisture up to 80%, dry power consumption is high, and firing method process cannot reclaim selenium metal simultaneously, also have other to need the poisonous metal be separated to pollute in firing method process, while being unfavorable for rare precious metal, reclaim enrichment.Therefore this slag actual is stored up idle always, namely takes up an area contaminate environment, have impact on again the rate of recovery of rare precious metal.
Summary of the invention
The object of the invention is to propose a kind of method that can reclaim rare precious metal fast from production silver-colored selenium process in waste water slag for shortcoming of the prior art, the method effectively raises precious and rare metals recovery rate, reduces production cost, simplifies technical process.
Following technical scheme is adopted for solving technical problem of the present invention:
The method of rare precious metal is reclaimed in a kind of waste water slag from producing silver-colored selenium process, be the waste water slag of producing waste water neutralize precipitation slag in silver-colored selenium process be raw material, waste water slag moisture content 80%, its chemical composition is: copper 5 ~ 15% selenium 0.2 ~ 5% silver medal 0.2 ~ 1%, platinum 0.1 ~ 200g/t, palladium 0.1 ~ 500g/t, gold 0.1 ~ 200g/t, rhodium iridium 0.1 ~ 200g/t, zinc 18 ~ 22%, arsenic 0.2 ~ 5%, nickel 1 ~ 3%, iron 1 ~ 6%, lead 0.5 ~ 1%, tellurium 0.1 ~ 2%, sulphur 4 ~ 10%, sulfate radical 15 ~ 30%.
From the waste water slag of producing silver-colored selenium process, reclaim a method for rare precious metal, its recycling step is as follows:
A. in reactor, add the waste water slag in silver-colored selenium production process, adding concentration is 17 ~ 19 mol/L sulphuric acid solns, reaction slag liquor ratio is made to be 5 ~ 5.5, the acidity of reaction slag liquid is 2.8 ~ 3.2 mol/L, at room temperature stirring reaction 30 ~ 60min, then room temperature sedimentation 5h ~ 24h, filters after sedimentation, obtain being enriched the leached mud of selenium precious metal and the leach liquor of a small amount of precious metal of remnants, next step is stand-by for the leach liquor of a small amount of precious metal of the remnants obtained;
B. get in the leach liquor placing response still of a small amount of precious metal of above-mentioned remnants and be heated to 80 ~ 95 DEG C, add precipitation agent, precipitation agent is the discharge waste liquid with S-WAT desulfurization in rare precious metal production process, and the add-on of precipitation agent is Cu in the leach liquor of remaining a small amount of precious metal 2+1.1 ~ 1.3 times of reaction theory consumption, then at 80 ~ 95 DEG C of reaction 30 ~ 120min minute, filter, and obtain liquid after cuprous sulfide slag and reaction.
The leached mud being enriched selenium precious metal obtained in described step a is sent into copper anode mud operation and is reclaimed rare precious metal.
The cuprous sulfide slag obtained in described step b delivers to copper weld pool system production of copper positive plate, obtains reacting rear liquid and delivers to white cigarette ash factory recovery zinc-nickel.
Precipitation agent in described step b is that to contain Sulfothiorine weight fraction be S-WAT desulfurization wastewater in the rare precious metal production process of 38 ~ 40%.
The present invention be a kind of can fast from the enriching and recovering method of producing rare precious metal in waste water slag silver-colored selenium process, be that to produce waste water neutralize precipitation slag in silver-colored selenium process be raw material.Take full advantage of the moisture of in precipitation slag 80%, directly use wet feed, use moderate amount of sulfuric acid selective dissolution base metal, rare precious metal major part is enriched in slag, makes rare precious metal Sync enrichment about 20 times, slag filter only 6%.Filter element grade in the leached mud obtained, close to copper anode mud, to be applicable to being connected existing copper anode sludge technical process merging treatment.The base metal majorities such as copper zinc arsenic ferronickel tellurium enter in leach liquor.Precipitation agent is added again in leach liquor, it is S-WAT desulfurization wastewater in the rare precious metal production process of 38 ~ 40% that precipitation agent is the use of Sulfothiorine weight fraction, copper is precipitated with cuprous sulfide form, the rare precious metal of co-precipitation simultaneously, copper and remaining precious and rare metals recovery is made to be greater than 99%, filter the cuprous sulfide slag reactant obtained and deliver to copper weld pool system production of copper positive plate, obtain reacting rear liquid and deliver to white cigarette ash factory recovery zinc-nickel.Adopt method of the present invention, by the precious and rare metals recovery in waste water slag in silver-colored selenium production process and the harmonious combination of existing rare precious metal system production technique, existing production is not impacted, flow process is simple, utilization of waste material recycling economy, production cost is low, metal recovery rate is high.
Accompanying drawing explanation
Fig. 1 is process flow sheet of the present invention.
Embodiment
the method of rare precious metal is reclaimed in a kind of waste water slag from producing silver-colored selenium process, first filter after in silver-colored for production selenium process, waste water slag adds sulfuric acid sedimentation, leach liquor with the S-WAT desulfurization wastewater of precious metal refinery system for precipitation agent sinks copper, the cuprous sulfide slag reactant obtained containing a small amount of rare precious metal returns produces positive plate technique into copper weld pool, after reclaim wherein remaining precious metal with the form of copper anode mud, reaction solution is delivered to white cigarette ash factory and is reclaimed zinc-nickel; Leached mud containing a large amount of rare precious metal enters existing copper anode sludge operation and reclaims rare precious metal.Its treating processes is followed successively by:
A. the waste water slag in silver-colored selenium production process is added in reactor, adding concentration is 17 ~ 19mol/L sulphuric acid soln, slag liquor ratio is 5 ~ 5.5, the acidity of reaction soln is made to be 2.8 ~ 3.2 mol/L, at room temperature stirring reaction 30 ~ 60min, then room temperature sedimentation 24h, filter after sedimentation, obtain being enriched the leached mud of selenium precious metal and the leach liquor of a small amount of precious metal of remnants, next step is stand-by for the leach liquor of a small amount of precious metal of the remnants obtained, and the leached mud being enriched selenium precious metal is sent into copper anode mud operation and reclaimed rare precious metal.
B. get in the leach liquor placing response still of a small amount of precious metal of above-mentioned remnants and be heated to 80 ~ 95 DEG C, add the discharge waste liquid with S-WAT desulfurization in rare precious metal production process, this waste liquid is amount to seven water sodium sulfite solutions and the material containing elemental sulfur with containing 35% during rare precious metal is produced, liquid is abandoned after boiling reaction, the discharge waste liquid of this S-WAT desulfurization is 38 ~ 40% containing the massfraction of Sulfothiorine, and wherein adding in rare precious metal production process with the discharge waste liquid consumption of S-WAT desulfurization is Cu in the leach liquor of remaining precious metal on a small quantity 2+1.1 ~ 1.3 times of reaction theory consumption, then at 80 DEG C ~ 95 DEG C reaction 30 ~ 120min minute, filter, be precipitated reactant and reaction solution, the reactant obtained delivers to copper weld pool system production of copper positive plate, obtains reaction solution and delivers to white cigarette ash factory recovery zinc-nickel.
The present invention is further illustrated below by way of concrete embodiment.
embodiment 1
In the silver-colored selenium process of a kind of production, waste water and precipitation slag put into reactor, waste water neutralize precipitation slag moisture 80%, chemical composition (mass percent) is copper 5% selenium 5% silver medal 0.20%, platinum 200g/t, palladium 0.1g/t, golden 200g/t, rhodium iridium 0.1g/t, zinc 22%, arsenic 0.2%, nickel 3%, iron 1.%, plumbous 1%, tellurium 0.1%, sulphur 10%, sulfate radical 15%.
Get above-mentioned waste water and precipitation slag raw material 20Kg, wherein slag liquor ratio is 5, adds the sulfuric acid 3.6L of 17mol/L, and make the acidity of solution be 2.8mol/L, stirring at normal temperature 1 hour, sedimentation 24h filters.The leached mud moisture content 38% obtained, chemical composition is: copper 2.15% selenium 29.5% silver medal 4.35%, platinum 0.375%, palladium 3g/t, gold 0.4%, rhodium iridium 5g/t, zinc 1.08%, arsenic 0.02%, nickel 0.05%, iron 0.04%, lead 11.1%, tellurium 0.86%, sulphur 19.6%, enriching and recovering rare precious metal rate is greater than 99%, the leached mud being enriched selenium precious metal is sent into copper anode mud operation and reclaims rare precious metal.The leach liquor of a small amount of precious metal of the remnants obtained is that 20L puts into reactor, leach liquor is heated to 95 DEG C, precipitation agent is added again in leach liquor, precipitation agent is the S-WAT desulfurization waste liquor in rare precious metal production process, precipitation agent is that to contain Sulfothiorine weight fraction be 38%, add-on is 1.8L, for Cu in the leach liquor of a small amount of precious metal of remnants 2+1.1 times of reaction theory consumption, reaction times 30min. filters.The reactant cuprous sulfide slag main component obtained is Cu53.73%, selenium 0.038%, silver 0.0063%, palladium 0.016%, S 26.21%, and leach liquor is delivered to white cigarette ash factory and reclaimed zinc-nickel.Whole removal process is sunk copper and rare precious metal rate and is greater than 99%.
embodiment 2
In the silver-colored selenium process of a kind of production, waste water and precipitation slag put into reactor, waste water neutralize precipitation slag moisture 80.3%, chemical composition (mass percent) is copper 15% selenium 0.2% silver medal 1%, platinum 0.1g/t, palladium 500g/t, golden 0.1g/t, rhodium iridium 200g/t, zinc 18. %, arsenic 5%, nickel 1%, iron 6%, plumbous 0.5 %, tellurium 2%, sulphur 4%, sulfate radical 30%.
Get above-mentioned waste water and precipitation slag raw material 20Kg, wherein slag liquor ratio is 5.5, adds 19mol/L sulfuric acid 3.0L, and make the acidity of solution be 3.2 mol/L stirring at normal temperature 30 minutes, sedimentation 5h filters.The leached mud moisture 40% obtained, chemical composition is: copper 7.5% selenium 4.33% silver medal 9.7%, platinum 3.46 g/t, palladium 0.973%, golden 2.8g/t, rhodium iridium 0.14%, zinc 1.54%, arsenic 0.36%, nickel 0.32%, iron 0.28%, lead 9.79%, tellurium 0.44%, sulphur 23.88%.Enriching and recovering rare precious metal rate is greater than 99%, leached mud is sent into copper anode mud operation and reclaims rare precious metal.The leach liquor obtained is that 20L puts into reactor, leach liquor is heated to 80 DEG C, then adds precipitation agent in leach liquor.Precipitation agent is the sub-sodium desulfurization wastewater 3.6L in rare precious metal production process, and sub-sodium desulfurization wastewater is 0.001g/L containing gold, makes the add-on of hypo solution be containing Cu in leach liquor 2+1.3 times of reaction times 30min. of reaction theory consumption filter.The reactant cuprous sulfide slag main component obtained is Cu57.28%, selenium 0.036%, silver 0.0017%, palladium 0.015%, S 27%, and leach liquor is delivered to white cigarette ash factory and reclaimed zinc-nickel.Whole removal process is sunk copper and rare precious metal rate and is greater than 99%.
embodiment 3
In the silver-colored selenium process of a kind of production, waste water and precipitation slag put into reactor, waste water neutralize precipitation slag moisture 80.46, chemical composition (mass percent) is copper 7.31% selenium 1.15% silver medal 0.34%, platinum 100/g/t, palladium 350g/t, golden 29g/t, rhodium iridium 20g/t, zinc 19.54%, arsenic 1.12%, nickel 2.09%, iron 1.28%, plumbous 0.50%, tellurium 0.30%, sulphur 6.93%, sulfate radical 21%.
Get above-mentioned waste water and precipitation slag raw material 20Kg, wherein slag liquor ratio is 5, adds 18mol/L sulfuric acid 3.3L, and make the acidity of solution be 3.0 mol/L stirring at normal temperature 60 minutes, sedimentation 10h filters.The leached mud moisture 43% obtained, chemical composition is: copper 2.13% selenium 12.45% silver medal 3.57%, platinum 0.156%, palladium 0.331%, gold 0.026%, rhodium iridium 0.04%, zinc 0.38%, arsenic 0.056%, nickel 0.22%, iron 0.59%, lead 8.55%, tellurium 0.25%, sulphur 22%.Enriching and recovering rare precious metal rate is greater than 99%, leached mud is sent into copper anode mud operation and reclaims rare precious metal.The leach liquor obtained is that 20L puts into reactor, leach liquor is heated to 85 DEG C, in leach liquor, add the S-WAT desulfurization waste liquor 2.2L in rare precious metal production process again, make the S-WAT desulfurization waste liquor add-on in rare precious metal production process be containing Cu in leach liquor 2+1.2 times of reaction theory consumption, reaction times 120min.Filter.The reactant cuprous sulfide slag main component obtained is Cu58.87%, selenium 0.14%, silver 0.024%, palladium 0.015%, S 27%, and the reaction solution obtained is delivered to white cigarette ash factory and reclaimed zinc-nickel.Whole removal process is sunk copper and rare precious metal rate and is greater than 99%.

Claims (1)

1. from the waste water slag of producing silver-colored selenium process, reclaim a method for rare precious metal, its recovery process process is followed successively by:
A. in reactor, add the waste water slag in silver-colored selenium production process, adding concentration is 17 ~ 19 mol/L sulphuric acid solns, reaction solution slag ratio is made to be 5.23 ~ 5.37, the acidity of reaction slag liquid is 2.8 ~ 3.2 mol/L, at room temperature stirring reaction 30 ~ 60min, then room temperature sedimentation 5h ~ 24h, filter after sedimentation, obtain being enriched the leached mud of selenium precious metal and the leach liquor of a small amount of precious metal of remnants, next step is stand-by for the leach liquor of a small amount of precious metal of the remnants obtained, and the leached mud being enriched selenium precious metal obtained is sent into copper anode mud operation and reclaimed rare precious metal;
B. get in the leach liquor placing response still of a small amount of precious metal of above-mentioned remnants and be heated to 80 ~ 95 DEG C, add precipitation agent, precipitation agent contains the discharge waste liquid that Sulfothiorine weight fraction is use S-WAT desulfurization in the rare precious metal production process of 38 ~ 40%, and the add-on of precipitation agent is Cu in the leach liquor of remaining a small amount of precious metal 2+1.1 ~ 1.3 times of reaction theory consumption, then at 80 ~ 95 DEG C of reaction 30 ~ 120min minute, filter, obtain cuprous sulfide slag and the rear liquid of reaction, the cuprous sulfide slag obtained delivers to copper weld pool system production of copper positive plate, obtains reacting rear liquid and delivers to white cigarette ash factory recovery zinc-nickel.
CN201210385800.0A 2012-10-12 2012-10-12 Method for recovering rare noble metal from waste water slag of process of producing silver and selenium Active CN102978400B (en)

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CN104445092A (en) * 2014-12-07 2015-03-25 金川集团股份有限公司 Method for preparing anhydrous sodium thiosulfate from platinum family metal desulfurization solution
CN106148719B (en) * 2016-08-29 2018-08-10 金川集团股份有限公司 A kind of method that silver is recycled in low silver-colored smelting slag
CN108384953B (en) * 2018-03-06 2021-07-23 昆明理工大学 Method for recovering noble metal from noble metal ion-containing solution

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钟勇.从高含硒、碲和贵金属富料中分离提取硒、碲研究.《中国优秀硕士学位论文全文数据库 工程科技I辑 (月刊)》.2012,(第2期),第37-39、54-55页. *

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