CN102560123A - Method for utilization and harmless treatment of multi-metal material containing arsenic and indium - Google Patents

Method for utilization and harmless treatment of multi-metal material containing arsenic and indium Download PDF

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Publication number
CN102560123A
CN102560123A CN201210040523XA CN201210040523A CN102560123A CN 102560123 A CN102560123 A CN 102560123A CN 201210040523X A CN201210040523X A CN 201210040523XA CN 201210040523 A CN201210040523 A CN 201210040523A CN 102560123 A CN102560123 A CN 102560123A
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Prior art keywords
indium
arsenic
solution
press filtration
slag
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曹亮发
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CHENZHOU FENGYUE ENVIRONMENTAL PROTECTION TECHNOLOGY CO LTD
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    • 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
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Abstract

The invention discloses a method for utilization and harmless treatment of multi-metal material containing arsenic and indium, comprising the steps of: dissolving most of metals like arsenic and indium into the solution through hydrometallurgy while lead and stannum into the slag; then precipitating indium by means of hydrolysis; afterwards, leaching out the precipitated indium with hydrochloric acid to obtain indium-rich solution, and obtaining coarse indium product through replacement and smelting; finally adding alkali to the arsenic-containing solution to produce harmless ferrite. With the invention, the arsenic removal rate is greater than 93%; arsenic is well separated from the valued metals so that the arsenic content in the valued metal slag is less than 1%, which is convenient for reclamation of valued metals; moreover the arsenic slag formed is a general solid waste which is easy to dispose, and the waste water meets the requirement of first-grade discharge standard to realize comprehensive and harmless reclamation of the arsenic-containing materials.

Description

Contain many metalliferous materials utilization of arsenic indium and method for innocent treatment
Technical field
The present invention provides a kind of technology of environmental protection hydrometallurgy, specifically is meant from containing the treatment process of the many metalliferous materials of arsenic indium.
Background technology
Arsenic is a kind of non-metallic element, and pearl has the ingot of metalluster, and matter is crisp poisonous, and the white arsenic toxicity that particularly is commonly called as arsenic is bigger.The sulfide that all contains a certain amount of arsenic in which kind of metallic sulfide ores, free arsenic are quite active.When in air, being heated to about 200 ℃, there is fluorescent to occur, in the time of 400 ℃, has a kind of bluish flame, and form the arsenic oxide arsenoxide cigarette of white.Free element is prone to and fluorine and nitrification, heating state also with most metal and nonmetal reacting.In pyrometallurgical smelting lead, copper process, arsenic volatilizees with metals such as zinc, indium, lead, tin, copper and gets in the flue dust, accumulates over a long period; Arsenic content is increasingly high, and valuable metal content is also increasingly high, and environment is more and more abominable; Handle quite difficulty, major part is that pack is stored up.
Disclosing publication number at Chinese patent is that CN101525693 has reported a kind of sulfuration and reducing oxidation and enrichment method that contains arsenic indium germanium low-grade material.In containing the plumbous zinc arsenic raw material of indium germanium, allocate a certain amount of coal dust into as reductive agent, add elemental sulfur simultaneously, and add sticker and carry out briquetting, the plumbous zinc arsenic material of indium germanium: lime: sulphur is 100: 20～40: 5～10: 2～4 by weight ratio; Process coal briquette or group's form and in shaft furnace, carry out sulfiding volatilization; Controlled temperature is under 1000～1200 ℃, and in certain redox condition, the sulfiding volatilization time is 1～3 hour; Plumbous zinc in the slag is below 2%; The content of indium germanium drops to 30～300 gram/tons, and flue dust leaches during for pH0.5 at the sulfuric acid terminal point, leach liquor with zinc dust precipitation to the indium germanium concentrate.Can be with lower production cost with enrichments such as valuable metal indium, germanium, lead, zinc and silver; Without draining; Germanium in the flue dust that obtains, indium, zinc just can leach 95% at pH0.5, and hydrogen arsenide can be handled in addition, and valuable metal lead, zinc, silver can comprehensively reclaim.
Existing arsenic gold mine rotary kiln dearsenicating technology, the high arsenic of this process using (containing arsenic 20%) gold ore, through rotary kiln baking, can produce commodity north arsenic (As2O3＞95%), again can low arsenic (As＜1.0%) calcining of output, improve golden yield.Above dearsenification all is to adopt thermal process, dust arrester installation is closed envelope require height, and white arsenic is prone to leak, and pollutes environment easily.
From the document of present announcement, all can only do single processing to containing the many metalliferous materials processing of arsenic indium, or the indium in the material is reclaimed, or just the arsenic in the material handled, at present the still unmatchful integrated conduct method that contains the many metalliferous materials of arsenic indium.
Summary of the invention
The object of the present invention is to provide a kind of many metalliferous materials utilization of arsenic indium and method for innocent treatment of containing.
Present method adopts wet method smelting process that the most of dissolving of metals such as arsenic, indium is got into solution, and plumbous, tin gets in the slag, utilizes hydrolysis that indium is precipitated then, and the indium that precipitates leaches with hydrochloric acid, and the rich solution of indium that obtains is through displacement, and founding obtains the thick indium of product; Arsenic containing solution adds alkaline purification again, generates harmless ferrite, and concrete process step is following:
1, the acid leaching: will contain the many metalliferous materials of arsenic indium and add in the sulphuric acid soln, and add oxygenant, controlled temperature 70-80 ℃, reaction times 4-5 hour, indium is most of to be got in the solution, is insoluble in the material slag input of acid, and control is sour 80-100g/L eventually, press filtration; Its reaction formula is:
In 2O 3+3H 2SO 4＝In 2(so 4) 3+3H 2O
In+3H 2SO 4＝In 2(SO 4) 3+3H 2
2InASO 4+3H 2SO 4＝In(SO 4) 3+2H 3ASO 4
ZnO+H 2SO 4＝ZnSO 4+H 2O
CdO+H 2SO 4＝CdSO 4+H 2O
Fe 2O 3+3H 2SO 4＝Fe 2(SO4) 3+3H 2O
AI 2O 3+3H 2SO 4＝AI 2(SO4) 3+3H 2O
ZnO Fe 2O 3+4H 2SO 4＝ZnSO 4+Fe 2(SO4) 3+4H 2O
2, the heavy indium of hydrolysis: in pressing filtering liquid, add alkaline matter, when pH value reaches 5-5.4, press filtration in a hour, 99.5% indium precipitates.Press filtration; Its reaction formula is:
In 2(so 4) 3+6NaOH＝2In(OH) 3+3Na 2SO 4
3, hydrochloric acid leaches: with the dissolving with hydrochloric acid generation indiumchloride solution of press filtration indium slag with an amount of 10mol, its reaction formula is:
2In(OH)3+6HCI＝2InCI3+6H2O
4, neutralization: indiumchloride solution adds a spot of alkaline matter, control pH value 2-2.5;
5, displacement: the solution of neutralization reaction is sent into displacement slot, replaces with zinc metal sheet, makes indium be reduced to zeroth order, gets the sponge indium;
6, founding: producing the sponge indium by the displacement operation and press group, send casting furnace to carry out founding, carry out electrolysis again, must purity be 99.99% electrolysis indium;
7, the heavy arsenic of hydrolysis: will sink that liquid adds ydrogen peroxide 50 behind the indium, and add alkaline matter then, control pH is 8.5～12; Kept 5～60 minutes, and added ferrous sulfate, control pH is 8～10; Under 60-90 ℃, reacted 30～60 minutes, can the reaction of the arsenic in the solution be generated harmless ferrite; Press filtration, solution send Sewage treatment systems to carry out deep purifying.
Advantage of the present invention: the wet method dearsenication effect is remarkable, and arsenic-removing rate is greater than 93%; Arsenic and valuable metal good separating effect, the valuable metal slag contains arsenic less than 1%; Be convenient to the recovery of valuable metal; The arsenic waste residue that forms is general solid waste, is convenient to dispose, and waste water has reached the requirement of first discharge standard, has realized the comprehensive recovery of arsenic-containing material and innoxious.
Description of drawings
Fig. 1 is a concrete process flow sheet of the present invention.
Embodiment
Embodiment 1
Raw material: cigarette ash, composition is following
The cigarette ash element Zn In Sn As Pb H 2O
Content (%) 7.74 2962(g/t) 10.57 8.99 43.5 0.1
The acid leaching: take by weighing cigarette ash 200g in beaker, add sulfuric acid 120ml, MnO at clear water 1000ml 215g when treating that the water-bath temperature rises to 95 ℃, places water-bath with beaker, and constant temperature stirs 5h.Acid: 90g/L filters eventually, respectively sample examination:
The slicker solder slag Pb Sn In As Zn Dried slag
Content (%) 44.46 10.7 451(g/t) 0.51 2.41 193.7
The filtrating result:
Filtrating Pb Sn In As Zn Volume ml
Content (g/L) 0.05 0.42 520(mg/L) 17.5 11.17 970
Indium is sunk in hydrolysis:
In pressing filtering liquid, add caustic soda 70 grams, when pH value reaches 5-5.4, press filtration in a hour, 99.5% indium precipitates.Press filtration.Get slag 2.6 grams.
Hydrochloric acid leaches:
With the dissolving with hydrochloric acid generation indiumchloride solution of press filtration indium slag with an amount of 10mol.
Arsenic is sunk in hydrolysis:
To sink that liquid adds ydrogen peroxide 50 behind the indium, and add alkaline matter then, control pH is 8.5～12; Kept 5～60 minutes, and added ferrous sulfate, control pH is 8～10; Under 60-90 ℃, reacted 30～60 minutes, can the reaction of the arsenic in the solution be generated harmless ferrite; Make solution contain arsenic and reach 0.05mg/L, press filtration, solution send Sewage treatment systems to carry out deep purifying.
The leaching yield of arsenic is 95.36%
Embodiment 2
Raw material: 2000 kilograms of cigarette ashes,
The cigarette ash element Zn In Sn As Pb H 2O
Content (%) 3.34 2066g/t 0 18.58 31.47 0.68
The acid leaching: at 15m 3Reactive tank in allocate clear water 10m into 3, add 1000 kilograms in sulfuric acid, make beginning acid reach 150g/l, MnO 2200 kilograms, heat up to stir, when temperature to 95 ℃, insulated and stirred 5h, sour 56g/l eventually.Press and consider, respectively sample examination: get solution 9.8m 3, 2683 kilograms of slags.
The slicker solder slag Pb Sn In As Zn H 2O
Content (%) 31.63 0 252g/t 1.32 0.34 26.56
The filtrating result:
Filtrating Pb Sn In As Zn Volume
Content (g/L) 0.06 0 375mg/L 35.2 0.65 9.8m 3
Indium is sunk in hydrolysis:
In pressing filtering liquid, add 450 kilograms in caustic soda, when pH value reaches 4-5, press filtration in a hour, 99.5% indium precipitates, and press filtration gets 5.2 kilograms of indium slags, moisture content 35%.
Hydrochloric acid leaches:
Press filtration indium slag dissolved under normal temperature with the hydrochloric acid of the 10mol of 6.5L generate indiumchloride solution.
Neutralization:
Indiumchloride solution adds 390 kilograms in caustic soda and oxygenant neutralization, and control pH value 2-2.5 filters.
Displacement:
Solution of indium is sent into displacement slot, replaces with zinc metal sheet, makes indium be reduced to zeroth order, gets the sponge indium.
Founding:
Produces sponge indium pressure by the displacement operation and roll into a ball, send casting furnace to carry out founding, obtain 3.55 kilograms of 99% thick indiums.
Arsenic is sunk in hydrolysis:
To sink that liquid adds 20 kilograms of dioxygens behind the indium, and add 10 kilograms in caustic soda then, control pH is 8.5～12; Kept 5～60 minutes, and added 1000 kilograms in ferrous sulfate, control pH is 8～10; Under 60-90 ℃, reacted 30～60 minutes, can the reaction of the arsenic in the solution be generated harmless ferrite; Make solution contain arsenic and reach 0.05mg/L, press filtration, solution send Sewage treatment systems to carry out deep purifying.
From above test result analysis:
The leaching yield of arsenic has reached 92.8%, and recrement satisfies next step comprehensive recovery requirement fully;
Waste water send sewage plant to utilize the biotechnological formulation deep purifying, has reached first discharge standard.

Claims (1)

1. one kind contains many metalliferous materials utilization of arsenic indium and method for innocent treatment, it is characterized in that, may further comprise the steps:
1), the acid leaching: will contain the many metalliferous materials of arsenic indium and add in the sulphuric acid soln, and add oxygenant, controlled temperature 70-80 ℃, reaction times 4-5 hour, indium is most of to be got in the solution, is insoluble in the material slag input of acid, and control is sour 80-100g/L eventually, press filtration;
2), the heavy indium of hydrolysis: in pressing filtering liquid, add alkaline matter, when pH value reaches 5-5.4, press filtration in a hour, 99.5% indium precipitates.Press filtration; Its reaction formula is:
In 2(so 4) 3+6NaOH＝2In(OH) 3+3Na 2SO 4
3), hydrochloric acid leaches: with the dissolving with hydrochloric acid generation indiumchloride solution of press filtration indium slag with an amount of 10mol, its reaction formula is:
4), neutralization: indiumchloride solution adds a spot of alkaline matter, control pH value 2-2.5;
5), displacement: the solution of neutralization reaction is sent into displacement slot, replaces with zinc metal sheet, makes indium be reduced to zeroth order, gets the sponge indium;
6), founding: producing the sponge indium by the displacement operation and press group, send casting furnace to carry out founding, carry out electrolysis again, must purity be 99.99% electrolysis indium;
7), the heavy arsenic of hydrolysis: will sink that liquid adds ydrogen peroxide 50 behind the indium, and add alkaline matter then, control pH is 8.5～12; Kept 5～60 minutes, and added ferrous sulfate, control pH is 8～10; Under 60-90 ℃, reacted 30～60 minutes, can the reaction of the arsenic in the solution be generated harmless ferrite; Press filtration, solution send Sewage treatment systems to carry out deep purifying.
CN201210040523XA 2012-02-22 2012-02-22 Method for utilization and harmless treatment of multi-metal material containing arsenic and indium Pending CN102560123A (en)

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Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103468959A (en) * 2013-10-10 2013-12-25 郴州市金贵银业股份有限公司 Method for treating high-arsenic, high-selenium and high-tellurium anode mud through oxygen pressure
CN103572041A (en) * 2013-10-25 2014-02-12 湖南省环境保护科学研究院 Wet deep dearsenification method for high-arsenic iron ores
CN103588240A (en) * 2013-11-27 2014-02-19 郴州市金贵银业股份有限公司 Green utilization method of waste acid
CN104561610A (en) * 2014-12-26 2015-04-29 河南豫光锌业有限公司 Method and device for treating washing water in refined indium production
CN104651622A (en) * 2015-02-16 2015-05-27 广西德邦科技有限公司 Method for separating indium from cadmium slag
CN106544513A (en) * 2016-11-09 2017-03-29 河南中原黄金冶炼厂有限责任公司 A kind of method of copper smelting by pyrometallurgy white cigarette dirt valuable metal recovery
CN110004295A (en) * 2019-03-27 2019-07-12 长春黄金研究院有限公司 The method of the recycling of gold smelting enterprise lean solution and deep treatment cyanogen copper arsenic and sodium salt
CN111270091A (en) * 2020-02-29 2020-06-12 河南豫光锌业有限公司 Method for reducing indium content in indium leaching slag

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Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103468959A (en) * 2013-10-10 2013-12-25 郴州市金贵银业股份有限公司 Method for treating high-arsenic, high-selenium and high-tellurium anode mud through oxygen pressure
CN103572041A (en) * 2013-10-25 2014-02-12 湖南省环境保护科学研究院 Wet deep dearsenification method for high-arsenic iron ores
CN103588240A (en) * 2013-11-27 2014-02-19 郴州市金贵银业股份有限公司 Green utilization method of waste acid
CN103588240B (en) * 2013-11-27 2016-02-10 郴州市金贵银业股份有限公司 A kind of green utilization method of dirty acid
CN104561610A (en) * 2014-12-26 2015-04-29 河南豫光锌业有限公司 Method and device for treating washing water in refined indium production
CN104651622A (en) * 2015-02-16 2015-05-27 广西德邦科技有限公司 Method for separating indium from cadmium slag
CN106544513A (en) * 2016-11-09 2017-03-29 河南中原黄金冶炼厂有限责任公司 A kind of method of copper smelting by pyrometallurgy white cigarette dirt valuable metal recovery
CN110004295A (en) * 2019-03-27 2019-07-12 长春黄金研究院有限公司 The method of the recycling of gold smelting enterprise lean solution and deep treatment cyanogen copper arsenic and sodium salt
CN111270091A (en) * 2020-02-29 2020-06-12 河南豫光锌业有限公司 Method for reducing indium content in indium leaching slag

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Application publication date: 20120711