CN101817553B - Method for treating arsenic-containing smoke dust - Google Patents
Method for treating arsenic-containing smoke dust Download PDFInfo
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- CN101817553B CN101817553B CN2010101381746A CN201010138174A CN101817553B CN 101817553 B CN101817553 B CN 101817553B CN 2010101381746 A CN2010101381746 A CN 2010101381746A CN 201010138174 A CN201010138174 A CN 201010138174A CN 101817553 B CN101817553 B CN 101817553B
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Abstract
The invention provides a method for synthesizing ferricarsenate from arsenic-containing smoke dust by leaching, pressure oxidation and conversion, and consolidating the ferricarsenate. The method comprises the following steps of: leaching the arsenic-containing smoke dust by using 10 to 30g/L of dilute sulfuric acid solution; mixing and stirring the smoke dust and powdered pyrite; adding the mixture into a closed stirring reactor; introducing oxygen into the reactor until the oxygen partial pressure is between 0.6 and 1.5MPa; heating the reactor to the temperature of between 100 and 160 DEG C, stirring the mixture to perform reaction for 2 to 4 hours; filtering the reaction product to obtain mixed solid of ferricarsenate and sulphur, and 10 to 30g/L of dilute sulfuric acid solution which is returned and leached; and solidifying the mixed solid to obtain environment-friendly hydrophobic solid with high strength. The method has no emission of waste gas or waste water in the treatment process, can solve the opening problem of arsenic in various arsenic-containing smoke dusts, and eliminates pollution of the arsenic-containing smoke dust to the environment.
Description
Technical field
The invention belongs to the non-ferrous metallurgy technology field.Relate to and a kind ofly leach, add the synthetic ferric arsenate of pyrite pressure oxidation and elementary sulfur and fixed method through sulfuric acid solution with arsenic-containing smoke dust.
Background technology
Arsenic is the mineral resources that relatively disperse, independent mineral deposit seldom, multi mineral symbiosis such as many and tin, lead, copper; In the smelting process of this type non-ferrous metal, arsenic mainly gets into other intermediate products of flue dust neutralization, causes a large amount of main metals to overstock in intermediate product on the one hand; Or harmful element such as arsenic circulation repeatedly in smelting process; Influencing the smelting technique economic indicator, is infringement operating personnel's health Jiankang on the other hand, causes the pollution of arsenic to environment.
In the nonferrous metallurgical process in the arsenic-containing smoke dust of output dearsenification mainly contain and produce the arsenic product and change the arsenate that is insoluble in water into and store up two kinds of methods.
The arsenic product of arsenic-containing material production mainly is white arsenic, and the method for employing mainly contains the pyrogenic process volatilization and wet method leaches two kinds.Wet processing leach to get into solution with hot water with arsenic, and condensing crystallizing obtains As after assorted through taking off again, the decolouring
2O
3Product, the leached mud Returning smelting.The technology that Chinese patent N1098442 provides a kind of wet method to extract white arsenic is raw material with the tin calcination fume, and heating at water adds natural limestone powder adjusting slip pH value when leaching; Filtrating adds ammoniacal liquor and regulates the pH value, filters, and filtrating is used activated carbon decolorizing; Condensing crystallizing obtains to contain As
2O
3More than 99.5% white arsenic product.Pyrogenic process volatilization is at high temperature with the arsenic oxidation in flue dust and other arsenic-containing materials or be reduced to As
2O
3Volatilization gets into flue gas, after cooling off, gathering dust, obtains As again
2O
3The flue dust of product or enrichment arsenic.Chinese patent CN1403603 provides a kind of arsenic removing method of anode mud with high As and Pb, is employed in rotary kiln and feeds steam roasting, and the flue dust that roasting produces is collected through condenser system and reclaimed As
2O
3, tail gas is handled the back discharging with alkali lye.Control suitable roasting condition, can remove most arsenic in the earth of positive pole, plumbous, antimony is then stayed in the calcining.This method raw material wide accommodation can be handled the various arsenic solid materials that contain, and arsenic is deviate from comparatively thorough, but the difficulty of governance of waste gas is big, needs complicated smoke processing system.
Be converted into the arsenate method that is insoluble in water, mainly contain two kinds of methods of calcium arsenate and ferric arsenate.Because the toxicity of white arsenic and other arsenic products is big, has limited its purposes and consumption, the method that the indissoluble arsenate that therefore is converted into environmental sound is stored up dearsenification more and more obtains paying attention to.
Chinese patent CN1155587 provides a kind of dearsenicating technology of high-arsenic material, the NaOH aqueous solution is mixed with high-arsenic material mix thoroughly, and at 300～650 ℃ of following medium temperature roasts, calcining leaches with hot water after the mixture oven dry, and leachate is with the compound of calcic or contain NH
4+, Mg
2+Compound precipitation gained arsenic containing solution in arsenic.This method needs high-temperature roasting, and it is bigger to consume energy.
Fang Zhao spreads out etc. and to have reported in a kind of high arsenic solution the method with the dearsenification process in " chemical industry metallurgical " 2I the 4th phase of rolling up in 2000; Nitric acid catalytic oxidation leachate with the high arsenic indissoluble gold ore deposit of iron content 30.46～47.62, arsenic 19.72～56.48 is a raw material; Adopt NaOH to make neutralization, hydrogen peroxide oxidation; The control endpoint pH is 5～6, normal pressure neutralization precipitation ferric arsenate, and liquid can reach the national standard of discharge of wastewater behind the heavy arsenic.
Summary of the invention
The purpose of this invention is to provide and a kind ofly change arsenic in the arsenic-containing smoke dust of output in the nonferrous metallurgical process method of the hydrophobic solid of intensity height, environmental sound into, reduce the circulation of arsenic in smelting process, and eliminate the harm of arsenic environment.
Realize that the technical scheme that above-mentioned purpose of the present invention is taked is: arsenic-containing smoke dust is leached with sulfuric acid solution; Leachate is pressed reacting dose and is added powdery pyrite; Pressure oxidation synthesizes ferric arsenate and sulphur mixture; To mixture heating, make the liquid-state sulfur of fusing be coated on the surface of calcium arsenate solid particle, cooling obtains hydrophobic solid.
Concrete process of the present invention is:
(1) sulfuric acid solution of arsenic-containing smoke dust with 10～30g/L leached, leachate adds powdery pyrite and mixed 0.5 hour, and leached mud is Returning smelting again;
(2) mixture is added in the airtight stirred reactor, aerating oxygen or air are heated to 100～160 ℃ to partial pressure of oxygen 0.6～1.5MPa; Stirring reaction 2～4 hours; Filtration obtains the hybrid solid of ferric arsenate and sulphur, and the sulfuric acid solution of 10～30g/L, and sulfuric acid solution returns leaching;
(3) hybrid solid with ferric arsenate and sulphur is heated to 120～150 ℃, and clamp dog or system ball cool off fixed again; Or, be heated to 120～150 ℃ again with the hybrid solid clamp dog of ferric arsenate and sulphur or system ball, and cool off fixedly, finally obtain the hydrophobic solid of environmental sound.
Said arsenic-containing smoke dust is the flue dust that contains arsenic 30～70wt% of output in Sn, Pb, the Cu non-ferrous metal pyrometallurgical smelting process.
Said powdery pyrite granularity was 100 mesh sieves, and addition is that iron and the mol ratio of the arsenic in the leachate in the pyrite is 1～2: 1.
Said clamp dog or system ball can adopt the method for compression moulding.
The invention has the beneficial effects as follows: with the arsenic in the arsenic flue dust with sulfuric acid solution leach back and pyrite be blended in the closed container with iron be oxidized to ferric iron, arsenic is oxidized to pentavalent arsenic and forms ferric arsenate; The generative process of oxidizing process and ferric arsenate is carried out in closed container; Part sulphur recycles after being oxidized to sulfuric acid, and processing procedure does not have waste gas, discharge of wastewater; Be molten into liquid state in the follow-up consolidation process process of the elementary sulfur of output in the oxidizing process; Be coated on the calcium arsenate solid particle the surface and as binding agent and void filler; With particle bond and fill the space, utilize the hydrophobicity of elementary sulfur, fixed back solid is a hydrophobic solid; Solved the stripping problem again that the calcium arsenate solid is stored up arsenic in the process, high, the environmental sound of intensity of fixed back solid; Effectively utilized the low-quality pyrite of the output in the nonferrous metal sulfide mineral ore dressing process, raw material sources are extensive; Can solve the open circuit problem of arsenic in the various flue dust that contain arsenic, eliminate the pollution of arsenic-containing smoke dust environment.
Description of drawings
Fig. 1 is a principle process chart of the present invention.
Specific embodiments
Embodiment 1
Flue dust composition: As48.34%; Pyrite composition: Fe43.28%, S36.57%, granularity-100 order.
With 1.0Kg arsenic-containing smoke dust and concentration is the sulfuric acid solution leaching of 21.74g/L, obtains the 11.2L leachate, and arsenic concentration is 41.03g/L.With mixing 0.5 hour in the 1.19Kg pyrite dust adding leachate, add in the airtight stirred reactor, aerating oxygen is to partial pressure of oxygen 1.0Mpa; Be heated to 130 ℃, stirring reaction 3 hours filters; Obtain the hybrid solid 2.11Kg of ferric arsenate and elementary sulfur, the sulfuric acid solution 10.3L. of 19.73g/L
Get the 1kg hybrid solid and be heated to 135 ℃, briquet is cooled to normal temperature consolidatedly, obtains the hydrophobic solid of intensity height, environmental sound; With 1kg hybrid solid briquet, be heated to 135 ℃ and be incubated 20 minutes, be cooled to normal temperature consolidatedly, obtain the hydrophobic solid of intensity height, environmental sound.
Embodiment 2
Flue dust composition: As48.34%; Pyrite composition: Fe43.28%, S36.57%, granularity-100 order.
With 1.0Kg arsenic-containing smoke dust and concentration is the sulfuric acid solution leaching of 12.74g/L, obtains the 11.4L leachate, and arsenic concentration is 38.59g/L; With mixing 0.5 hour in the 1.52Kg pyrite dust adding leachate, add in the airtight stirred reactor, aerating oxygen is to partial pressure of oxygen 1.5Mpa; Be heated to 100 ℃, stirring reaction 4 hours filters; Obtain the hybrid solid 2.53Kg of ferric arsenate and elementary sulfur, the sulfuric acid solution 10.4L of 11.43g/L.
Get the 1kg hybrid solid and be heated to 150 ℃, briquet is cooled to normal temperature consolidatedly, obtains the hydrophobic solid of intensity height, environmental sound; Get 1kg hybrid solid briquet, be heated to 150 ℃ and be incubated 10 minutes, be cooled to normal temperature consolidatedly, obtain the hydrophobic solid of intensity height, environmental sound.
Embodiment 3
Flue dust composition: As48.34%; Pyrite composition: Fe43.28%, S36.57%, granularity-100 order.
With 1.0Kg arsenic-containing smoke dust and concentration is the sulfuric acid solution leaching of 28.43g/L, obtains the 11.2L leachate, and arsenic concentration is 42.3g/L; With mixing 0.5 hour in the 1.52Kg pyrite dust adding leachate, add in the airtight stirred reactor, aerating oxygen is to partial pressure of oxygen 0.7Mpa; Be heated to 160 ℃, stirring reaction 2 hours filters; Obtain the hybrid solid 1.69Kg of ferric arsenate and elementary sulfur, the sulfuric acid solution 10.1L of 29.57g/L.
Get the 1kg hybrid solid and be heated to 120 ℃, briquet is cooled to normal temperature consolidatedly, obtains the hydrophobic solid of intensity height, environmental sound; Get 1kg hybrid solid briquet, be heated to 120 ℃ and be incubated 30 minutes, be cooled to normal temperature consolidatedly, obtain the hydrophobic solid of intensity height, environmental sound.
Claims (2)
1. the processing method of an arsenic-containing smoke dust; It is characterized in that: arsenic-containing smoke dust is leached with sulfuric acid solution; Leachate is pressed reacting dose and is added powdery pyrite, and pressure oxidation synthesizes ferric arsenate and sulphur mixture, and mixture is heated; Make the liquid-state sulfur of fusing be coated on the surface of ferric arsenate solid particle, cooling obtains hydrophobic solid; Said arsenic-containing smoke dust is the flue dust that contains arsenic 30～70wt% of output in Sn, Pb, the Cu non-ferrous metal pyrometallurgical smelting process; Said powdery pyrite granularity was 100 mesh sieves, and addition is that iron and the mol ratio of the arsenic in the leachate in the pyrite is 1～2:1; The concrete operations step is following,
(1) sulfuric acid solution of arsenic-containing smoke dust with 10～30g/L leached, leachate adds powdery pyrite and mixed 0.5 hour;
(2) mixture is added in the airtight stirred reactor, aerating oxygen or air are heated to 100～160 ℃ to partial pressure of oxygen 0.6～1.5MPa; Stirring reaction 2～4 hours; Filtration obtains the hybrid solid of ferric arsenate and sulphur, and the sulfuric acid solution of 10～30g/L, and sulfuric acid solution returns leaching;
(3) hybrid solid with ferric arsenate and sulphur is heated to 120～150 ℃, and clamp dog or system ball cool off fixed again; Or, be heated to 120～150 ℃ again with the hybrid solid clamp dog of ferric arsenate and sulphur or system ball, cool off fixed.
2. the processing method of arsenic-containing smoke dust according to claim 1 is characterized in that: the method for said clamp dog or system ball employing compression moulding.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102249609B (en) * | 2011-04-29 | 2013-06-12 | 昆明理工大学 | Arsenic-containing waste slag solidified body and preparation method thereof |
| CN102634672A (en) * | 2012-04-17 | 2012-08-15 | 金川集团有限公司 | Method for treating arsenic-containing waste copper slag |
| FI126884B (en) * | 2013-11-29 | 2017-07-14 | Outotec Finland Oy | Method and arrangement for separating arsenic from starting material |
| WO2015113141A1 (en) | 2014-01-31 | 2015-08-06 | Goldcorp Inc. | Process for separation of at least one metal sulfide compristng arsenic and/or antimony from a mixed sulfide concentrate |
| CN105734300B (en) * | 2014-12-08 | 2018-03-27 | 云南云铜锌业股份有限公司 | A kind of method that recovery copper, arsenic are cured as scorodite from copper fumes |
| CN106282534B (en) * | 2016-08-29 | 2017-08-25 | 长沙华时捷环保科技发展股份有限公司 | The stable curing method of arsenic acid scum |
| CN106834704A (en) * | 2016-11-18 | 2017-06-13 | 河南中原黄金冶炼厂有限责任公司 | A kind of white cigarette dirt valuable metal recovery and the method for harmless treatment |
| CN106834676B (en) * | 2016-12-21 | 2017-11-14 | 中南大学 | A kind of method that valuable metal and arsenic recycling harmlessness disposing are reclaimed from arsenic-containing smoke dust |
| CN106823235B (en) * | 2016-12-21 | 2017-12-22 | 中南大学 | A kind of method that regulation and control growth method prepares the solid arsenic mineral of high stability |
| CN106834718B (en) * | 2016-12-21 | 2017-11-14 | 中南大学 | A kind of arsenic-containing smoke dust comprehensive utilization and the method for arsenic harmlessness disposing |
| CN108754167A (en) * | 2018-06-28 | 2018-11-06 | 北京矿冶科技集团有限公司 | A kind of method that Copper making flue dust efficiently separates copper arsenic |
| CN113684368A (en) * | 2021-08-29 | 2021-11-23 | 中南大学 | Method for co-processing arsenic sulfide slag and arsenic-containing smoke dust in copper smelting |
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| US5234669A (en) * | 1991-08-08 | 1993-08-10 | Idaho Research Foundation, Inc. | Recovery of non-ferrous metals from smelter flue dusts and sludges |
| EP1187661B1 (en) * | 1999-06-22 | 2004-03-24 | Pâques Bio Systems B.V. | Process for immobilising arsenic waste |
| CN1569289A (en) * | 2004-05-12 | 2005-01-26 | 上海洁申实业有限公司 | Harmless treatment method for arsenic contained rejectamenta |
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| FI120315B (en) * | 2007-11-27 | 2009-09-15 | Outotec Oyj | A process for treating a pyrite concentrate containing gold, copper and arsenic |
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|---|---|---|---|---|
| US5234669A (en) * | 1991-08-08 | 1993-08-10 | Idaho Research Foundation, Inc. | Recovery of non-ferrous metals from smelter flue dusts and sludges |
| EP1187661B1 (en) * | 1999-06-22 | 2004-03-24 | Pâques Bio Systems B.V. | Process for immobilising arsenic waste |
| CN1569289A (en) * | 2004-05-12 | 2005-01-26 | 上海洁申实业有限公司 | Harmless treatment method for arsenic contained rejectamenta |
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Effective date of registration: 20160706 Address after: 661007 Honghe arsenic industry company, Gejiu City, Honghe Hani and Yi Autonomous Prefecture, Yunnan Patentee after: Honghe arsenic Industry Co Ltd Address before: 661000, Yunnan tin Refco Group Ltd, 121 East Jinhu Road, Gejiu City, Yunnan Patentee before: Yunnan Tin Group (Holding) Co., Ltd |