CN101817553A - Method for treating arsenic-containing smoke dust - Google Patents
Method for treating arsenic-containing smoke dust Download PDFInfo
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- CN101817553A CN101817553A CN 201010138174 CN201010138174A CN101817553A CN 101817553 A CN101817553 A CN 101817553A CN 201010138174 CN201010138174 CN 201010138174 CN 201010138174 A CN201010138174 A CN 201010138174A CN 101817553 A CN101817553 A CN 101817553A
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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 a kind of arsenic-containing smoke dust of using and leach, add the synthetic ferric arsenate of pyrite pressure oxidation and elementary sulfur and fixed method through sulphuric acid soln.
Background technology
Arsenic is comparison dispersive mineral wealth, independent mineral deposit seldom, multi mineral symbiosis such as many and tin, lead, copper, in the smelting process of this class non-ferrous metal, arsenic mainly enters flue dust other intermediates that neutralize, and 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 technology economic target, 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 to 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 leaches arsenic with hot water and enters solution, and condensing crystal 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, filtrate adds ammoniacal liquor and regulates the pH value, filters, and filtrate is used activated carbon decolorizing, condensing crystal 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 enters flue gas, obtains As again after cooling off, gathering dust
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, adopts at rotary kiln and feeds steam roasting, and the flue dust that roasting produces is collected by 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 anode sludge, plumbous, antimony is then stayed in the calcining.This method raw material wide accommodation can be handled the various arsenic solid materialss 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 Tricalcium 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 leach liquor is with calcareous compound 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 and the method for dearsenification process in " chemical industry metallurgical " 2I the 4th phase of rolling up in 2000, nitric acid catalyzed oxidation leach liquor 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, 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 sulphuric acid soln, leach liquor is pressed reacting weight and is added powdery pyrite, pressure oxidation synthesizes ferric arsenate and sulphur mixture, to mixture heating up, make the liquid-state sulfur of fusing be coated on the surface of Tricalcium arsenate solid particulate, cooling obtains hydrophobic solid.
Concrete processing method of the present invention is:
(1) sulphuric acid soln of arsenic-containing smoke dust with 10～30g/L leached, leach liquor 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 oxygen partial pressure 0.6～1.5MPa, stirring reaction 2～4 hours, filtration obtains the blended solid of ferric arsenate and sulphur, and the sulphuric acid soln of 10～30g/L, and sulphuric acid soln returns leaching;
(3) blended solid with ferric arsenate and sulphur is heated to 120～150 ℃, and clamp dog or system ball cool off fixed again; Or with the blended solid clamp dog of ferric arsenate and sulphur or system ball, reheat to 120～150 ℃ are cooled off fixedly, finally obtain the hydrophobic solid of environmental sound.
Described 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.
Described powdery pyrite granularity was 100 mesh sieves, and add-on is that the iron in the pyrite and the mol ratio of the arsenic in the leach liquor are 1～2: 1.
Described 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 sulphuric acid soln leach the back be blended in the encloses container with pyrite iron is oxidized to ferric iron, arsenic is oxidized to pentavalent arsenic and forms ferric arsenate, the generative process of oxidising process and ferric arsenate is carried out in encloses container, part sulphur recycles after being oxidized to sulfuric acid, and treating processes 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 oxidising process, be coated on the Tricalcium arsenate solid particulate 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 Tricalcium arsenate solid is stored up arsenic in the process, fixed back solid intensity height, environmental sound; 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 arsenical flue dust, eliminate the pollution of arsenic-containing smoke dust environment.
Description of drawings
Fig. 1 is a principle process flow sheet 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 sulphuric acid soln leaching of 21.74g/L, obtains the 11.2L leach liquor, and arsenic concentration is 41.03g/L.With mixing 0.5 hour in the 1.19Kg pyritic ashes adding leach liquor, add in the airtight stirred reactor, aerating oxygen is to oxygen partial pressure 1.0Mpa, be heated to 130 ℃, stirring reaction 3 hours filters, obtain the blended solid 2.11Kg of ferric arsenate and elementary sulfur, the sulphuric acid soln 10.3L. of 19.73g/L
Get the 1kg blended solid and be heated to 135 ℃, briquetting is cooled to normal temperature consolidatedly, obtains the hydrophobic solid of intensity height, environmental sound; With 1kg blended solid briquetting, 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 sulphuric acid soln leaching of 12.74g/L, obtain the 11.4L leach liquor, arsenic concentration is 38.59g/L, the 1.52Kg pyritic ashes is added in the leach liquor mixed 0.5 hour, adds in the airtight stirred reactor, aerating oxygen is to oxygen partial pressure 1.5Mpa, be heated to 100 ℃, stirring reaction 4 hours filters, obtain the blended solid 2.53Kg of ferric arsenate and elementary sulfur, the sulphuric acid soln 10.4L of 11.43g/L.
Get the 1kg blended solid and be heated to 150 ℃, briquetting is cooled to normal temperature consolidatedly, obtains the hydrophobic solid of intensity height, environmental sound; Get 1kg blended solid briquetting, 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 sulphuric acid soln leaching of 28.43g/L, obtain the 11.2L leach liquor, arsenic concentration is 42.3g/L, the 1.52Kg pyritic ashes is added in the leach liquor mixed 0.5 hour, adds in the airtight stirred reactor, aerating oxygen is to oxygen partial pressure 0.7Mpa, be heated to 160 ℃, stirring reaction 2 hours filters, obtain the blended solid 1.69Kg of ferric arsenate and elementary sulfur, the sulphuric acid soln 10.1L of 29.57g/L.
Get the 1kg blended solid and be heated to 120 ℃, briquetting is cooled to normal temperature consolidatedly, obtains the hydrophobic solid of intensity height, environmental sound; Get 1kg blended solid briquetting, 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 (5)
1. the treatment process of an arsenic-containing smoke dust, it is characterized in that: arsenic-containing smoke dust is leached with sulphuric acid soln, leach liquor is pressed reacting weight and is added powdery pyrite, pressure oxidation synthesizes ferric arsenate and sulphur mixture, to mixture heating up, make the liquid-state sulfur of fusing be coated on the surface of Tricalcium arsenate solid particulate, cooling obtains hydrophobic solid.
2. the treatment process of arsenic-containing smoke dust according to claim 1 is characterized in that:
(1) sulphuric acid soln of arsenic-containing smoke dust with 10～30g/L leached, leach liquor 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 oxygen partial pressure 0.6～1.5MPa, stirring reaction 2～4 hours, filtration obtains the blended solid of ferric arsenate and sulphur, and the sulphuric acid soln of 10～30g/L, and sulphuric acid soln returns leaching;
(3) blended solid with ferric arsenate and sulphur is heated to 120～150 ℃, and clamp dog or system ball cool off fixed again; Or with the blended solid clamp dog of ferric arsenate and sulphur or system ball, reheat to 120～150 ℃ are cooled off fixed.
3. the treatment process of arsenic-containing smoke dust according to claim 1, it is characterized in that: described 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.
4. the treatment process of arsenic-containing smoke dust according to claim 1, it is characterized in that: described powdery pyrite granularity was 100 mesh sieves, add-on is that the iron in the pyrite and the mol ratio of the arsenic in the leach liquor are 1～2: 1.
5. according to the treatment process of claim 2,3 or 4 described arsenic-containing smoke dusts, it is characterized in that: described clamp dog or system ball adopt the method for compression moulding.
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| CN2010101381746A CN101817553B (en) | 2010-04-02 | 2010-04-02 | Method for treating arsenic-containing smoke dust |
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| CN2010101381746A CN101817553B (en) | 2010-04-02 | 2010-04-02 | Method for treating arsenic-containing smoke dust |
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Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102249609A (en) * | 2011-04-29 | 2011-11-23 | 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 |
| CN105734300A (en) * | 2014-12-08 | 2016-07-06 | 云南云铜锌业股份有限公司 | Method for recovering copper from copper dust and immobilizing arsenic from copper dust into scorodite |
| CN105765090A (en) * | 2013-11-29 | 2016-07-13 | 奥图泰(芬兰)公司 | Method and arrangement of separating arsenic from starting materials |
| CN106282534A (en) * | 2016-08-29 | 2017-01-04 | 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 |
| CN106834676A (en) * | 2016-12-21 | 2017-06-13 | 中南大学 | A kind of method that valuable metal and arsenic resource harmlessness disposing are reclaimed from arsenic-containing smoke dust |
| CN106823235A (en) * | 2016-12-21 | 2017-06-13 | 中南大学 | A kind of method that regulation and control growth method prepares the solid arsenic mineral of high stability |
| CN106834718A (en) * | 2016-12-21 | 2017-06-13 | 中南大学 | A kind of arsenic-containing smoke dust comprehensive utilization and the method for arsenic harmlessness disposing |
| US9885095B2 (en) | 2014-01-31 | 2018-02-06 | Goldcorp Inc. | Process for separation of at least one metal sulfide from a mixed sulfide ore or concentrate |
| 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 |
| WO2023030165A1 (en) * | 2021-08-29 | 2023-03-09 | 中南大学 | Method for co-processing copper-smelting arsenic sulfide slag and arsenic-containing soot |
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Cited By (16)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102249609B (en) * | 2011-04-29 | 2013-06-12 | 昆明理工大学 | Arsenic-containing waste slag solidified body and preparation method thereof |
| CN102249609A (en) * | 2011-04-29 | 2011-11-23 | 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 |
| CN105765090A (en) * | 2013-11-29 | 2016-07-13 | 奥图泰(芬兰)公司 | Method and arrangement of separating arsenic from starting materials |
| US9885095B2 (en) | 2014-01-31 | 2018-02-06 | Goldcorp Inc. | Process for separation of at least one metal sulfide from a mixed sulfide ore or concentrate |
| US11124857B2 (en) | 2014-01-31 | 2021-09-21 | Goldcorp Inc. | Process for separation of antimony and arsenic from a leach solution |
| US10370739B2 (en) | 2014-01-31 | 2019-08-06 | Goldcorp, Inc. | Stabilization process for an arsenic solution |
| CN105734300A (en) * | 2014-12-08 | 2016-07-06 | 云南云铜锌业股份有限公司 | Method for recovering copper from copper dust and immobilizing arsenic from copper dust into scorodite |
| CN106282534A (en) * | 2016-08-29 | 2017-01-04 | 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 |
| CN106823235A (en) * | 2016-12-21 | 2017-06-13 | 中南大学 | A kind of method that regulation and control growth method prepares the solid arsenic mineral of high stability |
| 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 |
| CN106834718A (en) * | 2016-12-21 | 2017-06-13 | 中南大学 | A kind of arsenic-containing smoke dust comprehensive utilization and the method for arsenic harmlessness disposing |
| CN106834676A (en) * | 2016-12-21 | 2017-06-13 | 中南大学 | A kind of method that valuable metal and arsenic resource harmlessness disposing are reclaimed from arsenic-containing smoke dust |
| 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 |
| WO2023030165A1 (en) * | 2021-08-29 | 2023-03-09 | 中南大学 | Method for co-processing copper-smelting arsenic sulfide slag and arsenic-containing soot |
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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 |