CN106834714B - A kind of integrated conduct method of arsenic-containing material - Google Patents
A kind of integrated conduct method of arsenic-containing material Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
- C22B7/02—Working-up flue dust
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- A—HUMAN NECESSITIES
- A62—LIFE-SAVING; FIRE-FIGHTING
- A62D—CHEMICAL MEANS FOR EXTINGUISHING FIRES OR FOR COMBATING OR PROTECTING AGAINST HARMFUL CHEMICAL AGENTS; CHEMICAL MATERIALS FOR USE IN BREATHING APPARATUS
- A62D3/00—Processes for making harmful chemical substances harmless or less harmful, by effecting a chemical change in the substances
- A62D3/30—Processes for making harmful chemical substances harmless or less harmful, by effecting a chemical change in the substances by reacting with chemical agents
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- C22B13/00—Obtaining lead
- C22B13/02—Obtaining lead by dry processes
- C22B13/025—Recovery from waste materials
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- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
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- C22B13/04—Obtaining lead by wet processes
- C22B13/045—Recovery from waste materials
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- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B30/00—Obtaining antimony, arsenic or bismuth
- C22B30/02—Obtaining antimony
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- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
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- C22B30/04—Obtaining arsenic
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- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
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- C22B30/06—Obtaining bismuth
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Abstract
The present invention relates to a kind of integrated conduct methods of arsenic-containing material to reduce arsenic and accumulate in system and keep its innoxious including the production from valuable metals such as smelting smoke dust comprehensively reclaiming arsenic, antimony, lead, bismuths containing arsenic antimony lead.Method provided by the invention is soaked by normal pressure alkali, remove solvable arsenic in flue dust, trivalent arsenic is after catalysis oxidation is pentavalent arsenic in leachate, stable solid arsenic mineral is synthesized using distribution crystallisation, then solidify solid arsenic mineral by the way of stockpiling, leached mud is washed, reduction melting, aoxidizes the processes such as blowing, maximizes and recycles each valuable element.Arsenic is removed from flue dust, and makes antimony, lead, bismuth etc. and stayed in dearsenification slag as far as possible by the method, and the separation of arsenic and valuable metal and innoxious may be implemented.Comprehensive resource utilization rate of the present invention is high, and raw material wide adaptation range solves the cigarette ash generated in pollution problem in traditional handicraft extraction process, especially Lead-Zinc Sintering Process, and the advantage of this method is more obvious.
Description
Technical field
The invention belongs to metallurgical technology fields, and in particular to a kind of integrated conduct method of arsenic-containing material.
Background technique
In nature, arsenic is usually with mispickel (FeAsS), arsenic magnetic iron ore (FeAsS2), symplesite (FeAs2), sulphur arsenical copper
Mine (Cu3AsS3), realgar (As2S3), orpiment (As2S3) etc. mineral, be enriched in the non-ferrous metals such as copper, lead, zinc, nickel, cobalt, gold and silver
In ore；In Nonferrous Metallurgical Process, many high arsenic solid materials of output, such as roasting and melting flue dust.These materials are high containing arsenic
Up to 5~50%, also contain a large amount of valuable metal, directly returns and smelt process, lead to the circulative accumulation of arsenic in systems, because
This, usually should individually handle dearsenification.Arsenic belongs to severe toxicity, carcinogenic elements, applies gradually atrophy, in face of increasingly stringent environmental protection mark
How standard handles various high-arsenic materials, it has also become threatens the significant problem of nonferrous metallurgy industry existence.
The method of processing arsenic-containing smoke dust is mainly two classes at present, first is that fire concentrate, second is that wet separation.Pyrogenic process production
In, mainly using the difference of the oxide of arsenic and other elements oxide boiling point, separate arsenic with other elements.
CN103602835A discloses a kind of displacement reduction method and obtains crude arsenic and needle antimony, and CN103602834A discloses a kind of selective oxygen
Change-reduction obtains the not high As of purity2O3And needle antimony, CN104294053A disclose a kind of side of arsenic-containing smoke dust reduction volatilization arsenic
Method obtains arsenic trioxide purity and reaches 97.0% or more.But if contain the metal close with arsenic element property in flue dust
(such as antimony), then the arsenic trioxide purity obtained is not high.Mainly there are water logging, acidleach, alkali to soak three kinds of techniques in wet production, still
The products such as the not high arsenic trioxide of purity, natrium arsenicum can only be obtained, and the recycling of valuable metal powder is not made further research.
CN105567983A discloses a kind for the treatment of process of Copper making flue dust water logging-alkali leaching, separates arsenic with metal, the arsenic of preparation produces
Product are at a discount, still higher containing arsenic in leached mud.CN104357668A discloses a kind of waste acid leaching flue dust, electrodeposition dearsenification, acid
Leaching and electrolytic deposition process are easy to produce arsenic hydride.CN105648226A and CN105648227A discloses a kind of oxygen pressure alkali leaching realization arsenic
The method of antimony separation, more thoroughly, but the natrium arsenicum obtained in process is untreated, the valuable gold such as tellurium, antimony for the ratio of arsenic antimony separation
Belong to unrecovered.
There are many dearsenification, the research paper for extracting valuable metal and related patents report from flue dust, but there are valuable elements
Comprehensive recovery is low, and arsenic product market is limited, and there are potential security risks.Therefore, the existing technology has yet to be improved and developed.
Summary of the invention
In order to solve the problems, such as arsenic-containing smoke dust dearsenification and containing comprehensively recovering valuable metal, the present invention proposes a kind of arsenic-containing material
Integrated conduct method, suitable for nonferrous metallurgical process generate flue dust processing.Arsenic-containing smoke dust dearsenification may be implemented and have
Valence element comprehensive reutilization.The present invention has the advantages that environmental protection, economic, energy conservation, resource utilization are high, realizes the harmless of arsenic
Change.
The scheme of the invention is the Leaching way soaked by normal pressure alkali, solvable arsenic in flue dust is removed, and with catalysis oxidation
Trivalent arsenic is oxidized to pentavalent arsenic by mode, and oxidated solution consolidates arsenic mineral through being distributed crystallisation synthesizing high-stability, and leached mud is through flowing
The processes such as state washing, reduction melting, oxidation blowing, recycle each valuable element.The method is by arsenic from flue dust
It removes and solidifies, and antimony, lead, bismuth etc. are stayed in as far as possible in dearsenification slag, the separation of realization arsenic and valuable metal is simultaneously innoxious.This hair
Bright comprehensive resource utilization rate is high, and raw material wide adaptation range solves pollution problem in traditional handicraft extraction process, especially lead zinc
The cigarette ash that smelting process generates, advantage of the invention are more obvious.
A kind of integrated conduct method of arsenic-containing material of the present invention, comprising the following steps:
(1) normal pressure alkali soaks
Extraction temperature is room temperature~100 DEG C, the time is 30~240min, liquid solid product mass ratio be 3:1~20:1
(ml:g), under conditions of NaOH concentration is 0.1mol/L~6mol/L, mixing speed is 50~1000r/min to arsenic-containing smoke dust into
Row normal pressure alkali leaching processing；Filter to obtain leachate and leached mud；Liquid solid product mass ratio refers in terms of ml/g, NaOH solution with
The volume mass ratio of arsenic-containing smoke dust；The valuable element includes antimony, lead, bismuth；
(2) leachate catalysis oxidation
By way of catalysis oxidation, oxidizing gas and catalyst are added into leachate obtained by step (1), will leach
Most As in liquid3+It is transformed into As5+；Oxidated solution enters solid arsenic process；
(3) leachate consolidates arsenic
The initial pH value of leachate after oxidation obtained by step (2) is adjusted to 1.5~3, iron salt solutions are added thereto, make
The molar ratio of Fe and As is 1~8:1 in the leachate, carries out solid arsenic reaction, while neutralizer regulation reaction is added in pH value
It is carried out under the conditions of 1.5~3, makes Fe3+With AsO4 3-Reaction generates the solid arsenic mineral of high stability；Control reaction condition: temperature is room
Temperature~120 DEG C, reaction time are 1~10h, 50~500r/min of mixing speed；The iron salt solutions are ferrum sulfuricum oxydatum solutum, chlorination
At least one of ferrous solution or iron nitrate solution, the neutralizer be sodium carbonate, sodium bicarbonate or sodium hydroxide at least
It is a kind of；
(4) leached mud washs
Leached mud obtained by step (1) is used into fluidization wash, the solvable arsenic in leached mud is made to be down to 0.1% or less；
Washing lotion, which can be returned, leaches i.e. return step (1) for the feed liquid used with alkaline leaching；
(5) washery slag recycles valuable metal
Will washery slag obtained by step (4) it is dry after be incorporated charcoal, coal and appropriate soda ash, in reactor in 900~1200 DEG C,
Have and carry out reduction melting under C, CO conditioning, melting generates bubble slag, lead-antimony alloy and flue dust；
The flue dust is returned into reduction melting or normal pressure alkali soaks step；
Lead is sent to smelt the bubble slag；
The lead-antimony alloy is subjected to oxidation blowing, air (temperature preferably 650~800 is passed through under conditions of muffle
DEG C), obtain antimony vapour, blowing slag and lead bullion；The antimony vapour is aoxidized and generates antimony oxide, as stibium trioxide product；By institute
It states blowing slag and returns to reduction melting process；Lead is sent to refine the lead bullion.
Antimony liquid temperature in the necessary temperature of reactor and furnace is maintained using the big calorimetric that antimony oxidation generates；Due to melt body surface
The concentration of metallic antimony has comparative advantage, and metallic antimony property is more active than lead, bismuth, so that the antimony in aluminium alloy is oxidized to antimony oxide and waves
Hair enters flue dust, and lead, bismuth then stay in the lead of reactor bottom, realizes that a furnace is dual-purpose.
Arsenic-containing smoke dust (arsenic-containing material) of the present invention includes following main component by percentage to the quality:
Arsenic: 1%~60%, antimony: 1%~55%, lead: 0.1%~35%, zinc: 0.1%~30%, copper: 0.1%~
5%, tellurium: 0.01%~3%, selenium: 0.01%~3%.
The integrated conduct method of the above-mentioned arsenic-containing material of the present invention, wherein
Leaching described in step (1) is that normal pressure alkali soaks, and control NaOH concentration is 0.1mol/L~6mol/L, extraction temperature is
Room temperature~100 DEG C, time are 30~240min, liquid solid product mass ratio is 3:1~20:1 (ml:g), mixing speed be 50~
1000r/min。
In the process of catalysis oxidation described in step (2), the oxidizing gas is oxygen, air or oxygen-enriched air；It is excellent
The gas flow of selection of land, above-mentioned oxidizing gas is controlled in 1~20L/min.
In the process of catalysis oxidation described in step (2), the catalyst is KMnO4；Preferably, in reaction system As with
Mn molar ratio is controlled in 5:1~50:1.
In the process of catalysis oxidation described in step (2), the reaction temperature of catalytic oxidation system control is 30 DEG C~120
℃。
Oxidated solution described in step (3) consolidates arsenic and consolidates arsenic mineral using fractional crystallization regular way synthesizing high-stability.
It is the initial pH of oxidated solution that the condition of arsenic mineral is consolidated in distribution crystallisation synthesizing high-stability described in step (3)
Value is adjusted to 1.5~3, and iron salt solutions and neutralizer is added, makes Fe3+With AsO4 3-Reaction generates the solid arsenic mineral of high stability；It is described
The molar ratio of Fe and As is 1~8:1 in leachate, and reaction temperature is room temperature~120 DEG C, and the reaction time is 1~10h, stirring speed
50~500r/min is spent, the iron salt solutions are at least one of ferrum sulfuricum oxydatum solutum, ferric chloride solution or iron nitrate solution, institute
Stating neutralizer is at least one of sodium carbonate, sodium bicarbonate or sodium hydroxide.
Preferably, the addition speed control of the iron salt solutions and neutralizer is in 3ml/min~20ml/min.
The washing of leached mud described in step (4) is washed using fluidization wash tower.
Reduction melting described in step (5), oxidation blowing reactor used is blast furnace, reverberatory furnace, bottom convertor, side-blown
Furnace or top blast furnace, preferably reverberatory furnace or bottom convertor.
The advantages of the method for the present invention and good effect:
1, the present invention the solvable arsenic in arsenic flue dust is totally removed, the raw material arsenic after dearsenification by the way of the leaching of normal pressure alkali
Content is low, can the valuable metals such as synthetical recovery antimony, lead, bismuth, reduce the content of arsenic in product；
2, the present invention is by the way of catalysis oxidation, by As3+It is oxidized to As5+, solve the dysoxidizable problem of trivalent arsenic；
3, the present invention changes the pH value of feed way, accurate control synthesis process on the basis of original technology, using point
The solid arsenic mineral of cloth crystallisation synthesis stablizes stockpiling under the conditions of wide pH range 2~11 and strong reducing property, migrates As no longer,
Also so that the As of smelting system is had an ideal open circuit, be that a kind of process flow is simple, resource-effective, environmental-friendly
Method, and solid arsenic mineral that crystallisation prepares is distributed because its crystallinity is high, BET specific surface area is small, stable region field width, and
Has high stability, to be easy to store up；
4, the present invention uses fluidization wash, further decreases the content of arsenic in leached mud, recycling product quality can be improved；
5, the present invention recycles valuable metal using reduction melting, realizes that metal comprehensive reutilization maximizes.
In short, the reasonable process of the present invention is arranged in pairs or groups, by the conditional parameter in each process of strict control, arsenic is enable to pacify
Full disposition, antimony, lead, bismuth etc. are recycled and are efficiently used, and have achieved the purpose that environmental protection, economic, energy conservation, high resource utilization,
Realize the innoxious and maximum resource utilization of arsenic.Since the separation of arsenic and other elements avoids fire using wet processing
The not high problem of massive pollution and the utilization of resources brought by method, entire technique substantially three-waste free discharge, all resources
Obtain maximal efficiency utilization, products therefrom is convenient for subsequent processing and processing, so the present invention have environmental protection, economic, energy conservation,
The advantage of high resource utilization.
Detailed description of the invention
Fig. 1 is the method for the present invention flow diagram.
Specific embodiment
Technical solution of the present invention is described in detail below, wherein the percentage composition is mass fraction.
The arsenic-containing smoke dust (arsenic-containing material) being related to below includes following main component: arsenic quality percentage by percentage to the quality
Content 1%~60%, antimony mass percentage 1%~55%, lead mass percentage 0.1%~35%, zinc quality percentage contain
Amount 0.1%~30%, copper mass percentage composition 0.1~5%, tellurium mass percentage 0.01%~3%, selenium mass percentage
0.01%~3%.
As shown in Figure 1, a kind of integrated conduct method of arsenic-containing material, comprising the following steps:
1, normal pressure alkali soak process, control NaOH concentration be 0.1mol/L~6mol/L, extraction temperature be room temperature~100 DEG C,
Time is 30~240min, liquid solid product mass ratio is 3:1~20:1 (ml:g), mixing speed is 50~1000r/min.It is described
Liquid solid accumulates mass ratio and refers in terms of ml/g, the volume mass ratio of NaOH solution and arsenic-containing smoke dust.
2, oxidizing gas and catalyst is added by way of catalysis oxidation in catalysis oxidation process, will be exhausted in leachate
Most As3+It is transformed into As5+, oxidated solution enters solid arsenic process.Oxidizing gas be oxygen, air or oxygen-enriched air,
Catalyst is KMnO4.In 1~20L/min, As/Mn molar ratio is controlled in 5:1~50 for the gas flow control of oxidizing gas:
1, the temperature of catalytic oxidation system control is controlled at 30 DEG C~120 DEG C.
3, oxidated solution consolidates arsenic process, and the condition of control is that the initial pH value of oxidated solution is adjusted to 1.5~3, and molysite is added
Solution, while neutralizer is added makes Fe3+With AsO4 3-Reaction generates the solid arsenic mineral of high stability, and Fe/As molar ratio is 1~8,
Reaction temperature is room temperature~120 DEG C, and the reaction time is 1~10h, and 50~500r/min of mixing speed, the iron salt solutions are sulphur
At least one of sour ferrous solution, ferric chloride solution or iron nitrate solution, the neutralizer are sodium carbonate, sodium bicarbonate or hydrogen-oxygen
Change at least one of sodium, the addition speed control of the iron salt solutions and neutralizer is in 3ml/min~20ml/min.
4, leached mud washing procedure is washed leached mud 2~3 times using fluidization wash tower at room temperature, is made solvable in washery slag
The content < 0.1% of arsenic；Washing lotion, which can be returned, leaches i.e. return step (1) for the feed liquid used with alkaline leaching；
5, washery slag synthetical recovery process is incorporated charcoal, coal and a small amount of soda ash (Na after washery slag is dry2CO3), 900~1200
DEG C and have under the conditionings such as C, CO, the oxide of the valuable metals such as Sb, Pb, Bi is equally also reduced into simple substance form and enters lead
In antimony alloy.Pit ash and a small amount of arsenic, antimony, lead oxide light " the bubble slag " of more alveolar substances generated is reacted with soda ash,
Float on antimony liquid surface.After the completion of reduction, bubble slag is clawed, under conditions of aoxidizing 650 DEG C of blowing temperature~800 DEG C of muffle, to antimony
Primary air is blasted in liquid, so that antimony volatilization is generated a large amount of antimony vapours, while being passed through auxiliary air to reactor, is aoxidized antimony vapour
Antimony oxide is generated, maintains antimony liquid temperature in the necessary temperature of reactor and furnace using the big calorimetric that antimony oxidation generates.Due to
The concentration of melt body surface metal antimony has comparative advantage, and metallic antimony property is more active than lead, bismuth, and the antimony in aluminium alloy is made to be oxidized to three oxygen
Change two antimony and be volatized into flue dust, lead, bismuth then stay in the lead of reactor bottom, realize that a furnace is dual-purpose.The wherein reduction melting, oxidation
Blowing reactor used can be blast furnace, reverberatory furnace, bottom convertor, side-blown converter or top blast furnace, preferably reverberatory furnace or bottom convertor.
It is the embodiment of the present invention below.
Embodiment 1
It by percentage to the quality include following main component: Pb so that certain domestic Lead And Zinc Smelter is containing arsenic smoke dust as an example
5.26%, As 39.65%, Sn 0.5%, Sb 29.36%, Zn 0.12%, Se 0.04%.
The high-arsenic antimony flue dust of certain mass is weighed in reaction kettle, by liquid solid product mass ratio 10:1 (ml:g), is stirred
Speed 700r/min, NaOH concentration 1mol/L, 80 DEG C of extraction temperature, extraction time 2h condition carry out leaching experiment.Leach knot
Shu Hou removes slurry filtration separation；Arsenic leaching rate 72.36%. is measured, each element concentration in leachate: Pb 86.00ppm, Se
1.80ppm, Zn 20ppm, Sb 1.36g/L, As 28.69g/L.
Use the method for catalysis oxidation by As gained leachate3+It is oxidized to As5+, the condition of control is that oxygen flow is
In 10:1, catalytic oxidation system temperature is controlled at 90 DEG C for the molar ratio control of 5L/min, As and Mn, the results showed that, As3+Conversion
Rate is 98.45%.
Oxidated solution consolidates arsenic and consolidates arsenic mineral using the method synthesizing high-stability of distribution crystallisation, and control condition is will be initial
PH value is adjusted to 1.5, and iron nitrate solution and sodium carbonate is added, and Fe/As molar ratio is 2.5, and reaction temperature is 85 DEG C, and the reaction time is
4h, mixing speed 200r/min, the addition speed of iron nitrate solution are 8ml/min, and the addition speed of sodium carbonate is 8ml/min.
The solid arsenic mineral of synthesis meets GB5085.3-2007 (solid waste judging standard-leaching characteristic identification) regulation, can safe heap
It deposits.
Leached mud is washed leached mud 2 times according to liquid solid product mass ratio 5:1 (ml:g) using fluidization wash tower, and washery slag contains
Solvable arsenic 0.1%.
It is incorporated charcoal, coal and soda ash after washery slag is dry, reduction melting is carried out in 1200 DEG C of reverberatory furnaces, melting generates bubble
Slag, lead-antimony alloy and flue dust.Bubble slag send lead to smelt, and flue dust returns to reduction melting or the leaching of normal pressure alkali, lead-antimony alloy enter oxidation and blow
Refine process.Under the conditions of aoxidizing 700 DEG C of blowing temperature of muffle, primary air is blasted into lead-antimony alloy, while to reactor
It is passed through auxiliary air, antimony vapour oxidation is made to generate antimony oxide.
The antimony oxide of generation is as stibium trioxide product.The slag that blows returns former smelting system, and aoxidizes the lead bullion after blowing
Send lead rectification systems.Wherein Pb contains 70.46%, As containing 24.38%, Sb and contains 3.08% in lead-antimony alloy；The stibium trioxide powder of generation accords with
Closing the trade mark specified in GB/T 4062-2013 is Sb2O399.00 stibium trioxide powder；Contain Pb97.21% in lead bullion, contains
Sb1.08% contains As 0.37%.
Embodiment 2
It by percentage to the quality include following main component: Pb so that certain domestic Lead And Zinc Smelter is containing arsenic smoke dust as an example
10.39%, As 34.59%, Sn 1.45%, Sb 20.54%, Zn 0.11%, Se 0.24%.
The high-arsenic antimony flue dust of certain mass is weighed in reaction kettle, by liquid solid product mass ratio 10:1 (ml:g), is stirred
Speed 700r/min, NaOH concentration 3mol/L, 50 DEG C of extraction temperature, extraction time 4h condition carry out leaching experiment.Leach knot
Shu Hou removes slurry filtration separation；Arsenic leaching rate 52.06%. is measured, each element concentration Pb 87ppm, Se in leachate
0.52ppm, Zn 71ppm, Sb 1.24g/L, As 18.01g/L.
Leachate uses the method for catalysis oxidation by As3+It is oxidized to As5+, the condition of control is oxygen flow 10L/
In 40:1, catalytic oxidation system temperature is controlled at 30 DEG C for the molar ratio control of min, As and Mn, the results showed that, As3+Conversion ratio
It is 92.31%.
Oxidated solution consolidates arsenic and consolidates arsenic mineral using the method synthesizing high-stability of distribution crystallisation, and control condition is will be initial
PH value is adjusted to 2, and iron nitrate solution and sodium carbonate is added, and Fe/As molar ratio is 6, and reaction temperature is 120 DEG C, reaction time 4h,
Mixing speed 350r/min, the addition speed of iron nitrate solution are 5ml/min, and the addition speed of sodium carbonate is 5ml/min.Synthesis
Solid arsenic mineral meet GB5085.3-2007 (solid waste judging standard-leaching characteristic identification) regulation, can store up safely.
Leached mud is washed leached mud 2 times according to liquid solid product mass ratio 5:1 (ml:g) using fluidization wash tower, and washery slag contains
Solvable arsenic 0.1%.
It is incorporated charcoal, coal and soda ash after washery slag is dry, reduction melting is carried out in 1150 DEG C of reverberatory furnaces, melting generates bubble
Slag, lead-antimony alloy and flue dust.Bubble slag send lead to smelt, and flue dust returns to reduction melting or the leaching of normal pressure alkali, lead-antimony alloy enter oxidation and blow
Refine process.Under the conditions of aoxidizing 800 DEG C of blowing temperature of muffle, primary air is blasted into alloy, while being passed through to reactor
Auxiliary air makes antimony vapour oxidation generate antimony oxide.
The antimony oxide of generation is as stibium trioxide product.The slag that blows returns former smelting system, and aoxidizes the lead bullion after blowing
Send lead rectification systems.Wherein Pb contains 63.89%, As containing 29.36%, Sb and contains 4.67% in lead-antimony alloy；The stibium trioxide powder of generation accords with
Closing the trade mark specified in GB/T 4062-2013 is Sb2O399.00 stibium trioxide powder；Contain Pb96.14% in lead bullion, contains
Sb2.61% contains As 0.46%.
Embodiment 3
It by percentage to the quality include following main component: Pb so that certain domestic Lead And Zinc Smelter is containing arsenic smoke dust as an example
19.57%, As 24.26%, Sn 1.47%, Sb 30.45%, Zn 0.16%, Se 0.21%.
The high-arsenic antimony flue dust of certain mass is weighed in reaction kettle, by liquid solid product mass ratio 5:1 (ml:g), stirs speed
Spend the condition progress leaching experiment of 1000r/min, NaOH concentration 1mol/L, 30 DEG C of extraction temperature, extraction time 2h.Leaching terminates
Afterwards, slurry filtration separation is removed；Arsenic leaching rate 42.26%. is measured, each element concentration Pb 124ppm in leachate,
Se0.67ppm, Zn 107ppm, Sb 2.02g/L, As 10.25g/L.
Use the method for catalysis oxidation by As gained leachate3+It is oxidized to As5+, the condition of control is that oxygen flow is
In 20:1, catalytic oxidation system temperature is controlled at 120 DEG C for the molar ratio control of 1L/min, As and Mn, the results showed that, As3+Turn
Rate is 89.36%.
Oxidated solution consolidates arsenic and consolidates arsenic mineral using the method synthesizing high-stability of distribution crystallisation, and control condition is will be initial
PH value is adjusted to 2, and iron nitrate solution and sodium carbonate is added, and Fe/As molar ratio is 8, and reaction temperature is 120 DEG C, reaction time 4h,
Mixing speed 200r/min, the addition speed of iron nitrate solution are 10ml/min, and the addition speed of sodium carbonate is 10ml/min.It closes
At solid arsenic mineral meet GB5085.3-2007 (solid waste judging standard-leaching characteristic identification) regulation, can store up safely.
Leached mud is washed leached mud 2 times according to liquid solid product mass ratio 5:1 (ml:g) using fluidization wash tower, and washery slag contains
Solvable arsenic 0.1%.
It is incorporated charcoal, coal and soda ash after washery slag is dry, reduction melting is carried out in 1200 DEG C of reverberatory furnaces, melting generates bubble
Slag, lead-antimony alloy and flue dust.Bubble slag send lead to smelt, and flue dust returns to reduction melting or the leaching of normal pressure alkali, lead-antimony alloy enter oxidation and blow
Refine process.Under the conditions of aoxidizing 650 DEG C of blowing temperature of muffle, primary air is blasted into alloy, while being passed through to reactor
Auxiliary air makes antimony vapour oxidation generate antimony oxide.
The antimony oxide of generation is as stibium trioxide product.The slag that blows returns former smelting system, and aoxidizes the lead bullion after blowing
Send lead rectification systems.Wherein Pb contains 66.96%, As containing 27.89%, Sb and contains 4.21% in lead-antimony alloy；The stibium trioxide powder of generation accords with
Closing the trade mark specified in GB/T 4062-2013 is Sb2O399.00 stibium trioxide powder；Contain Pb96.69% in lead bullion, contains
Sb2.12% contains As 0.49%.
Although above the present invention is described in detail with a general description of the specific embodiments,
On the basis of the present invention, it can be made some modifications or improvements, this will be apparent to those skilled in the art.Cause
This, these modifications or improvements, fall within the scope of the claimed invention without departing from theon the basis of the spirit of the present invention.
Claims (8)
1. a kind of integrated conduct method of arsenic-containing material, which comprises the following steps:
(1) normal pressure alkali soaks
Extraction temperature is room temperature~100 DEG C, the time is 30~240min, liquid solid product mass ratio be 3:1~20:1, NaOH it is dense
Arsenic-containing smoke dust is carried out at the leaching of normal pressure alkali under conditions of degree is 0.1mol/L~6mol/L, mixing speed is 50~1000r/min
Reason；Filter to obtain leachate and leached mud；The liquid solid accumulates mass ratio and refers in terms of mL/g, the body of NaOH solution and arsenic-containing smoke dust
Product mass ratio；Valuable element includes antimony, lead, bismuth；
The arsenic-containing smoke dust includes following main component: arsenic by percentage to the quality: 1%~60%, antimony: and 1%~55%, lead:
0.1%~35%, zinc: 0.1%~30%, copper: 0.1%~5%, tellurium: 0.01%~3%, selenium: 0.01%~3%；
(2) leachate catalysis oxidation
By way of catalysis oxidation, oxidizing gas and catalyst are added into leachate obtained by step (1), it will be in leachate
The As of the overwhelming majority3+It is transformed into As5+；Oxidated solution enters solid arsenic process；
(3) leachate consolidates arsenic
The initial pH value of leachate after oxidation obtained by step (2) is adjusted to 1.5~3, iron salt solutions are added thereto, is made described
The molar ratio of Fe and As is 1~8:1 in leachate, carries out solid arsenic reaction, at the same be added neutralizer regulation reaction pH value 1.5~
It is carried out under the conditions of 3, makes Fe3+With AsO4 3-Reaction generates the solid arsenic mineral of high stability；Control reaction condition: temperature be room temperature~
120 DEG C, the reaction time is 1~10h, 50~500r/min of mixing speed；The iron salt solutions are ferrum sulfuricum oxydatum solutum, iron chloride is molten
At least one of liquid or iron nitrate solution, the neutralizer are at least one of sodium carbonate, sodium bicarbonate or sodium hydroxide；
(4) leached mud washs
Leached mud obtained by step (1) is used into fluidization wash, the solvable arsenic in leached mud is made to be down to 0.1% or less；
(5) washery slag recycles valuable metal
Will washery slag obtained by step (4) it is dry after be incorporated charcoal, coal and appropriate soda ash, in reactor in 900~1200 DEG C, have C,
Reduction melting is carried out under CO conditioning, melting generates bubble slag, lead-antimony alloy and flue dust；By the flue dust return reduction melting or
Normal pressure alkali soaks step；Lead is sent to smelt the bubble slag；
The lead-antimony alloy is subjected to oxidation blowing, is passed through air under conditions of muffle, obtains antimony vapour, blowing slag and thick
Lead；The antimony vapour is aoxidized and generates antimony oxide；The blowing slag is returned into reduction melting process；Send the lead bullion to lead
Refining.
2. the integrated conduct method of arsenic-containing material according to claim 1, which is characterized in that aoxidized described in step (2)
Property gas be oxygen, air or oxygen-enriched air.
3. the integrated conduct method of arsenic-containing material according to claim 2, which is characterized in that aoxidized described in step (2)
Property gas gas flow control in 1~20L/min.
4. the integrated conduct method of arsenic-containing material according to claim 1-3, which is characterized in that in step (2)
The catalyst is KMnO4。
5. the integrated conduct method of arsenic-containing material according to claim 4, which is characterized in that As and Mn in step (2)
Molar ratio is controlled in 5:1~50:1.
6. the integrated conduct method of arsenic-containing material according to claim 1-3, which is characterized in that in step (2)
The temperature of the catalytic oxidation system control is 30 DEG C~120 DEG C.
7. the integrated conduct method of arsenic-containing material according to claim 1-3, which is characterized in that in step (4)
The leached mud washing is washed using fluidization wash tower.
8. the integrated conduct method of arsenic-containing material according to claim 1-3, which is characterized in that in step (5)
The reduction melting, reactor used oxidation blowing are blast furnace, reverberatory furnace, bottom convertor, side-blown converter or top blast furnace.
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