CN106834712B - A kind of method that arsenic-containing smoke dust dearsenification and distribution crystallisation synthesize solid arsenic mineral - Google Patents
A kind of method that arsenic-containing smoke dust dearsenification and distribution crystallisation synthesize solid arsenic mineral Download PDFInfo
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- CN106834712B CN106834712B CN201611191987.5A CN201611191987A CN106834712B CN 106834712 B CN106834712 B CN 106834712B CN 201611191987 A CN201611191987 A CN 201611191987A CN 106834712 B CN106834712 B CN 106834712B
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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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- 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
- C22B13/00—Obtaining lead
- C22B13/04—Obtaining lead by wet processes
- C22B13/045—Recovery from waste materials
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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
- C22B30/00—Obtaining antimony, arsenic or bismuth
- C22B30/02—Obtaining antimony
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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
- C22B30/04—Obtaining arsenic
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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
- 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
- C22B7/006—Wet processes
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Abstract
The invention belongs to metallurgical technology fields, more particularly to a kind of method that arsenic-containing smoke dust dearsenification and distribution crystallisation synthesize solid arsenic mineral, this method successively includes the water logging of oxygen pressure, leachate consolidates arsenic, leached mud washs and washery slag recycling four steps of valuable metal, this method presses water logging by oxygen, remove solvable arsenic in flue dust, leachate synthesizes stable solid arsenic mineral through Steppecd crystallization, then solidifies 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 synthesize stable solid arsenic mineral, and make antimony, lead, bismuth etc. by the method to be stayed in as far as possible in leached mud, realizes that the separation of arsenic and valuable metal is simultaneously innoxious.Comprehensive resource utilization rate of the present invention is high, raw material wide adaptation range, solves the flue dust that pollution problem in traditional handicraft extraction process, especially Lead-Zinc Sintering Process generate, 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 arsenic-containing smoke dust dearsenification and distribution crystallisation synthesize solid arsenic minerals
The method of object.
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 forms exist, be enriched in copper, lead, zinc, nickel, cobalt, gold and silver etc.
In nonferrous metallic ores；In Nonferrous Metallurgical Process, many high arsenic solid materials of output, such as roasting and melting flue dust.These objects
Material is up to 5~50% containing arsenic, meanwhile, a large amount of valuable metal is also contained in material, if directly returning to smelting process, will lead to
The circulative accumulation of arsenic in systems.Therefore, dearsenification usually should individually be handled.Arsenic belongs to severe toxicity, carcinogenic elements, and application is gradually withered
How contracting, in face of increasingly stringent environmental protection standard, handle various high-arsenic materials, it has also become threatens the weight of nonferrous metallurgy industry existence
Big problem.
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.Chinese patent
CN103602835A discloses a kind of method that displacement reduction method obtains crude arsenic and needle antimony, and Chinese patent CN103602834A is announced
The method that a kind of selective oxidation-reduction obtains the not high As2O3 and needle antimony of purity, Chinese patent CN104294053A are announced
A kind of method of arsenic-containing smoke dust reduction volatilization arsenic obtains arsenic trioxide purity and reaches 97.0% or more.But if flue dust
In contain the metal (such as antimony) close with arsenic element property, then the arsenic trioxide purity obtained is high.It is main in wet production
There are water logging, acidleach, alkali to soak three kinds of techniques, but can only obtain the products such as the not high arsenic trioxide of purity, natrium arsenicum, and right
The recycling of valuable metal powder does not make further research.Chinese patent CN105567983A discloses a kind of Copper making flue dust water logging-alkali
The treatment process of leaching, separates arsenic with metal, but being not thorough of separating with other elements of arsenic, still higher containing arsenic in leached mud.
Chinese patent CN104357668A discloses a kind of method for leaching flue dust with waste acid, electrodeposition dearsenification, and acidleach and electrolytic deposition process hold
It is also easy to produce arsenic hydride.Chinese patent CN105648226A and CN105648227A disclose a kind of oxygen pressure alkali leaching realization arsenic antimony separation
Method, more thoroughly, but the natrium arsenicum obtained in process, without market, the valuable metals such as tellurium, antimony do not return the ratio of arsenic antimony separation
It receives.
In conclusion dearsenification, the research paper for extracting valuable metal and related patents report are many but existing from flue dust
For technology there are still valuable metal comprehensive recovery is low, arsenic product market is limited, there are problems that potential security risk.Cause
This, 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 from cigarette containing arsenic
The method of valuable metal and arsenic harmlessness disposing is recycled in dirt.The present invention has environmental protection, economic, energy conservation, resource utilization high
Advantage realizes the harmless treatment of arsenic, specifically adopts the following technical scheme that
A kind of method that arsenic-containing smoke dust dearsenification and distribution crystallisation synthesize solid arsenic mineral, includes the following steps:
(1) oxygen presses water logging: taking arsenic-containing smoke dust in reaction kettle, water is added thereto, oxidisability gas is passed through into reaction kettle
Body, carries out oxygen leaching under 120~300 DEG C, 0.1~3.5Mpa, after oxygen leaching, through solid-liquor separation, obtains containing arsenic
Leachate and leached mud；
(2) leachate consolidates arsenic: carrying out solid arsenic using distribution crystallisation, the pH value of leachate obtained by regulating step (1) to 1.5
~3, iron salt solutions are added into leachate, while neutralizer regulation reaction is added and carries out under the conditions of pH value 1.5~3, make Fe3+
With AsO4 3-Reaction generates the solid arsenic mineral of high stability；
(3) leached mud washs: washing to step (1) resulting leached mud, obtains washing lotion and washery slag, controls in washery slag
Arsenic content is less than 0.1%, wherein the washing lotion return step (1) carries out oxygen and presses water logging；
(4) washery slag recycles valuable metal: after the washery slag that step (3) obtains is dry, mixing and is gone back with charcoal, coal and soda ash
Former melting generates flue dust, bubble slag and lead-antimony alloy；
The flue dust is returned into the reduction melting or normal pressure water logging；
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, obtain antimony vapour, blowing slag and
Lead bullion；The antimony vapour is aoxidized and generates antimony oxide, as stibium trioxide product；The blowing slag is returned into reduction melting process
Ingredient；Lead is sent to refine the lead bullion.
The particularly suitable following arsenic-containing smoke dust of processing of method of the invention, by percentage to the quality, the arsenic-containing smoke dust includes
Following main component: 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%.
Preferably, in step (1), extraction temperature is 150~260 DEG C.
Preferably, in step (1), leaching pressure is 1.5~2MPa.
Preferably, the water logging of the pressure of oxygen described in step (1) carries out under stiring, the speed of the stirring be 50r/min~
500r/min。
Preferably, in step (1), the liquid-solid ratio of water and arsenic-containing smoke dust is 3:1~20:1 (ml:g).
Preferably, in step (1), extraction time is 30~240min, and optimal is 120~200min.
Preferably, oxidizing gas of the present invention is selected from least one of oxygen, air, oxygen-enriched air.
As the preferable technical solution of the present invention, the operation of step (1) specifically: take arsenic-containing smoke dust in reaction kettle, press
It is 3:1~20:1 (ml:g) meter according to the liquid solid of water and arsenic-containing smoke dust product mass ratio, water is added thereto, is passed through into reaction kettle
Oxidizing gas carries out oxygen leaching, when control is leached under 150~260 DEG C, 1.5~2Mpa, 50r/min~500r/min
Between be 120~200min.Such condition can realize the abundant leaching of arsenic, and realization arsenic is sufficiently separated with other metals.
Wherein, step (2) carries out solid arsenic using distribution crystallisation.Substance commonly used in the art can be used in the iron salt solutions,
Present invention preferably employs at least one of ferrum sulfuricum oxydatum solutum, iron nitrate solution, ferric chloride solution, the neutralizer is preferably used
At least one of sodium carbonate, sodium bicarbonate, sodium hydroxide.
Preferably, the addition speed control of iron salt solutions is in 3ml/min~15ml/min, the addition speed control of neutralizer
In 3ml/min~15ml/min.
Preferably, the molar ratio of As is 1~5 in Fe and washing lotion in molysite.
Preferably, distribution crystallisation carries out under the conditions of room temperature is to 120 DEG C, most preferably carries out at 80~120 DEG C, such
Under the conditions of, Gu arsenic is more complete.
It is distributed in crystallization process, 50~500r/min of mixing speed.
Preferably, in step (3), leached mud washing uses fluidization wash tower, generally wash 2~3 this can make
The content of arsenic is less than 0.1% in gained washery slag.
In step (4), antimonial is reduced to metallic antimony in reactor, and the impurity such as Pb, Bi, Sn are also reduced into list
Matter enters in needle antimony alloy, pit ash and a small amount of arsenic, antimony, lead oxide that generated more alveolar substances are reacted with soda ash is light
" bubble slag ", floats on antimony liquid surface.After the completion of reduction, bubble slag is clawed, under conditions of muffle, blasts primary air into antimony liquid,
So that antimony volatilization is generated a large amount of antimony vapours, while being passed through auxiliary air to reactor, antimony vapour oxidation is made to generate antimony oxide, benefit
Antimony liquid temperature in the necessary temperature of reactor and furnace is maintained with the big calorimetric that antimony oxidation generates.It is dense due to melt body surface metal antimony
Degree has comparative advantage, and metallic antimony property is more active than lead, bismuth, tin, make the antimony in aluminium alloy be oxidized to antimony oxide volatilize into
Enter flue dust, lead, bismuth, tin etc. then stays in the lead of reactor bottom, realizes that a furnace is dual-purpose.
Preferably, in step (4), the temperature of the reduction melting is 900~1200 DEG C.
Preferably, in step (4), the temperature of the oxidation blowing is 650~800 DEG C.
Preferably, in step (4), the reduction melting and oxidation blowing are using blast furnace, reverberatory furnace, bottom convertor, side-blown
Any one in furnace, top blast furnace.
The scheme of the invention is pressing water logging by oxygen, solvable arsenic in flue dust is removed, and trivalent arsenic is oxidized to pentavalent arsenic, soaked
Liquid consolidates arsenic mineral through distribution crystallisation synthesizing high-stability out, and leached mud is through works such as fluidization wash, reduction melting, oxidation blowing
Sequence recycles each valuable element.Arsenic is removed and is solidified from flue dust by the method, and antimony, lead, bismuth, tin etc. to the greatest extent may be used
It can stay in dearsenification slag, the separation of realization arsenic and valuable metal is simultaneously innoxious.Comprehensive resource utilization rate of the present invention is high, and raw material adapts to
Range is wide, solves the flue dust that pollution problem in traditional handicraft extraction process, especially Lead-Zinc Sintering Process generate, this method
Advantage is more obvious.
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 in such a way that oxygen presses water logging
Content is low, can the valuable metals such as synthetical recovery antimony, lead, reduce the content of arsenic in product；
2, the present invention presses water logging using oxygen, 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 the solid arsenic mineral prepared using distribution crystallisation is because its crystallinity is high, BET specific surface area is small, stability region
Width, and have 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.
6, the reasonable process collocation of the present invention enables arsenic safe disposal, and antimony, lead, bismuth etc. are recycled and efficiently used,
Achieve the purpose that environmental protection, economic, energy conservation, high resource utilization, realizes the innoxious and maximum resource utilization of arsenic.Due to arsenic
It is not high that separation with other elements using wet processing avoids massive pollution and the utilization of resources brought by pyrogenic process
The problem of, entire technique substantially three-waste free discharge, all resources obtain maximal efficiency utilization, and products therefrom is convenient for subsequent
Processing and processing, so the present invention has the advantage of environmentally friendly, economic, energy conservation, high resource utilization.
Detailed description of the invention
Fig. 1 is process flow chart of the invention.
Specific embodiment
Technical solution of the present invention is described in detail below, the process flow of embodiment please refers to Fig. 1.The wherein percentage
Content is mass number.
Embodiment 1:
By taking certain domestic Lead And Zinc Smelter is containing arsenic smoke dust as an example, raw material main component is Pb 1.57%, As 48.56%, Sn
0.51%, Sb 21.24%, Zn 0.73%, Te 0.35%, Se 0.25%.It is handled using following steps:
(1) oxygen presses water logging: weighing the high-arsenic antimony flue dust of certain mass in reaction kettle, control condition is that liquid consolidates volume mass
Than 10:1, mixing speed 300r/min, 160 DEG C of extraction temperature, partial pressure of oxygen 2Mpa, extraction time 2h, after leaching, material is removed
Slurry is separated by filtration, and obtains arsenic leaching solution and leached mud；
Through detecting: arsenic leaching rate 61.53%, each element concentration Pb 709.60ppm, Se 31.02ppm, Sb in leachate
1.26g/L, Te 123.28ppm, As 29.88g/L.
(2) leachate consolidates arsenic: the resulting leachate of step (1) consolidates arsenic mineral using distribution crystallisation synthesizing high-stability,
The condition of control are as follows: the initial pH value for adjusting leachate is 1.5, is 2.5 addition iron nitrate solutions according to Fe/As molar ratio, together
When be added sodium carbonate regulation reaction carried out under the conditions of pH value 3, make Fe3+With AsO4 3-Reaction generates the solid arsenic mineral of high stability,
The addition speed of iron nitrate solution is 5ml/min, and the addition speed of sodium carbonate is 5ml/min；
Through detecting, the solid arsenic mineral of synthesis meets GB5085.3-2007 (solid waste judging standard-leaching characteristic identification)
Regulation, can store up safely.
(3) leached mud washs: step (1) resulting leached mud is according to liquid-solid ratio 5:1 using the washing leaching of fluidization wash tower
It slags tap 2 times, obtains washery slag and washing lotion；
Through detecting: washing lotion 9.62g/L containing arsenic, washery slag contain solvable arsenic 0.1%.
(4) washery slag recycles valuable metal: being incorporated charcoal, coal and soda ash after the washery slag of step (3) is dry, reflects at 1150 DEG C
Reduction melting is carried out in furnace, melting generates bubble slag, lead-antimony alloy and flue dust.Bubble slag send lead to smelt, flue dust return reduction melting or
Oxygen presses water logging, and lead-antimony alloy enters oxidation blowing process.Aoxidize the operation of blowing are as follows: in 700 DEG C of blowing temperature of muffle and oxidation
Under conditions of, primary air is blasted into lead-antimony alloy, while being passed through auxiliary air to reactor, antimony vapour oxidation is made to generate three
Two antimony are aoxidized, 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.
Through detecting: Pb contains 3.76% containing 75.67%, As containing 18.96%, Sb in lead-antimony alloy；The stibium trioxide powder of generation meets
The trade mark specified in GB/T 4062-2013 is Sb2O399.00 stibium trioxide powder；Contain Pb 97.65% in lead bullion, contains Sb
1.85%, contain As 0.52%.
Embodiment 2:
By taking certain domestic Lead And Zinc Smelter is containing arsenic smoke dust as an example, raw material main component is Pb 6.88%, As 36.51%, Sn
1.11%, Sb 29.77%, Zn 0.54%, Te 0.24%, Se 0.05%.It is handled using following steps:
(1) oxygen presses water logging: weighing the high-arsenic antimony flue dust of certain mass in reaction kettle, control condition is that liquid consolidates volume mass
Than 20:1, mixing speed 300r/min, 160 DEG C of extraction temperature, partial pressure of oxygen 0.5Mpa, extraction time 2h, after leaching, remove
Slurry filtration separation, obtains arsenic leaching solution and leached mud；
Through detecting: arsenic leaching rate 51.29%, each element concentration Pb 515.20ppm, Se 31.56ppm, Sb in leachate
0.88g/L, Te 122.26ppm, As 9.36g/L.
(2) leachate consolidates arsenic: the resulting leachate of step (1) consolidates arsenic mineral using distribution crystallisation synthesizing high-stability,
The condition of control are as follows: the initial pH value for adjusting leachate is adjusted to 2, is 5 addition iron nitrate solutions according to Fe/As molar ratio, simultaneously
Sodium carbonate regulation reaction is added to carry out under the conditions of pH value 2, makes Fe3+With AsO4 3-Reaction generates the solid arsenic mineral of high stability, nitre
The addition speed of sour ferrous solution is 5ml/min, and the addition speed of sodium carbonate is 5ml/min；
Through detecting, the solid arsenic mineral of synthesis meets GB5085.3-2007 (solid waste judging standard-leaching characteristic identification)
Regulation, can store up safely.
(3) leached mud washs: step (1) resulting leached mud is according to liquid-solid ratio 5:1 using the washing leaching of fluidization wash tower
It slags tap 2 times, obtains washery slag and washing lotion；
Through detecting: washing lotion 8.45g/L containing arsenic, washery slag contain solvable arsenic 0.1%.
(4) washery slag recycles valuable metal: being incorporated charcoal, coal and soda ash after the washery slag of step (3) is dry, reflects at 1100 DEG C
Reduction melting is carried out in furnace, melting generates bubble slag, lead-antimony alloy and flue dust.Bubble slag send lead to smelt, flue dust return reduction melting or
Oxygen presses water logging, and lead-antimony alloy enters oxidation blowing process.Aoxidize the operation of blowing are as follows: in 800 DEG C of blowing temperature of muffle and oxidation
Under conditions of, primary air is blasted into lead-antimony alloy, while being passed through auxiliary air to reactor, antimony vapour oxidation is made to generate three
Two antimony are aoxidized, 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.
Through detecting: Pb contains 5.58% containing 64.98%, As containing 28.27%, Sb in lead-antimony alloy；The stibium trioxide powder of generation meets
The trade mark specified in GB/T 4062-2013 is Sb2O399.00 stibium trioxide powder；Contain Pb 95.25% in lead bullion, contains Sb
2.75%, contain As 0.67%.
Embodiment 3:
By taking certain domestic Lead And Zinc Smelter is containing arsenic smoke dust as an example, raw material main component is Pb 5.46%, As 30.29%, Sn
0.98%, Sb 29.58%, Zn 0.68%, Te 0.26%, Se 0.07%.It is handled using following steps:
(1) oxygen presses water logging: weighing the high-arsenic antimony flue dust of certain mass in reaction kettle, control condition is that liquid consolidates volume mass
Than 10:1, mixing speed 300r/min, 200 DEG C of extraction temperature, partial pressure of oxygen 2.5Mpa, extraction time 4h, after leaching, remove
Slurry filtration separation, obtains arsenic leaching solution and leached mud；
Through detecting: arsenic leaching rate 64.52%, each element concentration Pb 956.35ppm, Se 18.91ppm, Sb in leachate
0.93g/L, Te 144.92ppm, As 19.54g/L.
(2) leachate consolidates arsenic: the resulting leachate of step (1) consolidates arsenic mineral using distribution crystallisation synthesizing high-stability,
The condition of control are as follows: the initial pH value for adjusting leachate is 2, is 2.5 addition iron nitrate solutions according to Fe/As molar ratio, simultaneously
Sodium carbonate regulation reaction is added to carry out under the conditions of pH value 1.5, makes Fe3+With AsO4 3-Reaction generates the solid arsenic mineral of high stability,
The addition speed of iron nitrate solution is 5ml/min, and the addition speed of sodium carbonate is 5ml/min；
Through detecting: the solid arsenic mineral of synthesis meets GB5085.3-2007 (solid waste judging standard-leaching characteristic identification)
Regulation, can store up safely.
(3) leached mud washs: step (1) resulting leached mud is according to liquid-solid ratio 5:1 using the washing leaching of fluidization wash tower
It slags tap 2 times, obtains washery slag and washing lotion；
Through detecting: washing lotion 5.46g/L containing arsenic, washery slag contain solvable arsenic 0.1%.
(4) washery slag recycles valuable metal: being incorporated charcoal, coal and soda ash after the washery slag of step (3) is dry, reflects at 1200 DEG C
Reduction melting is carried out in furnace, melting generates bubble slag, lead-antimony alloy and flue dust.Bubble slag send lead to smelt, flue dust return reduction melting or
Oxygen presses water logging, and lead-antimony alloy enters oxidation blowing process.Aoxidize the operation of blowing are as follows: in 650 DEG C of blowing temperature of muffle and oxidation
Under conditions of, primary air is blasted into lead-antimony alloy, while being passed through auxiliary air to reactor, antimony vapour oxidation is made to generate three
Two antimony are aoxidized, 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.
Through detecting: Pb contains 6.45% containing 65.27%, As containing 26.67%, Sb in lead-antimony alloy；The stibium trioxide powder of generation meets
The trade mark specified in GB/T 4062-2013 is Sb2O399.00 stibium trioxide powder；Contain Pb 95.89% in lead bullion, contains Sb
2.98%, contain As 0.64%.
Although above having used general explanation, specific embodiment and test, the present invention is made to retouch in detail
It states, but on the basis of the present invention, it can be made some modifications or improvements, this is apparent to those skilled in the art
's.Therefore, these modifications or improvements without departing from theon the basis of the spirit of the present invention, belong to claimed
Range.
Claims (12)
1. a kind of method that arsenic-containing smoke dust dearsenification and distribution crystallisation synthesize solid arsenic mineral, which comprises the steps of:
(1) oxygen presses water logging: it takes arsenic-containing smoke dust in reaction kettle, water is added thereto, oxidizing gas is passed through into reaction kettle, in
It 120~300 DEG C, carries out oxygen leaching under 0.1~3.5MPa, after oxygen leaching, through solid-liquor separation, obtains arsenic leaching solution
And leached mud；
(2) leachate consolidates arsenic: solid arsenic is carried out using distribution crystallisation, the pH value of leachate obtained by regulating step (1) to 1.5~3,
Iron salt solutions are added into leachate, while neutralizer regulation reaction is added and is carried out under the conditions of pH value 1.5~3, make Fe3+With
AsO4 3-Reaction generates the solid arsenic mineral of high stability；
(3) leached mud washs: washing to step (1) resulting leached mud, obtains washing lotion and washery slag, controls arsenic in washery slag and contain
Amount is less than 0.1%, wherein the washing lotion return step (1) carries out oxygen and presses water logging；
(4) washery slag recycles valuable metal: after the washery slag that step (3) obtains is dry, mixing restore with charcoal, coal and soda ash and melt
Refining generates flue dust, bubble slag and lead-antimony alloy；
The flue dust is returned into the reduction melting or oxygen presses water logging；
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, as stibium trioxide product；Blowing slag return reduction melting process is matched
Material；Lead is sent to refine the lead bullion.
2. according to the method described in claim 1, it is characterized by: by percentage to the quality, the flue dust includes following main
Ingredient: 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%.
3. according to the method described in claim 1, it is characterized by: the liquid of water and arsenic-containing smoke dust consolidates volume mass in step (1)
Than for 3:1~20:1, unit mL:g；And/or extraction temperature is 150~260 DEG C, leaching pressure is 1.5~2MPa；With/
Or, the oxygen pressure water logging carries out under stiring, the speed of the stirring is 50r/min~500r/min.
4. according to the method described in claim 1, it is characterized by: the oxidizing gas is oxygen, air in step (1)
Or oxygen-enriched air.
5. method according to any one of claims 1 to 4, it is characterised in that: in step (2), the iron salt solutions are selected from
At least one of ferrum sulfuricum oxydatum solutum, iron nitrate solution, ferric chloride solution.
6. according to the method described in claim 5, it is characterized by: in step (2), As rubs in Fe and washing lotion in iron salt solutions
You are than being 1~5.
7. according to the method described in claim 5, it is characterized by: distribution crystallisation carries out under the conditions of room temperature is to 120 DEG C.
8. the method according to the description of claim 7 is characterized in that distribution crystallisation carries out under the conditions of 80~120 DEG C.
9. -4,6 described in any item methods according to claim 1, it is characterised in that: in step (4), the behaviour of the oxidation blowing
As: under conditions of muffle, primary air is blasted into lead-antimony alloy, antimony volatilization is made to generate a large amount of antimony vapours, while to anti-
It answers device to be passed through auxiliary air, antimony vapour oxidation is made to generate antimony oxide.
10. according to the method described in claim 9, it is characterized in that, oxidation blowing carries out under the conditions of 650~800 DEG C.
11. according to the method described in claim 1, it is characterized by: in step (4), the temperature of the reduction melting is 900~
1200℃。
12. -4,6,11 described in any item methods according to claim 1, it is characterised in that: in step (3), the leaching pulp water
It washes using fluidization wash tower；And/or in step (4), the reduction melting and oxidation blowing use blast furnace, reverberatory furnace, bottom
Blown converter, side-blown converter, any one in top blast furnace.
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