CN106834718B - A kind of arsenic-containing smoke dust comprehensive utilization and the method for arsenic harmlessness disposing - Google Patents
A kind of arsenic-containing smoke dust comprehensive utilization and the method for arsenic harmlessness disposing 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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- 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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- 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
- C22B30/04—Obtaining arsenic
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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
- C22B7/006—Wet processes
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- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
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Abstract
A kind of method that the present invention provides arsenic-containing smoke dust comprehensive utilization and arsenic harmlessness disposing, this method is using oxygen pressure water logging, the solid arsenic of leachate, leached mud washs and the operation of washery slag recovery valuable metal, water logging is pressed by oxygen, remove solvable arsenic in flue dust, by arsenic in leachate using regulation and control growth method, fractional crystallisation method, the heavy arsenic method of lime, combination more than one or both of precipitation transformation method, synthesize stable solid arsenic mineral, then solid arsenic mineral is solidified by the way of stockpiling or cement solidification, leached mud is scrubbed, reduction melting, the processes such as oxidation blowing, maximize and recycle each valuable element.The method removes arsenic from flue dust, and antimony, lead, bismuth etc. is stayed in as far as possible in dearsenification slag, realizes the separation of arsenic and valuable metal and innoxious.Comprehensive resource utilization rate of the present invention is high, and raw material wide adaptation range solves cigarette ash caused by pollution problem in traditional handicraft extraction process, particularly Lead-Zinc Sintering Process, and the advantage of this method is more obvious.
Description
Technical field
The invention belongs to metallurgical technology field, and in particular to the side of a kind of arsenic-containing smoke dust comprehensive utilization and arsenic harmlessness disposing
Method.
Background technology
In nature, arsenic is generally with mispickel (FeAsS), arsenic magnetic iron ore (FeAsS2), symplesite (FeAs2), sulphur arsenical copper
Ore deposit (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 containing substantial amounts of valuable metal, directly return and smelt flow, cause the circulative accumulation of arsenic in systems, because
This, generally should individually handle dearsenification.Arsenic category severe toxicity, carcinogenic elements, it applies progressively atrophy, in face of increasingly strict environmental protection mark
Standard, how to handle various high-arsenic materials, it has also become threaten the significant problem of nonferrous metallurgy industry existence.
The method of processing arsenic-containing smoke dust is mainly two classes at present, when fire concentrate, second, wet separation.Pyrogenic process produces
In, mainly using the oxide of arsenic and the difference of other elements oxide boiling point, arsenic is separated with other elements.
CN103602835A discloses a kind of method replaced reducing process and obtain crude arsenic and needle antimony, and CN103602834A discloses a kind of choosing
Selecting property oxidationreduction obtains the not high As of purity2O3With the method for needle antimony, CN104294053A discloses a kind of arsenic-containing smoke dust also
The method of former volatilized arsenic, obtain arsenic trioxide purity and reach more than 97.0%.But if contain and arsenogen disposition in flue dust
The close metal of matter (such as antimony), then the arsenic trioxide purity obtained is not high.Mainly there are water logging, acidleach, alkali leaching in wet production
Three kinds of techniques, but the products such as the not high arsenic trioxide of purity, natrium arsenicum can only be obtained, and to the recovery of valuable metal powder not
Make further research.CN105567983A discloses a kind of handling process of Copper making flue dust water logging-alkali leaching, makes arsenic and metal point
From the arsenic product of preparation is at a discount, still higher containing arsenic in leached mud.CN104357668A discloses one kind waste acid and leaches cigarette
Dirt, electrodeposition dearsenification, acidleach and electrolytic deposition process easily produce arsenic hydride.CN105648226A and CN105648227A discloses oxygen pressure
The method that the separation of arsenic antimony is realized in alkali leaching, more thoroughly, but the natrium arsenicum obtained in process is untreated, tellurium, antimony for the ratio of arsenic antimony separation
It is unrecovered Deng valuable metal.
In summary, dearsenification, the research paper for extracting valuable metal and 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, the problem of potential potential safety hazard be present.Cause
This, prior art could be improved and develop.
The content of the invention
In order to solve arsenic-containing smoke dust dearsenification and problem containing comprehensively recovering valuable metal, the present invention proposes a kind of from cigarette containing arsenic
The method that valuable metal and arsenic harmlessness disposing are reclaimed in dirt.The present invention has environmental protection, economic, energy-conservation, resource utilization high
Advantage, the harmless treatment of arsenic is realized, is specifically adopted the following technical scheme that：
A kind of arsenic-containing smoke dust comprehensive utilization and the method for arsenic harmlessness disposing, it is characterised in that：Comprise the following steps：
(1) oxygen pressure water logging：Take arsenic-containing smoke dust to add water thereto in reactor, oxidisability gas is passed through into reactor
Body, oxygen leaching is carried out under 120~300 DEG C, 0.1~3.5Mpa, after oxygen leaching terminates, through separation of solid and liquid, obtain containing arsenic
Leachate and leached mud；
(2) the solid arsenic of leachate：Using one kind in regulation and control growth method, fractional crystallisation method, the heavy arsenic method of lime, precipitation transformation method
Or two or more combinations synthesizes stable solid arsenic mineral, then by the way of stockpiling or cement solidification to leachate processing
Solidify the solid arsenic mineral；
(3) leached mud washs：Leached mud obtained by step (1) is washed, obtains washing lotion and washery slag, is controlled in washery slag
Arsenic content is less than 0.1%, wherein, the washing lotion return to step (1) carries out oxygen pressure water logging；
(4) washery slag recovery valuable metal：After the washery slag that step (4) obtains is dried, mix and gone back with charcoal, coal and soda ash
Former melting, generation 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 into generation antimony oxide, as stibium trioxide product；The blowing slag is returned into reduction melting process
Dispensing；Lead is sent to refine the lead bullion.
The particularly suitable following arsenic-containing smoke dust of processing of method of the present 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, in step (1), the liquid solid product mass ratio of water and arsenic-containing smoke dust is 3:1~20:1(ml：g).
Preferably, in step (1), oxygen pressure water logging is carried out under agitation, the speed of the stirring for 50r/min~
500r/min。
Preferably, in step (1), extraction time is 30~240min, and optimal is 120~200min.
Preferably, in step (1), the oxidizing gas is selected from least one of oxygen, air, oxygen-enriched air.
As the preferable technical scheme of the present invention, the operation of step (1) is specially：Arsenic-containing smoke dust is taken to be pressed in reactor
It is 3 according to the liquid solid of water and arsenic-containing smoke dust product mass ratio:1~20:1 (ml/g) is counted, and is added water thereto, is passed through into reactor
Oxidizing gas, oxygen leaching is carried out under 150~260 DEG C, 1.5~2MPa, 50r/min~500r/min, when control is leached
Between be 120~200min.Such a condition can realize the abundant leaching of arsenic, realize being sufficiently separated for arsenic and other metals.
Preferably, step (2) is using the solid arsenic of regulation and control growth method, the operation of the regulation and control growth method：Regulating step (1) institute
The pH value of leachate is obtained to 1.5~3,75~90 DEG C is warming up to, ferrous salt solution is added in a manner of continuous charging as heavy arsenic
Agent, it is ferric ion to be continually fed into oxidizing gas by ferrous ions, while adds nertralizer regulation and control reaction in pH value
Carried out under the conditions of 1.5~3, make Fe3+With AsO4 3-The solid arsenic mineral of reaction generation high stability.
Regulate and control in growth method, ferrous salt solution and nertralizer as a solution with reaction carry out be slowly added to react
In system, the addition speed of the two is about 3~20ml/min.
Preferably, the ferrous salt solution in copperas solution, solution of ferrous chloride, ferrous nitrate solution extremely
Few one kind.
Preferably, the nertralizer is selected from least one of sodium carbonate, sodium acid carbonate, sodium hydroxide.
Preferably, the oxidizing gas is selected from least one of oxygen, air, oxygen-enriched air.
Preferably, As mol ratio is 2~5 in Fe and washing lotion in ferrous salt solution, and optimal is 2~3.
Preferably, step (2) is using the solid arsenic of fractional crystallisation method, the operation of the fractional crystallisation method：Regulating step (1) institute
The pH value of leachate is obtained to 1.5~3, iron salt solutions are added into leachate, while add nertralizer regulation and control reaction in pH value 1.5
Carried out under the conditions of~3, make Fe3+With AsO4 3-The solid arsenic mineral of reaction generation high stability.
Wherein, the iron salt solutions can use material commonly used in the art, and present invention preferably employs ferrum sulfuricum oxydatum solutum, ferric nitrate
At least one of solution, ferric chloride solution.
Preferably, As mol ratio is 1~8 in Fe and washing lotion in molysite.
Preferably, fractional crystallisation method is most preferably carried out in room temperature to carrying out under the conditions of 120 DEG C at 80~120 DEG C, such a
Under the conditions of, Gu arsenic is more complete.
Preferably, during fractional crystallisation, 50~500r/min of mixing speed.
Preferably, in fractional crystallisation, the nertralizer is selected from least one of sodium carbonate, potassium carbonate, sodium hydroxide.Iron
Salting liquid and nertralizer with reaction be slowly added in reaction system as a solution, and the addition speed of the two is about
3~20ml/min.
Preferably, it is using the solid arsenic of the heavy arsenic method of lime, the operation of the heavy arsenic method of the lime in step (2)：Regulating step (1)
The pH value of gained leachate adds CaO and Ca (OH) in a manner of continuous charging to 1.5~3 into leachate2In one kind or
Two kinds of solid arsenic, obtain solid arsenic mineral.
Preferably, Gu arsenic is carried out under the conditions of 10~90 DEG C, further preferably in 40~90 DEG C of progress.
Preferably, CaO and Ca (OH)2In Ca and leachate in As mol ratio (i.e. Ca/As) be 2~8, further it is excellent
Elect 3~5 as.
Preferably, solid arsenic, concrete operations are by the way of lime sinks arsenic method and precipitation transformation method combination in step (2)：
The pH value of leachate obtained by regulating step (1) adds CaO and Ca in a manner of continuous charging to 1.5~3 into leachate
(OH)2One or both of solid arsenic, obtain arsenic acid calcium precipitate；Iron salt solutions are added in a manner of continuous charging as heavy arsenical,
Nertralizer regulation and control reaction is added simultaneously to carry out under the conditions of pH value 1.5~3, makes Fe3+With AsO4 3-Reaction generation high stability is consolidated
Arsenic mineral.
Preferably, the heavy arsenic of lime is carried out under the conditions of 10~90 DEG C, further preferably in 40~90 DEG C of progress.
Preferably, CaO and Ca (OH)2In Ca and leachate in As mol ratio (i.e. Ca/As) be 2~8, further it is excellent
Elect 3~5 as.
Preferably, Fe and As in leachate mol ratio (i.e. Fe/As) is 1~5, more preferably 2~3 in molysite.
Preferably, the iron salt solutions are selected from least one of ferrum sulfuricum oxydatum solutum, ferric chloride solution, iron nitrate solution,
The nertralizer is selected from least one of sodium carbonate, potassium carbonate, sodium hydroxide, and iron salt solutions and nertralizer are as a solution
With reaction be slowly added in reaction system, the addition speed of the two is about 3~20ml/min..
In step (2), the operation of cement solidification is：With the cement cladding solid arsenic mineral；Preferably, the cement and arsenic
The weight ratio of sour calcium precipitate is (2~10)：1；It is further preferred that doped with coal dust, the addition of the coal dust in the cement
Measure as the 20~60% of cement weight.
Preferably, the condition of the cement solidification is the weight ratio 2 according to cement and solid arsenic mineral：1~10：1, use cement
The solid arsenic mineral of cladding.The weight ratio more preferably 4：1.
Fine coal is added in cement can strengthen solidification effect, and fine coal addition is the 20~60% of cement, is preferably
40%.
Preferably, in step (3), leached mud washing use fluidization wash tower, typically washing 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 the impurity such as metallic antimony, Pb, Bi, Sn and is also reduced into list in reactor
Matter enters in needle antimony alloy, and oxide and the soda ash reaction of pit ash and a small amount of arsenic, antimony, lead generate more alveolar substances gently
" bubble slag ", float over antimony liquid surface.After the completion of reduction, bubble slag is clawed, under conditions of muffle, primary air is blasted into antimony liquid,
Antimony volatilization is produced a large amount of antimony vapours, while auxiliary air is passed through to reactor, make antimony vapour oxidation generation antimony oxide, profit
Antimony liquid temperature degree in the necessary temperature of the big calorimetric maintenance reaction device caused by antimony aoxidizes and stove.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. is then stayed in the lead of reactor bottom, realizes that a stove 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 stove, top blast stove.
The solution of the present invention is to press water logging by oxygen, removes solvable arsenic in flue dust, and trivalent arsenic is oxidized into pentavalent arsenic, is soaked
Go out liquid arsenic using knot more than one or both of regulation and control growth method, fractional crystallisation method, the heavy arsenic method of lime, precipitation transformation method
Close, the arsenical in leachate is solidified in the form of solid arsenic mineral, then solidified by the way of stockpiling or cement solidification
Gu arsenic mineral, leached mud makes each valuable element be recycled utilization through processes such as fluidization wash, reduction melting, oxidation blowing.
Arsenic is removed and solidified from flue dust by the method, and antimony, lead, bismuth etc. stay in dearsenification slag as far as possible, realizes arsenic and valuable metal
Separation and innoxious.Comprehensive resource utilization rate of the present invention is high, raw material wide adaptation range, solves in traditional handicraft extraction process
Cigarette ash caused by pollution problem, particularly Lead-Zinc Sintering Process, the advantage of this method are more obvious.
The advantages of the inventive method and good effect：
1st, the present invention all removes the solvable arsenic in arsenic flue dust, the raw material arsenic after dearsenification by the way of oxygen presses water logging
Content is low, can the valuable metal such as synthetical recovery antimony, lead, bismuth, reduce the content of arsenic in product；
2nd, the present invention is using oxygen pressure water logging, by As3+It is oxidized to As5+, solve the dysoxidizable problem of trivalent arsenic；
3rd, in the present invention, leachate is on the basis of original technology using regulation and control growth method, fractional crystallisation method, the heavy arsenic of lime
Combination more than one or both of method and precipitation transformation method, stable solid arsenic mineral is synthesized, then using stockpiling or cement
The mode of solidification solidifies solid arsenic mineral, and the solid arsenic mineral after solidifying is steady under the conditions of wide pH scopes 2~11 and strong reducing property
Fixed stockpiling, makes As no longer migrate, also makes the As of smelting system have an ideal open circuit, is a kind of technological process letter
List, resources conservation, environment-friendly method；
4th, the present invention uses fluidization wash, further reduces the content of arsenic in leached mud, can improve recovery product quality；
5th, the present invention realizes that metal comprehensive reutilization maximizes using reduction melting recovery valuable metal.
6th, the rational process collocation of the present invention, enable the valuable element such as arsenic safe disposal, antimony, lead, bismuth be recycled and
Effectively utilize, reached environmental protection, economic, energy-conservation, the purpose of high resource utilization, realize that the innoxious and utilization of resources of arsenic is maximum
Change.Because the separation of arsenic and other elements avoids massive pollution caused by pyrogenic process and resource using wet processing
Using it is not high the problem of, whole technique substantially three-waste free discharge, all resources obtain maximal efficiency utilization, products therefrom is just
In follow-up processing and processing, so the present invention has environmental protection, economic, energy-conservation, the advantage of high resource utilization.
Brief description of the drawings
Fig. 1 is the process chart of the present invention.
Embodiment
Fig. 1 refer to the detailed narration of technical scheme, the technological process of embodiment below.Wherein described percentage
Content is mass number.
Embodiment 1：
So that certain domestic Lead And Zinc Smelter contains 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%, is handled using following steps：
(1) oxygen pressure water logging：The high-arsenic antimony flue dust of certain mass is weighed in reactor, control condition is the solid volume mass of liquid
Than 10:1, mixing speed 300r/min, 160 DEG C, partial pressure of oxygen 2Mpa, extraction time 2h of extraction temperature, leaching remove material after terminating
Slurry is separated by filtration, and obtains leachate and leached mud；
After testing：Arsenic leaching rate 68.64%, each element concentration Pb 709.60ppm, Se 31.02ppm, Sb in leachate
1.26g/L, Te 123.28ppm, As 33.33g/L.
(2) the solid arsenic of growth method is regulated and controled：It will heat up to 90 DEG C, rise to pre- after the pH value of leachate obtained by step (1) is adjusted into 2
By ferrous nitrate solution liquid and sodium carbonate (constant purpose control system pH value is 2) while it is slowly added into molten containing arsenic after constant temperature degree
In liquid, and it is passed through oxidizing gas and makes Fe2+It is oxidized to Fe3+, 12h is reacted, prepares the solid arsenic mineral of high stability；Wherein, nitric acid is sub-
The addition speed of ferrous solution is 5ml/min, and the addition speed of sodium carbonate is 5ml/min, oxygen flow 10L/min, Fe/As moles
Than 2.
After testing：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：Leached mud accumulates mass ratio 5 according to liquid solid obtained by step (1):1 uses fluidization wash tower
Wash leached mud 2 times, obtain washing lotion and washery slag；Washing lotion returns to leaching process and prepares solution；
After testing：Washing lotion 9.62g/L containing arsenic, washery slag contain solvable arsenic 0.1%.
(4) washery slag recovery valuable metal：The washery slag of step (3) is incorporated charcoal, coal and soda ash after drying, in 1150 DEG C of reflections
Reduction melting, melting generation bubble slag, lead-antimony alloy and flue dust are carried out in stove.Bubble slag send lead to smelt, flue dust return reduction melting or
Oxygen presses water logging, and lead-antimony alloy enters oxidation blowing process.Aoxidizing blowing operation is：In muffle and aoxidize 700 DEG C of blowing temperature
Under the conditions of, primary air is blasted into lead-antimony alloy, while auxiliary air is passed through to reactor, make antimony vapour oxidation three oxygen of generation
Change two antimony, the antimony oxide of generation is as stibium trioxide product.The slag that blows returns former smelting system, and the lead bullion aoxidized after blowing is sent
Lead rectification systems.
After testing：Pb contains 3.76% containing 18.96%, Sb containing 75.67%, As 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, containing Sb
1.85%, containing As 0.52%.
Embodiment 2：
So that certain domestic Lead And Zinc Smelter contains 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%, is handled using following steps：
(1) oxygen pressure water logging：The high-arsenic antimony flue dust of certain mass is weighed in reactor, control condition is the solid volume mass of liquid
Than 20:1, mixing speed 300r/min, 160 DEG C, partial pressure of oxygen 0.5Mpa, extraction time 2h of extraction temperature, leaching remove after terminating
Slurry filtration separates, and obtains leachate and leached mud；
After testing：Arsenic leaching rate 72.68%, each element concentration Pb 515.20ppm, Se 31.56ppm, Sb in leachate
0.88g/L, Te 122.26ppm, As 13.27g/L.
(2) the solid arsenic of fractional crystallisation method：The initial pH value for adjusting leachate is 1.5, is 1.5 additions according to Fe/As mol ratios
Molysite, iron nitrate solution is added into leachate, while add sodium carbonate regulation and control reaction and carried out under the conditions of pH value 1.5, make Fe3+
With AsO4 3-The solid arsenic mineral of reaction generation high stability, the addition speed of iron nitrate solution are 5ml/min, the addition of sodium carbonate
Speed is 5ml/min；
After testing：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：Leached mud obtained by step (1) accumulates mass ratio 5 according to liquid solid:1 uses fluidization wash
Tower washing leached mud 2 times, obtains washing lotion and washery slag；
After testing：Washing lotion 8.45g/L containing arsenic, washery slag contain solvable arsenic 0.1%.
(4) washery slag recovery valuable metal：Charcoal, coal and soda ash are incorporated after washery slag is dried obtained by step (3), it is anti-at 1100 DEG C
Penetrate and reduction melting is carried out in stove, melting generation bubble slag, lead-antimony alloy and flue dust.Bubble slag send lead to smelt, and flue dust returns to reduction melting
Or oxygen pressure water logging, lead-antimony alloy enter oxidation blowing process.Aoxidizing blowing operation is：In muffle and 800 DEG C of blowing temperature of oxidation
Under conditions of, primary air is blasted into lead-antimony alloy, while auxiliary air is passed through to reactor, make antimony vapour oxidation generation 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.
After testing：Pb contains 5.58% containing 28.27%, Sb containing 64.98%, As 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, containing Sb
2.75%, containing As 0.67%.
Embodiment 3：
So that certain domestic Lead And Zinc Smelter contains 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%, is handled using following steps：
(1) oxygen pressure water logging：The high-arsenic antimony flue dust of certain mass is weighed in reactor, control condition is the solid volume mass of liquid
Than 10:1, mixing speed 300r/min, 200 DEG C, partial pressure of oxygen 2.5Mpa, extraction time 4h of extraction temperature, after leaching terminates, remove
Slurry filtration separates, and obtains leachate and leached mud；
After testing：Arsenic leaching rate 62.75%, each element concentration Pb 956.35ppm, Se 18.91ppm, Sb in leachate
0.93g/L, Te 144.92ppm, As 19.01g/L.
(2) the solid arsenic of leachate：Arsenic method is sunk using lime, the pH value of leachate is adjusted to 1.5, in a manner of continuous charging to
Calcium oxide is added in leachate, it is 6 to control Ca/As mol ratios, consolidates arsenic 40 hours in 40 DEG C；
(3) precipitation is converted into solid arsenic mineral：Ferric chloride solution, the control of Fe/As mol ratios are added into the solution of step (2)
5, while add sodium carbonate and carried out as nertralizer, regulation and control reaction in 1.5 times stabilizations of pH value, ultimately generate consolidating for high stability
Arsenic mineral, the addition speed of ferric chloride solution is 5ml/min, and the addition speed of sodium carbonate is 5ml/min.
After testing, the solid arsenic mineral of synthesis meets GB5085.3-2007 (solid waste judging standard-leaching characteristic identification)
Regulation, can store up safely.
(4) leached mud washs：Leached mud obtained by step (1) accumulates mass ratio 5 according to liquid solid:1 uses fluidization wash
Tower washing leached mud 2 times, obtains washing lotion and washery slag；
After testing：Washing lotion 5.46g/L containing arsenic, washery slag contain solvable arsenic 0.1%.
(5) washery slag recovery valuable metal：Washery slag obtained by step (4) is incorporated charcoal, coal and soda ash after drying, at 1200 DEG C
Reduction melting, melting generation bubble slag, lead-antimony alloy and flue dust are carried out in reverberatory furnace.Bubble slag send lead to smelt, and it is molten that flue dust returns to reduction
Refining or oxygen leaching, lead-antimony alloy enter oxidation blowing process.Aoxidizing the operation blown is：In muffle and oxidation blowing temperature
Under conditions of 650 DEG C, primary air is blasted into lead-antimony alloy, while auxiliary air is passed through to reactor, aoxidizes antimony vapour
Antimony oxide is generated, the antimony oxide of generation is as stibium trioxide product.The slag that blows returns former smelting system, and after aoxidizing blowing
Lead bullion send lead rectification systems.
After testing：Pb contains 6.45% containing 26.67%, Sb containing 65.27%, As 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, containing Sb
2.98%, containing As 0.64%.
Embodiment 4：
So that certain domestic Lead And Zinc Smelter contains arsenic smoke dust as an example, raw material main component is Pb 9.58%, As 28.31%, Sn
1.89%, Sb 23.89%, Zn 0.78%, Te 0.35%, Se 0.07%, is handled using following steps：
(1) oxygen pressure water logging：The high-arsenic antimony flue dust of certain mass is weighed in reactor, control condition is the solid volume mass of liquid
Than 10:1, mixing speed 300r/min, 160 DEG C, partial pressure of oxygen 1Mpa, extraction time 2h of extraction temperature, after leaching terminates, remove material
Slurry is separated by filtration, and obtains leachate and leached mud；
After testing：Arsenic leaching rate 71.24%, each element concentration Pb 653.81ppm, Se 34.86ppm, Sb in leachate
0.87g/L, Te 132.59ppm, As 20.17g/L.
(2) the solid arsenic of leachate：Arsenic method is sunk using lime, the pH value of leachate is to 1.5 obtained by regulating step (1), with continuous
The mode of charging adds CaO as heavy arsenical, and Ca/As mol ratios are 5, are settled 50 hours in 60 DEG C, obtain solid arsenic mineral；
(3) cement solidification：Cement is taken, the fine coal of cement weight 40% is added thereto, obtains mixture；According to cement and admittedly
Arsenic mineral weight is than 4：1, with the obtained mixture cladding solid arsenic mineral；
(4) leached mud washs：Leached mud obtained by step (1) accumulates mass ratio 5 according to liquid solid:1 uses fluidization wash
Tower washing leached mud 2 times, obtains washing lotion and washery slag；
After testing：Washing lotion 4.51g/L containing arsenic, washery slag contain solvable arsenic 0.1%.
(5) washery slag recovery valuable metal：Washery slag obtained by step (4) is incorporated charcoal, coal and soda ash after drying, at 1200 DEG C
Reduction melting, melting generation bubble slag, lead-antimony alloy and flue dust are carried out in reverberatory furnace.Bubble slag send lead to smelt, and it is molten that flue dust returns to reduction
Refining or oxygen leaching, lead-antimony alloy enter oxidation blowing process.Aoxidizing the operation blown is：In muffle and oxidation blowing temperature
Under conditions of 800 DEG C, primary air is blasted into lead-antimony alloy, while auxiliary air is passed through to reactor, aoxidizes antimony vapour
Antimony oxide is generated, the antimony oxide of generation is as stibium trioxide product.The slag that blows returns former smelting system, and after aoxidizing blowing
Lead bullion send lead rectification systems.
After testing：Pb contains 5.89% containing 27.26%, Sb containing 66.34%, As 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 95.87% in lead bullion, containing Sb
3.24%, containing As 0.71%.
Although above the present invention is made to retouch in detail with general explanation, embodiment and experiment
State, 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, are belonged to claimed
Scope.
Claims (12)
1. a kind of arsenic-containing smoke dust comprehensive utilization and the method for arsenic harmlessness disposing, it is characterised in that：Comprise the following steps：
(1) oxygen pressure water logging：Take arsenic-containing smoke dust to add water thereto in reactor, oxidizing gas is passed through into reactor, in
120~300 DEG C, oxygen leaching is carried out under 0.1~3.5MPa, after oxygen leaching terminates, through solid-liquor separation, obtains arsenic leaching solution
And leached mud；
(2) the solid arsenic of leachate：Using one kind or two in regulation and control growth method, fractional crystallisation method, the heavy arsenic method of lime, precipitation transformation method
The combination of the kind above is synthesized stable solid arsenic mineral, alternatively, consolidated by the way of stockpiling or cement solidification to leachate processing
Change the solid arsenic mineral；
It is described regulation and control growth method operation be：The pH value of leachate is warming up to 75~90 to 1.5~3 obtained by regulating step (1)
DEG C, ferrous salt solution is added in a manner of continuous charging as heavy arsenical, is continually fed into oxidizing gas by ferrous ions
For ferric ion, while add nertralizer regulation and control reaction and carried out under the conditions of pH value 1.5~3, make Fe3+With AsO4 3-Reaction life
Into the solid arsenic mineral of high stability；
The operation of the fractional crystallisation method is：The pH value of leachate adds to 1.5~3 into leachate obtained by regulating step (1)
Iron salt solutions, while add nertralizer regulation and control reaction and carried out under the conditions of pH value 1.5~3, make Fe3+With AsO4 3-Reaction generation is high
The solid arsenic mineral of stability；
The solid arsenic by the way of lime sinks arsenic method and precipitation transformation method combination, concrete operations are：Leachate obtained by regulating step (1)
PH value to 1.5~3, in a manner of continuous charging into leachate add CaO and Ca (OH)2One or both of solid arsenic,
Obtain arsenic acid calcium precipitate；Iron salt solutions are added in a manner of continuous charging as heavy arsenical, while adds nertralizer regulation and control reaction and exists
Carried out under the conditions of pH value 1.5~3, make Fe3+With AsO4 3-The solid arsenic mineral of reaction generation high stability；
(3) leached mud washs：Fluidization wash is carried out to the leached mud obtained by step (1), obtains washing lotion and washery slag, controls washery slag
Middle arsenic content is less than 0.1%, wherein, the washing lotion return to step (1) carries out oxygen pressure water logging；
(4) washery slag recovery valuable metal：After the washery slag that step (4) obtains is dried, mix reduce with charcoal, coal and soda ash and melt
Refining, generation 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, obtains antimony vapour, blowing slag and thick
Lead；The antimony vapour is aoxidized into generation antimony oxide, as stibium trioxide product；The blowing slag is returned into reduction melting process to match somebody with somebody
Material；Lead is sent to refine the lead bullion；
By percentage to the quality, the flue 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%.
2. according to the method for claim 1, it is characterised in that：In step (1), the solid volume mass of liquid of water and arsenic-containing smoke dust
Than for 3:1~20:1(ml：g)；And/or extraction temperature is 150~260 DEG C, leaching pressure is 1.5~2MPa；It is and/or described
Oxygen pressure water logging is carried out under agitation, and the mixing speed is 50r/min~500r/min.
3. according to the method for claim 1, it is characterised in that：Step (2) is using the solid arsenic of regulation and control growth method, the ferrous salt
As mol ratio is 2~5 in Fe and washing lotion in solution；And/or the ferrous salt solution is selected from copperas solution, protochloride
At least one of ferrous solution, ferrous nitrate solution；And/or the oxidizing gas is in oxygen, air, oxygen-enriched air
At least one；And/or the nertralizer is selected from least one of sodium carbonate, sodium acid carbonate, sodium hydroxide.
4. according to the method for claim 1, it is characterised in that：Step (2) is molten using the solid arsenic of fractional crystallisation method, the molysite
Liquid is selected from least one of ferrum sulfuricum oxydatum solutum, iron nitrate solution, ferric chloride solution；And/or in the molysite in Fe and washing lotion
As mol ratio is 1~8；And/or the fractional crystallisation method in room temperature to carrying out under the conditions of 120 DEG C；And/or the distribution knot
Crystallization is carried out under agitation, and the speed of the stirring is 50~500r/min；And/or the nertralizer is selected from sodium carbonate, carbonic acid
At least one of hydrogen sodium, sodium hydroxide.
5. according to the method for claim 1, it is characterised in that：Using the solid arsenic of the heavy arsenic method of lime, the lime in step (2)
The operation of heavy arsenic method is：The pH value of leachate is to 1.5~3 obtained by regulating step (1), in a manner of continuous charging into leachate
Add CaO and Ca (OH)2One or both of solid arsenic, obtain solid arsenic mineral.
6. according to the method for claim 5, it is characterised in that the solid arsenic is carried out under the conditions of 10~90 DEG C；And/or
The CaO and Ca (OH)2In Ca and leachate in As mol ratio be 2~8.
7. according to the method described in claim any one of 1-6, it is characterised in that：The heavy arsenic method of lime is used in step (2) and is sunk
The solid arsenic of mode that shallow lake conversion method combines, the heavy arsenic of the lime are carried out under the conditions of 10~90 DEG C；And/or the CaO and Ca
(OH)2In Ca and leachate in As mol ratio be 2~8；And/or the iron salt solutions are selected from ferrum sulfuricum oxydatum solutum, iron chloride
At least one of solution, iron nitrate solution；And/or the nertralizer is in sodium carbonate, sodium acid carbonate, sodium hydroxide
It is at least one.
8. according to the method for claim 1, it is characterised in that：In step (2), the operation of cement solidification is：With cement bag
Cover the solid arsenic mineral.
9. according to the method for claim 8, it is characterised in that the weight ratio of the cement and solid arsenic mineral is (2~10)：
1。
10. method according to claim 8 or claim 9, it is characterised in that doped with coal dust in the cement, the coal dust
Addition is the 20~60% of cement weight.
11. according to the method for claim 1, it is characterised in that：In step (4), the temperature of the reduction melting for 900~
1200℃；And/or the operation of the oxidation blowing is：Under conditions of muffle, primary air is blasted into lead-antimony alloy, is made
Antimony volatilization produces a large amount of antimony vapours, while is passed through auxiliary air to reactor, makes antimony vapour oxidation generation antimony oxide；It is preferred that
Ground, the oxidation blowing are carried out under the conditions of 650~800 DEG C.
12. the method according to any one of claim 1-6 or described in 11, it is characterised in that：In step (3), the leaching wash heat
Wash and use fluidization wash tower；And/or in step (4), the reduction melting and oxidation blowing are using blast furnace, reverberatory furnace, bottom
Any one in blown converter, side-blown converter, top blast stove.
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| CN102634666B (en) * | 2012-04-24 | 2013-06-05 | 葫芦岛锌业股份有限公司 | Method for dearsenicating fresh high-arsenium lead anode slime under oxygen pressure |
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