CN106834718A - 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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- CN106834718A CN106834718A CN201611192967.XA CN201611192967A CN106834718A CN 106834718 A CN106834718 A CN 106834718A CN 201611192967 A CN201611192967 A CN 201611192967A CN 106834718 A CN106834718 A CN 106834718A
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- arsenic
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- antimony
- leachate
- lead
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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
-
- 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
-
- 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
-
- 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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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
Abstract
A kind of method that the present invention provides arsenic-containing smoke dust comprehensive utilization and arsenic harmlessness disposing, the method presses water logging using oxygen, the solid arsenic of leachate, leached mud is washed and washery slag reclaims the operation of valuable metal, water logging is pressed by oxygen, solvable arsenic in removing flue dust, by arsenic in leachate using regulation and control growth method, fractional crystallisation method, the heavy arsenic method of lime, one or more combination in precipitation transformation method, the solid arsenic mineral of synthesizing stable, then using store up or cement solidification by the way of solidify solid arsenic mineral, leached mud is scrubbed, reduction melting, the operations 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 that arsenic is separated and innoxious with valuable metal.Comprehensive resource utilization rate of the present invention is high, raw material wide adaptation range, solves the cigarette ash that pollution problem in traditional handicraft extraction process, particularly Lead-Zinc Sintering Process are produced, 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 arsenic solid materials high 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 arsenic circulative accumulation in systems, because
This, generally should individually process dearsenification.Arsenic category severe toxicity, carcinogenic elements, it applies progressively atrophy, in face of increasingly strict environmental protection mark
How standard, process various high-arsenic materials, it has also become threatens the significant problem of nonferrous metallurgy industry existence.
The method for the treatment of arsenic-containing smoke dust is mainly two classes at present, and one is fire concentrate, and two is wet separation.Pyrogenic process is produced
In, the oxide of arsenic and the difference of other elements oxide boiling point are mainly used, arsenic is separated with other elements.
CN103602835A discloses a kind of method for replacing reducing process acquisition crude arsenic and needle antimony, and CN103602834A discloses a kind of choosing
Selecting property oxidationreduction obtains purity As not high2O3With the method for needle antimony, CN104294053A discloses a kind of arsenic-containing smoke dust also
The method of former volatilized arsenic, obtains arsenic trioxide purity and reaches more than 97.0%.But if contain and arsenogen disposition in flue dust
The close metal of matter (such as antimony), the then arsenic trioxide purity for obtaining is not high.It is main in wet production to there is water logging, acidleach, alkali to soak
Three kinds of techniques, but the products such as purity arsenic trioxide not high, natrium arsenicum can only be obtained, and valuable metal powder is reclaimed not
Make further research.CN105567983A discloses a kind of handling process of Copper making flue dust water logging-alkali leaching, makes arsenic with 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 disclose oxygen pressure
The method that arsenic antimony is separate is realized in alkali leaching, and more thoroughly, but the natrium arsenicum for obtaining in process is untreated, tellurium, antimony for the ratio that arsenic antimony is separate
It is unrecovered Deng valuable metal.
In sum, dearsenification, the research paper of extraction valuable metal and Patents report are many but existing from flue dust
Technology is low there are still valuable metal comprehensive recovery, and arsenic product market is limited, there is a problem of potential potential safety hazard.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, economy, energy-conservation, resource utilization high
Advantage, realizes the harmless treatment of arsenic, specifically adopts 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：Arsenic-containing smoke dust is taken in reactor, water is added thereto to, to being passed through oxidisability gas in reactor
Body, in 120~300 DEG C, carries out oxygen leaching under 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 the 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 to leachate treatment, the solid arsenic mineral of synthesizing stable, then using store up or cement solidification by the way of
The solidification solid arsenic mineral；
(3) leached mud washing：Leached mud obtained by step (1) is washed, washing lotion and washery slag is obtained, in control 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 reclaims valuable metal：After the washery slag that step (4) is obtained is dried, mix with charcoal, coal and soda ash and gone back
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 carried out into oxidation blowing, air is passed through under conditions of muffle, obtain antimony vapour, blowing slag and
Lead bullion；By antimony vapour oxidation generation antimony oxide, as stibium trioxide product；The blowing slag is returned into reduction melting operation
Dispensing；Lead is sent to refine the lead bullion.
The particularly suitable following arsenic-containing smoke dust for the treatment of of the method for 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), water is 3 with the liquid solid product mass ratio of arsenic-containing smoke dust: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 are selected from least one in oxygen, air, oxygen-enriched air.
Used as the present invention preferably technical scheme, the operation of step (1) is specially：Arsenic-containing smoke dust is taken in reactor, is pressed
Liquid solid product mass ratio according to water and arsenic-containing smoke dust is 3:1~20:1 (ml/g) is counted, and is added thereto to water, to being passed through in reactor
Oxidizing gas, in 150~260 DEG C, carry out oxygen leaching, when control is leached under 1.5~2MPa, 50r/min~500r/min
Between be 120~200min.This kind of condition can realize the abundant leaching of arsenic, realize being sufficiently separated for arsenic and other metals.
Preferably, using the solid arsenic of regulation and control growth method, the operation of the regulation and control growth method is step (2)：Regulating step (1) institute
The pH value of leachate is obtained to 1.5~3,75~90 DEG C are warming up to, ferrous salt solution as heavy arsenic is added in the way of continuous charging
Agent, it is ferric ion to be continually fed into oxidizing gas by ferrous ions, while adding 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.
In regulation and control growth method, ferrous salt solution and nertralizer are as a solution as the carrying out of reaction is slowly added to reaction
In system, the addition speed of the two is about 3~20ml/min.
Preferably, the ferrous salt solution be selected from copperas solution, solution of ferrous chloride, ferrous nitrate solution in extremely
Few one kind.
Preferably, the nertralizer is selected from least one in sodium carbonate, sodium acid carbonate, NaOH.
Preferably, the oxidizing gas are selected from least one in oxygen, air, oxygen-enriched air.
Preferably, the mol ratio of As is 2~5 in Fe and washing lotion in ferrous salt solution, and optimal is 2~3.
Preferably, using the solid arsenic of fractional crystallisation method, the operation of the fractional crystallisation method is step (2)：Regulating step (1) institute
The pH value of leachate is obtained to 1.5~3, to iron salt solutions are added in leachate, while adding 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, present invention preferably employs ferrum sulfuricum oxydatum solutum, ferric nitrate
At least one in solution, ferric chloride solution.
Preferably, the mol ratio of As 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, this kind of
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 sodium carbonate, potassium carbonate, at least one in NaOH.Iron
Salting liquid and nertralizer are slowly added in reaction system with the carrying out of reaction as a solution, and the addition speed of the two is about
3~20ml/min.
Preferably, using the lime solid arsenic of heavy arsenic method in step (2), the operation of the heavy arsenic method of the lime is：Regulating step (1)
The pH value of gained leachate to 1.5~3, in the way of continuous charging in leachate add CaO and Ca (OH)2In 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 carried out at 40~90 DEG C.
Preferably, CaO and Ca (OH)2In Ca and leachate in the mol ratio (i.e. Ca/As) of As be 2~8, it is further excellent
Elect 3~5 as.
Preferably, arsenic is consolidated by the way of the heavy arsenic method of lime and precipitation transformation method are combined in step (2), concrete operations are：
Regulating step (1) gained leachate pH value to 1.5~3, in the way of continuous charging in leachate add CaO and Ca
(OH)2In one or two solid arsenic, obtain arsenic acid calcium precipitate；Iron salt solutions as heavy arsenical are added in the way of continuous charging,
Add nertralizer regulation and control reaction simultaneously is carried out under the conditions of pH value 1.5~3, makes Fe3+With AsO4 3-Reaction generates consolidating for high stability
Arsenic mineral.
Preferably, the heavy arsenic of lime is carried out under the conditions of 10~90 DEG C, is further preferably carried out at 40~90 DEG C.
Preferably, CaO and Ca (OH)2In Ca and leachate in the mol ratio (i.e. Ca/As) of As be 2~8, it is further excellent
Elect 3~5 as.
Preferably, the mol ratio (i.e. Fe/As) of Fe and As in leachate is 1~5, more preferably 2~3 in molysite.
Preferably, the iron salt solutions are selected from least one in ferrum sulfuricum oxydatum solutum, ferric chloride solution, iron nitrate solution,
The nertralizer be selected from sodium carbonate, potassium carbonate, at least one in NaOH, iron salt solutions and nertralizer are as a solution
As the carrying out of reaction is 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：The solid arsenic mineral is coated with cement；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 is the 20~60% of cement weight.
Preferably, the condition of the cement solidification is to compare 2 according to the weight of 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, preferably
40%.
Preferably, in step (3), leached mud washing uses fluidization wash tower, typically 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 the impurity such as metallic antimony, Pb, Bi, Sn and is also reduced into list in reactor
Matter enters in needle antimony alloy, and pit ash and a small amount of arsenic, antimony, the oxide of lead react that to generate many alveolar substances light with soda ash
" bubble slag ", floats over antimony liquid surface.After the completion of reduction, bubble slag is clawed, under conditions of muffle, to blasting primary air in antimony liquid,
Antimony is volatilized and produce a large amount of antimony vapours, while being passed through auxiliary air to reactor, antimony vapour is aoxidized generation antimony oxide, profit
Antimony liquid temperature degree in the big necessary temperature of calorimetric maintenance reaction device and stove for producing is aoxidized with antimony.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 to stay in the lead of reactor bottom, realize 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, solvable arsenic in removing flue dust by oxygen, and trivalent arsenic is oxidized into pentavalent arsenic, is soaked
Go out liquid arsenic using one or more the knot in 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 solid arsenic mineral form, then using store up or cement solidification by the way of solidify
Gu arsenic mineral, leached mud makes each valuable element be recycled utilization through operations such as fluidization wash, reduction melting, oxidation blowing.
Arsenic is removed and solidified by the method from flue dust, and antimony, lead, bismuth etc. are stayed 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, in solving traditional handicraft extraction process
The cigarette ash that pollution problem, particularly Lead-Zinc Sintering Process are produced, the advantage of this method is more obvious.
The advantage and good effect of the inventive method：
1st, the present invention is all removed the solvable arsenic in arsenic flue dust, the raw material arsenic after dearsenification by the way of oxygen pressure 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 presses water logging using oxygen, 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
Then one or more combination in method and precipitation transformation method, the solid arsenic mineral of synthesizing stable uses and stores up or cement
The mode of solidification solidifies solid arsenic mineral, and the solid arsenic mineral after solidification is steady under the conditions of pH scopes 2~11 wide and strong reducing property
Surely store up, As is no longer migrated, also making the As of smelting system has an ideal open circuit, be 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 reclaims valuable metal using reduction melting, realizes that metal comprehensive reutilization is maximized.
6th, the rational operation collocation of the present invention, enable the valuable elements such as arsenic safe disposal, antimony, lead, bismuth be recycled and
Effectively utilize, reached environmental protection, economy, energy-conservation, the purpose of resource utilization high, realize that the innoxious and utilization of resources of arsenic is maximum
Change.Use wet processing and avoid massive pollution and the resource that pyrogenic process is brought by arsenic is separated with other elements
Using problem not high, whole technique substantially three-waste free discharge, all resources obtain maximal efficiency utilization, and products therefrom is just
In follow-up treatment and processing, so the present invention has environmental protection, economy, energy-conservation, the advantage of resource utilization high.
Brief description of the drawings
Fig. 1 is process chart of the invention.
Specific embodiment
Below to the detailed narration of technical scheme, the technological process of embodiment refer to Fig. 1.Wherein described percentage
Content is mass number.
Embodiment 1：
So that domestic certain 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%, is processed 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 of extraction temperature, partial pressure of oxygen 2Mpa, extraction time 2h, 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 regulation and control growth method：Be will heat up to 90 DEG C after the pH value of step (1) gained leachate is adjusted into 2, risen to pre-
By ferrous nitrate solution liquid and sodium carbonate (it is 2 that purpose control system pH value is constant) while being 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, prepare 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 washing：Step (1) gained leached mud accumulates mass ratio 5 according to liquid solid:1 uses fluidization wash tower
Washing leached mud 2 times, obtains 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 contains solvable arsenic 0.1%.
(4) washery slag reclaims valuable metal：The washery slag of step (3) allocates charcoal, coal and soda ash into 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 operation.Aoxidizing blowing operation is：In muffle and 700 DEG C of blowing temperature of oxidation
Under the conditions of, to primary air is blasted in lead-antimony alloy, while being passed through auxiliary air to reactor, antimony vapour is aoxidized three oxygen of generation
Change two antimony, the antimony oxide of generation is used as stibium trioxide product.Blowing slag returns former smelting system, and the lead bullion aoxidized after blowing send
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 domestic certain 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%, is processed 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 of extraction temperature, partial pressure of oxygen 0.5Mpa, extraction time 2h, leaching are removed after terminating
Slurry filtration is separated, 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, to iron nitrate solution is added in leachate, while add sodium carbonate regulation and control to react being carried out under the conditions of pH value 1.5, makes Fe3+
With AsO4 3-The solid arsenic mineral of reaction generation high stability, the addition speed of iron nitrate solution is 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 washing：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 contains solvable arsenic 0.1%.
(4) washery slag reclaims valuable metal：Step (3) gained washery slag allocates charcoal, coal and soda ash into after drying, anti-at 1100 DEG C
Penetrating carries out reduction melting 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 presses water logging, lead-antimony alloy enters oxidation blowing operation.Aoxidizing blowing operation is：In muffle and 800 DEG C of blowing temperature of oxidation
Under conditions of, to primary air is blasted in lead-antimony alloy, while being passed through auxiliary air to reactor, antimony vapour is aoxidized generation three
Two antimony are aoxidized, the antimony oxide of generation is used as stibium trioxide product.Blowing slag 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 domestic certain 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%, is processed 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 of extraction temperature, partial pressure of oxygen 2.5Mpa, extraction time 4h after leaching terminates, are removed
Slurry filtration is separated, 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：Using the heavy arsenic method of lime, the pH value of leachate is adjusted to 1.5, in the way of continuous charging to
Calcium oxide is added in leachate, it is 6 to control Ca/As mol ratios, and arsenic is consolidated 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 in solution to step (2)
5, while adding sodium carbonate as nertralizer, regulation and control reaction is carried out in 1.5 times stabilizations of pH value, ultimately generates 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 washing：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 contains solvable arsenic 0.1%.
(5) washery slag reclaims valuable metal：Washery slag obtained by step (4) allocates charcoal, coal and soda ash into 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 operation.Aoxidizing the operation blown is：In muffle and oxidation blowing temperature
Under conditions of 650 DEG C, to primary air is blasted in lead-antimony alloy, while being passed through auxiliary air to reactor, aoxidize antimony vapour
Generation antimony oxide, the antimony oxide of generation is used as stibium trioxide product.Blowing slag 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 domestic certain Lead And Zinc Smelter is containing 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 processed 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 of extraction temperature, partial pressure of oxygen 1Mpa, extraction time 2h 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：Using the heavy arsenic method of lime, the pH value of regulating step (1) gained leachate to 1.5, 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 to, mixture is obtained；According to cement and admittedly
Arsenic mineral weight compares 4：1, coat the solid arsenic mineral with obtained mixture；
(4) leached mud washing：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 contains solvable arsenic 0.1%.
(5) washery slag reclaims valuable metal：Washery slag obtained by step (4) allocates charcoal, coal and soda ash into 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 operation.Aoxidizing the operation blown is：In muffle and oxidation blowing temperature
Under conditions of 800 DEG C, to primary air is blasted in lead-antimony alloy, while being passed through auxiliary air to reactor, aoxidize antimony vapour
Generation antimony oxide, the antimony oxide of generation is used as stibium trioxide product.Blowing slag 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 having used general explanation, specific embodiment and experiment, the present invention is made to retouch in detail
State, but on the basis of the present invention, it can be made some modifications or improvements, this is to those skilled in the art apparent
's.Therefore, these modifications or improvements without departing from theon the basis of the spirit of the present invention, belong to claimed
Scope.
Claims (10)
1. the method for a kind of comprehensive utilization of arsenic-containing smoke dust and arsenic harmlessness disposing, it is characterised in that：Comprise the following steps：
(1) oxygen pressure water logging：Arsenic-containing smoke dust is taken in reactor, water is added thereto to, to being passed through oxidizing gas in reactor, in
120~300 DEG C, oxygen leaching is carried out under 0.1~3.5MPa, after oxygen leaching terminates, through solid-liquor separation, obtain arsenic leaching solution
And leached mud；
(2) the solid arsenic of leachate：Using the 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 kind of the above to leachate treatment, the solid arsenic mineral of synthesizing stable, alternatively, using store up or cement solidification by the way of consolidate
Change the solid arsenic mineral；
(3) leached mud washing：Fluidization wash is carried out to the leached mud obtained by step (1), washing lotion and washery slag is obtained, washery slag is controlled
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 reclaims valuable metal：After the washery slag that step (4) is obtained 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 carried out into oxidation blowing, air is passed through under conditions of muffle, antimony vapour, blowing slag and thick is obtained
Lead；By antimony vapour oxidation generation antimony oxide, as stibium trioxide product；The blowing slag is returned into reduction melting operation to match somebody with somebody
Material；Lead is sent to refine the lead bullion.
2. method according to claim 1, it is characterised in that：By percentage to the quality, the flue dust includes following main
Composition：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. method according to claim 1, it is characterised in that：In step (1), the solid volume mass of liquid of water and arsenic-containing smoke dust
Than being 3:1~20:1(ml：g)；And/or, extraction temperature is 150~260 DEG C, and leaching pressure is 1.5~2Mpa；And/or, it is described
Oxygen pressure water logging is carried out under agitation, and the mixing speed is 50r/min~500r/min.
4. method according to claim 1, it is characterised in that：Step (2) is using the solid arsenic of regulation and control growth method, the regulation and control life
The operation of regular way is：The pH value of regulating step (1) gained leachate is warming up to 75~90 DEG C, with continuous charging to 1.5~3
Mode adds ferrous salt solution as heavy arsenical, and it is ferric ion to be continually fed into oxidizing gas by ferrous ions, together
When add nertralizer regulation and control reaction carried out under the conditions of pH value 1.5~3, make Fe3+With AsO4 3-The solid arsenic of reaction generation high stability
Mineral；
Preferably, the mol ratio of As is 2~5 in Fe and washing lotion in ferrous salt solution；And/or, the ferrous salt solution is selected from sulphur
At least one in sour ferrous iron solution, solution of ferrous chloride, ferrous nitrate solution；And/or, the oxidizing gas are selected from oxygen
At least one in gas, air, oxygen-enriched air；And/or, the nertralizer is selected from sodium carbonate, sodium acid carbonate, NaOH
It is at least one.
5. method according to claim 1, it is characterised in that：Step (2) is using the solid arsenic of fractional crystallisation method, the distribution knot
The operation of crystallization is：The pH value of regulating step (1) gained leachate to 1.5~3, to adding iron salt solutions in leachate, while
Add nertralizer regulation and control reaction is carried out under the conditions of pH value 1.5~3, makes Fe3+With AsO4 3-The solid arsenic minerals of reaction generation high stability
Thing；
Preferably, the iron salt solutions are selected from ferrum sulfuricum oxydatum solutum, iron nitrate solution, at least one in ferric chloride solution；With/
Or, the mol ratio of As is 1~8 in Fe and washing lotion in molysite；And/or, fractional crystallisation method is in room temperature to carrying out under the conditions of 120 DEG C；
And/or, fractional crystallisation is carried out under agitation, and the speed of the stirring is 50~500r/min；And/or, the nertralizer is selected from
At least one in sodium carbonate, sodium acid carbonate, NaOH.
6. method according to claim 1, it is characterised in that：Using the lime solid arsenic of heavy arsenic method, the lime in step (2)
The operation of heavy arsenic method is：Regulating step (1) gained leachate pH value to 1.5~3, in leachate in the way of continuous charging
Add CaO and Ca (OH)2In one or two solid arsenic, obtain solid arsenic mineral；
Preferably, Gu arsenic is carried out under the conditions of 10~90 DEG C；And/or, CaO and Ca (OH)2In Ca and leachate in As mole
Than being 2~8.
7. the method according to 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 mode that shallow lake conversion method is combined consolidates arsenic, and concrete operations are：Regulating step (1) gained leachate pH value to 1.5~3, with continuous
The mode of charging is to addition CaO and Ca (OH) in leachate2In one or two solid arsenic, obtain arsenic acid calcium precipitate；Continuously to add
The mode of material adds solution as heavy arsenical, while add nertralizer regulation and control to react being carried out under the conditions of pH value 1.5~3, makes Fe3+
With AsO4 3-The solid arsenic mineral of reaction generation high stability；
Preferably, the heavy arsenic of lime is carried out under the conditions of 10~90 DEG C；And/or, CaO and Ca (OH)2In Ca and leachate in As
Mol ratio is 2~8；And/or, the iron salt solutions are selected from least in ferrum sulfuricum oxydatum solutum, ferric chloride solution, iron nitrate solution
Kind；And/or, the nertralizer is selected from least one in sodium carbonate, sodium acid carbonate, NaOH.
8. the method according to claim 1-6, it is characterised in that：In step (2), the operation of cement solidification is：Use cement
The cladding solid arsenic mineral；Preferably, the cement and the weight ratio of solid arsenic mineral are (2~10)：1；It is further preferred that institute
State doped with coal dust in cement, the addition of the coal dust is the 20~60% of cement weight.
9. method according to 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, to primary air is blasted in lead-antimony alloy, make
Antimony volatilization produces a large amount of antimony vapours, while being passed through auxiliary air to reactor, antimony vapour is aoxidized generation antimony oxide；It is preferred that
Ground, the oxidation blowing is carried out under the conditions of 650~800 DEG C.
10. the method according to any one of claim 1-6 or 9, it is characterised in that：In step (3), the leached mud washing
Using fluidization wash tower；And/or, in step (4), the reduction melting and oxidation blowing are using blast furnace, reverberatory furnace, bottom blowing
Any one in stove, side-blown converter, top blast stove.
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| CN109371252A (en) * | 2018-12-12 | 2019-02-22 | 刘义冬 | A kind of device and method of pyrogenic process and wet method combined processing antimony regulus arsenic alkaline slag |
| CN112941312A (en) * | 2021-03-12 | 2021-06-11 | 刘义冬 | Comprehensive recovery process for antimony and arsenic smelting alkaline residue |
| CN113862464A (en) * | 2021-08-29 | 2021-12-31 | 中南大学 | Method for recovering copper and scattered metal in black copper sludge |
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