CN106834708A - A kind of integrated conduct method of arsenic-containing smoke dust - Google Patents
A kind of integrated conduct method of arsenic-containing smoke dust Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
- C22B7/02—Working-up flue dust
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- A—HUMAN NECESSITIES
- A62—LIFE-SAVING; FIRE-FIGHTING
- A62D—CHEMICAL MEANS FOR EXTINGUISHING FIRES OR FOR COMBATING OR PROTECTING AGAINST HARMFUL CHEMICAL AGENTS; CHEMICAL MATERIALS FOR USE IN BREATHING APPARATUS
- A62D3/00—Processes for making harmful chemical substances harmless or less harmful, by effecting a chemical change in the substances
- A62D3/30—Processes for making harmful chemical substances harmless or less harmful, by effecting a chemical change in the substances by reacting with chemical agents
- A62D3/33—Processes for making harmful chemical substances harmless or less harmful, by effecting a chemical change in the substances by reacting with chemical agents by chemical fixing the harmful substance, e.g. by chelation or complexation
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- C22B13/00—Obtaining lead
- C22B13/02—Obtaining lead by dry processes
- C22B13/025—Recovery from waste materials
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- 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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- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B30/00—Obtaining antimony, arsenic or bismuth
- C22B30/06—Obtaining bismuth
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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
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- A62—LIFE-SAVING; FIRE-FIGHTING
- A62D—CHEMICAL MEANS FOR EXTINGUISHING FIRES OR FOR COMBATING OR PROTECTING AGAINST HARMFUL CHEMICAL AGENTS; CHEMICAL MATERIALS FOR USE IN BREATHING APPARATUS
- A62D2101/00—Harmful chemical substances made harmless, or less harmful, by effecting chemical change
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Abstract
The present invention relates to a kind of integrated conduct method of arsenic-containing smoke dust, including the production from valuable metals such as the smelting smoke dust comprehensively reclaiming arsenic containing arsenic antimony lead, antimony, lead, bismuths, reduce arsenic and accumulated in system and make its innoxious.Soaked by normal pressure alkali, solvable arsenic in removing flue dust, after trivalent arsenic is pentavalent arsenic through catalysis oxidation in leachate, the solid arsenic mineral of synthesizing stable is combined using one or more in regulation and control growth method, fractional crystallisation method, lime heavy arsenic method and precipitation transformation method, then using store up or cement solidification by the way of solidify solid arsenic mineral, the operations such as leached mud is scrubbed, reduction melting, 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, it is possible to achieve 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 produced in 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 a kind of integrated conduct method of arsenic-containing smoke dust.
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 displacement reducing process and obtains crude arsenic and needle antimony, and CN103602834A discloses a kind of selective oxygen
Change-reduction acquisition purity As not high2O3And needle antimony, CN104294053A discloses a kind of side of arsenic-containing smoke dust reduction volatilization arsenic
Method, obtains arsenic trioxide purity and reaches more than 97.0%.But if contain the metal close with arsenic element property in flue dust
(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 the recovery of valuable metal powder is not made further research.
CN105567983A discloses a kind of handling process of Copper making flue dust water logging-alkali leaching, arsenic is separated with metal, and the arsenic of preparation is produced
Product are at a discount, still higher containing arsenic in leached mud.One kind waste acid that CN104357668A discloses leaches flue dust, electrodeposition dearsenification, acid
Leaching and electrolytic deposition process easily produce arsenic hydride.CN105648226A and CN105648227A disclose a kind of oxygen pressure alkali leaching and realize arsenic
Antimony separate method, arsenic antimony separate ratio more thoroughly, but the natrium arsenicum for obtaining in process is untreated, the valuable gold such as tellurium, antimony
Category is unrecovered.
Dearsenification, the research paper of extraction valuable metal and Patents report are many from flue dust, but there is valuable element
Comprehensive recovery is low, and arsenic product market is limited, there is potential potential safety hazard.Therefore, 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 arsenic-containing smoke dust
Integrated conduct method, it is adaptable to nonferrous metallurgical process produce flue dust treatment.Arsenic-containing smoke dust dearsenification can be realized and had
Valency element comprehensive reutilization.The present invention has the advantages that environmental protection, economy, energy-conservation, resource utilization are high, realizes the harmless of arsenic
Change.
The solution of the present invention is soaked by normal pressure alkali, solvable arsenic in removing flue dust, and by three by way of catalysis oxidation
Valency arsenic is oxidized to pentavalent arsenic, any one in the heavy arsenic method of the regulated growth method of leachate, fractional crystallisation method, lime, precipitation transformation method
Kind or the solid arsenic mineral of several combination synthesizing high-stabilities, leached mud through operations such as fluidization wash, reduction melting, oxidation blowing,
Each valuable element is set to be recycled utilization.Arsenic is removed and solidified by the method from flue dust, and antimony, lead, bismuth etc. are stayed in as far as possible
In dearsenification slag, realize that arsenic is separated and innoxious with valuable metal.Comprehensive resource utilization rate of the present invention is high, raw material accommodation
Extensively, pollution problem in traditional handicraft extraction process is solved.Particularly in Lead-Zinc Sintering Process produce cigarette ash, this method it is excellent
Gesture is more obvious.
A kind of integrated conduct method of arsenic-containing smoke dust of the present invention, comprises the following steps：
(1) normal pressure alkali leaching
Extraction temperature be room temperature~100 DEG C, the time be 30~240min, liquid solid product mass ratio be 3:1~20:1
(ml:G), NaOH concentration is 0.1mol/L~6mol/L, mixing speed to enter to arsenic-containing smoke dust under conditions of 50~1000r/min
The leaching of row normal pressure alkali is processed；Filter to obtain leachate and leached mud；Liquid solid product mass ratio refer in terms of ml/g, NaOH solution with
The volume mass ratio of arsenic-containing smoke dust；
(2) leachate catalysis oxidation
By way of catalysis oxidation, to oxidizing gas and catalyst is added in step (1) gained leachate, will leach
As in liquid3+It is transformed into As5+；
(3) the solid arsenic of oxidated solution
By the leachate after step (2) gained oxidation using regulation and control growth method, fractional crystallisation method, the heavy arsenic method of lime, precipitation
The solid arsenic mineral of any one or a few method synthesizing stable for combining in conversion method, then stores up or coats solidification with cement；
(4) leached mud washing
Step (1) gained leached mud is used into fluidization wash, the solvable arsenic in leached mud is down to less than 0.1%；
Washing lotion can be returned and leach i.e. return to step (1) for alkaline leaching feed liquid used；
(5) washery slag reclaims valuable metal
Will step (4) gained washery slag dry after allocate charcoal, coal and appropriate soda ash into, in reactor in 900~1200 DEG C,
Having under C, CO conditioning carries out reduction melting, melting generation bubble slag, lead-antimony alloy and flue dust；The flue dust is returned into reduction molten
Refining or normal pressure alkali leaching step；Lead is sent to smelt the bubble slag；The lead-antimony alloy is carried out into oxidation blowing, under conditions of muffle
Air (preferably 650~800 DEG C of temperature) is passed through, antimony vapour, blowing slag and lead bullion is obtained；By antimony vapour oxidation three oxygen of generation
Change two antimony, as stibium trioxide product；The blowing slag is returned into reduction melting operation；Lead is sent to refine the lead bullion.
Antimony liquid temperature degree in the big necessary temperature of calorimetric maintenance reaction device and stove produced using antimony oxidation；Due to melt body surface
The concentration of metallic antimony has comparative advantage, and metallic antimony property is more active than lead, bismuth, the antimony in aluminium alloy is oxidized to antimony oxide and waves
Hair enters flue dust, and lead, bismuth are then stayed in the lead of reactor bottom, realize that a stove is dual-purpose.
Arsenic-containing smoke dust of the present invention includes following main component by percentage to the quality:Arsenic:1%~60%, antimony:1%
~55%, lead:0.1%~35%, zinc:0.1%~30%, copper:0.1%~5%, tellurium:0.01%~3%, selenium:0.01%~
3%.
A kind of above-mentioned integrated conduct method of arsenic-containing smoke dust of the present invention, wherein
It is the leaching of normal pressure alkali to be leached described in step (1), and it is that 0.1mol/L~6mol/L, extraction temperature are to control NaOH concentration
Room temperature~100 DEG C, time are 30~240min, liquid solid product mass ratio is 3:1~20:1(ml:G), mixing speed be 50~
1000r/min。
Described in step (2) in the operation of catalysis oxidation, oxidizing gas are oxygen, air or oxygen-enriched air, preferably oxygen
The gas flow of the property changed gas is controlled in 1~20L/min.
Described in step (2) in the operation of catalysis oxidation, the catalyst is KMnO4；It is preferred that As and Mn in reaction system
Mol ratio is controlled 5:1~50:1.
Described in step (2) in the operation of catalysis oxidation, 30 DEG C~120 DEG C of the temperature of preferred catalytic oxidation system control.
Regulating and controlling growth method described in step (3) includes：Gained pH of leaching solution is adjusted to 1.5~3, oxidation is being continually fed into
Property gas while add heavy arsenical ferrous salt solution, in 75~90 DEG C of 5~24h of reaction of temperature, while adding nertralizer regulation and control
Reaction is reacted under the conditions of pH value 1.5~3, makes Fe3+With AsO4 3-The solid arsenic mineral of reaction generation high stability；Wherein, oxygen
The property changed gas flow is 1~20L/min, and the mol ratio for making Fe and As in reaction system is 2~5:1.The oxidizing gas are
Oxygen, air or oxygen-enriched air；The ferrous salt solution is in copperas solution, solution of ferrous chloride or ferrous nitrate solution
At least one, the nertralizer be sodium carbonate, sodium acid carbonate or NaOH at least one.Preferably, the ferrous iron
The addition speed control of salting liquid and nertralizer is in 3ml/min~20ml/min.
Fractional crystallisation method includes described in step (3)：The initial pH value of gained leachate is adjusted to 1.5~3, iron is added
Salt, the mol ratio for making Fe and As in the leachate is 1~8:1, while adding nertralizer regulation and control reaction in pH value 1.5~3
Reacted under part, made Fe3+With AsO4 3-The solid arsenic mineral of reaction generation high stability；Control reaction condition：Temperature be room temperature~
120 DEG C, the reaction time is 1~10h, 50~500r/min of mixing speed, and the iron salt solutions are ferrum sulfuricum oxydatum solutum, iron chloride is molten
At least one in liquid or iron nitrate solution, the nertralizer is at least one in sodium carbonate, sodium acid carbonate or NaOH.
Preferably, the addition speed control of the iron salt solutions and nertralizer is in 3ml/min~20ml/min.
The heavy arsenic method of lime described in step (3) includes：PH of leaching solution after gained is aoxidized is adjusted to 1.5~3, with continuous
The mode of charging adds CaO, Ca (OH)2In one or two as heavy arsenical, make Ca and As in the leachate mole
Than being 2~8:1, the sedimentation time is 5~100 hours, and reaction temperature is 10 DEG C~90 DEG C.
Precipitation transformation method includes described in step (3)：To molysite is added in step (2) gained reaction system, make reactant
The mol ratio of Fe and As is controlled 1~5 in system:1, while it is anti-to add nertralizer regulation and control reaction to be carried out under the conditions of pH value 1.5~3
Should, make Fe3+With AsO4 3-The solid arsenic mineral of reaction generation high stability；The iron salt solutions are ferrum sulfuricum oxydatum solutum, ferric chloride solution
Or at least one in iron nitrate solution, the nertralizer is at least one in sodium carbonate, sodium acid carbonate or NaOH.It is excellent
The addition speed control of selection of land, the iron salt solutions and nertralizer is in 3ml/min~20ml/min.
The control condition of cement solidification is in step (3), and 2 are compared according to the weight of cement and solid arsenic mineral:1~10:1, it is excellent
Elect 4 as:1, coat solid arsenic mineral with cement.Research finds that fine coal is added in cement can strengthen solidification effect, fine coal addition
It is the 20~60% of cement hardener, preferably 40% that amount is excellent.
The washing of leached mud described in step (4) is using the washing of fluidization wash tower.
Reduction melting described in step (5), the reactor used by oxidation blowing are blast furnace, reverberatory furnace, bottom convertor, side-blown
Stove or top blast stove, preferably reverberatory furnace or bottom convertor.
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 the leaching of normal pressure alkali
Content is low, can the valuable metal such as synthetical recovery antimony, lead, bismuth, reduce the content of arsenic in product；
2nd, it is of the invention by the way of catalysis oxidation, by As3+It is oxidized to As5+, it is subsequently to consolidate arsenic operation to have done follow-up preparation
Work；
3rd, the present invention changes feed way, the pH value of precise control building-up process on the basis of original technology, using tune
The solid arsenic mineral for combining synthesis one or more in control growth method, fractional crystallisation method, lime heavy arsenic method and precipitation transformation method exists
Stabilization is stored up under the conditions of pH scopes 2~11 wide and strong reducing property, As is no longer migrated, and also making the As of smelting system has one
Ideal open circuit, is a kind of simple technological process, 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.
In a word, the rational operation collocation of the present invention, by strictly controlling the conditional parameter in each operation, arsenic is pacified
The valuable metals such as full disposal, antimony, lead, bismuth are recycled and effectively utilize, and have reached environmental protection, economy, energy-conservation, resource utilization high
Purpose, realize the innoxious and maximum resource utilization of arsenic.Wet processing is used because arsenic is separated with other elements
Avoid massive pollution and utilization of resources problem not high that pyrogenic process is brought, whole technique substantially three-waste free discharge,
All resources obtain maximal efficiency utilization, and products therefrom is easy to follow-up treatment and processing, so the present invention has environmental protection, warp
Ji, energy-conservation, the advantage of resource utilization high.
Brief description of the drawings
Fig. 1 is the inventive method schematic flow sheet.
Specific embodiment
Below to the detailed narration of technical scheme, wherein the percentage composition is mass fraction.
Arsenic weight/mass percentage composition 1%~60%, antimony weight/mass percentage composition 1%~55%, lead weight/mass percentage composition 0.1%~
35%, zinc weight/mass percentage composition 0.1%~30%, copper mass percentage composition 0.1~5%, tellurium weight/mass percentage composition 0.01%~
3%, selenium weight/mass percentage composition 0.01%~3%.
As shown in figure 1, a kind of integrated conduct method of arsenic-containing smoke dust, comprises the following steps：
1st, normal pressure water logging operation, extraction temperature be room temperature~100 DEG C, time be 30~240min, the solid volume mass of liquid
Than being 3:1~20:1(ml:G), mixing speed be 50~1000r/min under conditions of arsenic-containing smoke dust is carried out at normal pressure water logging
Reason, makes arsenic and a small amount of antimony be dissolved into alkali leaching leachate, and the valuable metal such as most of antimony, lead, bismuth is stayed in leached mud.It is described
Liquid solid product mass ratio refers to the volume mass ratio of NaOH solution and arsenic-containing smoke dust in terms of ml/g.
2nd, leachate catalysis oxidation operation, by way of catalysis oxidation, adds oxidizing gas and catalyst, will leach
The As of the overwhelming majority in liquid3+It is transformed into As5+, oxidated solution enters into solid arsenic operation.Oxidizing gas are oxygen, air or richness
Oxygen air, catalyst is KMnO4.In 1~20L/min, As/Mn mol ratios are controlled 5 for the gas flow control of oxidizing gas:
1~50:1, the temperature control of catalytic oxidation system control is at 30 DEG C~120 DEG C.
3rd, the solid arsenic operation of oxidated solution, the solid arsenic of oxidated solution using regulation and control growth method, fractional crystallisation method, the heavy arsenic method of lime and
One or more in precipitation transformation method combination, the solid arsenic mineral of synthesizing stable, then using store up or cement solidification by the way of
The solid arsenic mineral of solidification.
4th, leached mud washing procedure, fluidization wash is used 2~3 times by leached mud, and the solvable arsenic in leached mud is down to
Less than 0.1%；Washing lotion can be returned and leach i.e. return to step (1) for alkaline leaching feed liquid used.
5th, washery slag reclaims valuable metal operation, and washery slag allocates charcoal, coal and a small amount of soda ash (Na into after drying2CO3), 900~
1200 DEG C and under having a conditionings such as C, CO, the oxide such as Sb, Pb, Bi is equally also reduced into simple substance form and enters lead-antimony alloy
In.Pit ash and a small amount of arsenic, antimony, the oxide of lead and soda ash react light " the bubble slag " of many alveolar substances for being generated, and float over antimony
Liquid surface.After the completion of reduction, bubble slag is clawed, under conditions of 650~800 DEG C of muffle of temperature, 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 Sb2O3, using antimony oxygen
Change in the big necessary temperature of calorimetric maintenance reaction device and stove for producing.Because the concentration of melt body surface metal antimony has comparative advantage,
Metallic antimony property is more active than lead, bismuth, the antimony in aluminium alloy is oxidized to Sb2O3Flue dust is volatized into, lead, bismuth then stay in reactor
In the lead of bottom, realize that a stove is dual-purpose.
Embodiment 1
So that domestic certain Lead And Zinc Smelter is containing arsenic smoke dust as an example, it includes following main component by percentage to the quality：Pb
5.26%, As 39.65%, Sn 0.5%, Sb 29.36%, Zn 0.12%, Se 0.04%.
The high-arsenic antimony flue dust of certain mass is weighed in reactor, mass ratio 10 is accumulated by liquid solid:1(ml:G), stir
Speed 700r/min, NaOH concentration 1mol/L, 80 DEG C of extraction temperature, the condition of extraction time 2h carry out leaching experiment.Leach knot
Shu Hou, removes slurry filtration and separates, arsenic leaching rate 72.36%., each element concentration Pb 86.00ppm, Se in leachate
1.80ppm, Zn 20ppm, Sb 1.36g/L, As 28.69g/L.
Leachate is using the method for catalysis oxidation by As3+It is oxidized to As5+, the condition for controlling is that oxygen flow is 5L/
Min, As/Mn mol ratio are controlled 10:1, as a result catalytic oxidation system temperature control shows at 90 DEG C, As3+Conversion ratio be
98.45%.
Using the solid arsenic mineral of regulation and control growth method synthesizing high-stability, the condition for controlling is to adjust washing lotion pH value to oxidated solution
Be will heat up after to 2 to 90 DEG C, risen to ferrous nitrate solution and sodium carbonate after predetermined temperature, while being slowly added into arsenic containing solution
In, and be passed through oxygen and make Fe2+It is oxidized to Fe3+, the addition speed of ferrous nitrate solution is 5ml/min, the addition speed of sodium carbonate
It is 5ml/min, oxygen flow 10L/min, Fe/As mol ratio 2 prepares the solid arsenic mineral of high stability, synthesis under reaction time 12h
Solid arsenic mineral meet GB5085.3-2007 (solid waste judging standard-leaching characteristic identification) regulation, can store up safely.Press
Weight according to cement and solid arsenic mineral compares 6:1, coat solid arsenic mineral with cement.Fine coal is added in cement, fine coal addition is
The 30% of cement hardener.
Leached mud accumulates mass ratio 5 according to liquid solid:1(ml:G) leached mud is washed 2 times using fluidization wash tower, washery slag contains
Solvable arsenic 0.1%.
Washery slag allocates charcoal, coal and soda ash into after drying, and reduction melting, melting generation bubble are carried out in 1200 DEG C of reverberatory furnaces
Slag, lead-antimony alloy and flue dust.Bubble slag send lead to smelt, and flue dust returns to reduction melting or the leaching of normal pressure alkali, and lead-antimony alloy blows into oxidation
Refining operation.Under the conditions of the muffle of 700 DEG C of blowing temperature of oxidation, to primary air is blasted in alloy, while being passed through to reactor
Auxiliary air, makes antimony vapour aoxidize generation Sb2O3, the Sb of generation2O3As stibium trioxide product.Blowing slag returns former smelting system, and
Lead bullion after oxidation blowing send lead rectification systems.Pb contains containing 24.38%, Sb containing 70.46%, As wherein in lead-antimony alloy
3.08%；The stibium trioxide powder of generation meets the trade mark specified in GB/T 4062-2013 for Sb2O399.00 stibium trioxide powder；In lead bullion
Containing Pb97.21%, containing Sb1.08%, containing As 0.37%.
Embodiment 2
So that domestic certain Lead And Zinc Smelter is containing arsenic smoke dust as an example, it includes following main component by percentage to the quality：
Pb10.39%, As 34.59%, Sn 1.45%, Sb 20.54%, Zn 0.11%, Se 0.24%.
The high-arsenic antimony flue dust of certain mass is weighed in reactor, mass ratio 10 is accumulated by liquid solid:1(ml:G), stir
Speed 700r/min, NaOH concentration 3mol/L, 50 DEG C of extraction temperature, extraction time 4h carry out leaching experiment.After leaching terminates, move
Go out slurry to be separated by filtration, arsenic leaching rate 52.06%., each element concentration Pb 87ppm, Se 0.52ppm, Zn in leachate
71ppm, Sb 1.24g/L, As 18.01g/L.
Leachate is using the method for catalysis oxidation by As3+It is oxidized to As5+, the condition for controlling is that oxygen flow is 10L/
Min, As/Mn mol ratio are controlled 40:1, as a result catalytic oxidation system temperature control shows at 30 DEG C, As3+Conversion ratio be
93.54%.
The method that the solid arsenic of oxidated solution uses fractional crystallisation method, control condition is that initial pH value is adjusted into 1.5, adds nitric acid
Ferrous solution and sodium carbonate, Fe/As mol ratios are 2.5, and reaction temperature is 85 DEG C, and the reaction time is 4h, mixing speed 200r/min,
The addition speed of iron nitrate solution is 5ml/min, and the addition speed of sodium carbonate is 5ml/min.The solid arsenic mineral of synthesis meets
GB5085.3-2007 (solid waste judging standard-leaching characteristic identification) specifies, can store up safely.According to cement and solid arsenic minerals
The weight of thing compares 4:1, coat solid arsenic mineral with cement.Fine coal is added in cement, fine coal addition is cement hardener
40%.
Leached mud accumulates mass ratio 5 according to liquid solid:1(ml:G) leached mud is washed 2 times using fluidization wash tower, washery slag contains
Solvable arsenic 0.1%.
Washery slag allocates charcoal, coal and soda ash into after drying, and reduction melting, melting generation bubble are carried out in 1150 DEG C of reverberatory furnaces
Slag, lead-antimony alloy and flue dust.Bubble slag send lead to smelt, and flue dust returns to reduction melting or the leaching of normal pressure alkali, and lead-antimony alloy blows into oxidation
Refining operation.Under the conditions of the muffle of 800 DEG C of blowing temperature of oxidation, to primary air is blasted in alloy, while being passed through to reactor
Auxiliary air, makes antimony vapour aoxidize generation Sb2O3, the Sb of generation2O3As stibium trioxide product.Blowing slag returns former smelting system, and
Lead bullion after oxidation blowing send lead rectification systems.Pb contains containing 29.36%, Sb containing 63.89%, As wherein in lead-antimony alloy
4.67%；The stibium trioxide powder of generation meets the trade mark specified in GB/T 4062-2013 for Sb2O399.00 stibium trioxide powder；In lead bullion
Containing Pb96.14%, containing Sb2.61%, containing As 0.46%.
Embodiment 3
So that domestic certain Lead And Zinc Smelter is containing arsenic smoke dust as an example, it includes following main component by percentage to the quality：Pb
19.57%, As 24.26%, Sn 1.47%, Sb 30.45%, Zn 0.16%, Se 0.21%.
The high-arsenic antimony flue dust of certain mass is weighed in reactor, mass ratio 5 is accumulated by liquid solid:1(ml:G) speed, is stirred
Degree 1000r/min, NaOH concentration 1mol/L, 30 DEG C of extraction temperature, extraction time 2h carry out leaching experiment.After leaching terminates, move
Go out slurry to be separated by filtration, arsenic leaching rate 42.26%., each element concentration Pb 124ppm, Se 0.67ppm, Zn in leachate
107ppm, Sb 2.02g/L, As 10.25g/L.
Leachate is using the method for catalysis oxidation by As3+It is oxidized to As5+, the condition for controlling is that oxygen flow is 1L/
Min, As/Mn mol ratio are controlled 20:1, as a result catalytic oxidation system temperature control shows at 120 DEG C, As3+Conversion ratio be
87.67%.
The pH value of oxidated solution is adjusted to 1.5, CaO and Ca (OH) is added in the way of continuous charging2As heavy arsenical,
Ca/As mol ratios are 6, and the sedimentation time is 40 hours, and reaction temperature is 40 DEG C.Iron nitrate solution and carbon are added in arsenic removal process
Arsenate ionic reaction in sour sodium, ferric ion and solution generates the solid arsenic mineral of high stability, the control of Fe/As mol ratios
5.The addition speed of iron nitrate solution is 5ml/min, and the addition speed of sodium carbonate is 5ml/min, and the solid arsenic mineral of synthesis is accorded with
GB5085.3-2007 (solid waste judging standard-leaching characteristic identification) regulations are closed, can be stored up safely.According to cement and solid arsenic
The weight of mineral compares 5:1, coat solid arsenic mineral with cement.Fine coal is added in cement, fine coal addition is cement hardener
30%.
Leached mud accumulates mass ratio 5 according to liquid solid:1(ml:G) leached mud is washed 2 times using fluidization wash tower, washery slag contains
Solvable arsenic 0.1%.
Washery slag allocates charcoal, coal and soda ash into after drying, and reduction melting, melting generation bubble are carried out in 1200 DEG C of reverberatory furnaces
Slag, lead-antimony alloy and flue dust.Bubble slag send lead to smelt, and flue dust returns to reduction melting or the leaching of normal pressure alkali, and lead-antimony alloy blows into oxidation
Refining operation.Under the conditions of the muffle of 650 DEG C of blowing temperature of oxidation, to primary air is blasted in alloy, while being passed through to reactor
Auxiliary air, makes antimony vapour aoxidize generation Sb2O3, the Sb of generation2O3As stibium trioxide product.Blowing slag returns former smelting system, and
Lead bullion after oxidation blowing send lead rectification systems.Pb contains containing 27.89%, Sb containing 66.96%, As wherein in lead-antimony alloy
4.21%；The stibium trioxide powder of generation meets the trade mark specified in GB/T 4062-2013 for Sb2O399.00 stibium trioxide powder；In lead bullion
Containing Pb96.69%, containing Sb2.12%, containing As 0.49%.
Embodiment 4
So that domestic certain Lead And Zinc Smelter is containing arsenic smoke dust as an example, it includes following main component by percentage to the quality：Pb
14.23%, As 27.54%, Sn 1.41%, Sb 21.25%, Zn 0.27%, Se 0.15%.
The high-arsenic antimony flue dust of certain mass is weighed in reactor, mass ratio 10 is accumulated by liquid solid:1(ml:G), stir
Speed 700r/min, NaOH concentration 1mol/L, 80 DEG C of extraction temperature, extraction time 2h carry out leaching experiment.After leaching terminates, move
Go out slurry to be separated by filtration, arsenic leaching rate 44.58%., each element concentration Pb 142ppm, Se 0.78ppm, Zn in leachate
76ppm, Sb 1.57g/L, As 12.28g/L.
Leachate is using the method for catalysis oxidation by As3+It is oxidized to As5+, the condition for controlling is that oxygen flow is 5L/
Min, As/Mn mol ratio are controlled 20:1, as a result catalytic oxidation system temperature control shows at 60 DEG C, As3+Conversion ratio be
94.78%.
The pH value of oxidated solution is adjusted to 1.5, CaO, Ca (OH) are added in the way of continuous charging2In one or two
Used as heavy arsenical, Ca/As mol ratios are 5, and the sedimentation time is 50 hours, and reaction temperature is 60 DEG C, the solid arsenic mineral calcium arsenate of generation.
Weight according to cement and solid arsenic mineral compares 5:1, coat solid arsenic mineral with cement.Fine coal, fine coal addition are added in cement
It is the 40% of cement hardener.
Leached mud accumulates mass ratio 5 according to liquid solid:1(ml:G) leached mud is washed 2 times using fluidization wash tower, washery slag contains
Solvable arsenic 0.1%.
Washery slag allocates charcoal, coal and soda ash into after drying, and reduction melting, melting generation bubble are carried out in 1200 DEG C of reverberatory furnaces
Slag, lead-antimony alloy and flue dust.Bubble slag send lead to smelt, and flue dust returns to reduction melting or the leaching of normal pressure alkali, and lead-antimony alloy blows into oxidation
Refining operation.Under the conditions of the muffle for aoxidizing 750 DEG C of blowing, to primary air is blasted in alloy, while being passed through to reactor secondary
Air, makes antimony vapour aoxidize generation Sb2O3, the Sb of generation2O3As stibium trioxide product.Blowing slag returns former smelting system, and aoxidizes
Lead bullion after blowing send lead rectification systems.Pb contains 3.51% containing 29.56%, Sb containing 64.58%, As wherein in lead-antimony alloy；It is raw
Into stibium trioxide powder meet the trade mark specified in GB/T 4062-2013 for Sb2O399.00 stibium trioxide powder；Contain in lead bullion
Pb95.95%, containing Sb2.47%, containing As 0.56%.
Although above the present invention is described in detail with a general description of the specific embodiments,
On the basis of the present invention, it can be made some modifications or improvements, this will be apparent to those skilled in the art.Cause
This, these modifications or improvements, belong to the scope of protection of present invention without departing from theon the basis of the spirit of the present invention.
Claims (9)
1. a kind of integrated conduct method of arsenic-containing smoke dust, it is characterised in that comprise the following steps：
(1) normal pressure alkali leaching
Extraction temperature be room temperature~100 DEG C, the time be 30~240min, liquid solid product mass ratio be 3:1~20:1(ml:g)、
NaOH concentration is 0.1mol/L~6mol/L, mixing speed to carry out normal pressure to arsenic-containing smoke dust under conditions of 50~1000r/min
Alkali leaching is processed；Filter to obtain leachate and leached mud；Liquid solid product mass ratio refers to NaOH solution and cigarette containing arsenic in terms of ml/g
The volume mass ratio of dirt；
(2) leachate catalysis oxidation
By way of catalysis oxidation, to oxidizing gas and catalyst is added in step (1) gained leachate, by leachate
As3+It is transformed into As5+；
(3) the solid arsenic of oxidated solution
By the leachate after step (2) gained oxidation using regulation and control growth method, fractional crystallisation method, the heavy arsenic method of lime, precipitation conversion
The solid arsenic mineral of any one or a few method synthesizing stable for combining in method, then stores up or coats solidification with cement；
(4) leached mud washing
Step (1) gained leached mud is used into fluidization wash, the solvable arsenic in leached mud is down to less than 0.1%；
(5) washery slag reclaims valuable metal
Will step (4) gained washery slag dry after allocate charcoal, coal and appropriate soda ash into, in reactor in 900~1200 DEG C, have C,
Reduction melting, melting generation bubble slag, lead-antimony alloy and flue dust are carried out under CO conditionings；By the flue dust return reduction melting or
Normal pressure alkali soaks step；Lead is sent to smelt the bubble slag；
The lead-antimony alloy is 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；The blowing slag is returned into reduction melting operation；Lead is sent by the lead bullion
Refining.
2. method according to claim 1, it is characterised in that the arsenic-containing smoke dust includes following master by percentage to the quality
Want 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 and 2, it is characterised in that oxidizing gas described in step (2) are oxygen, sky
Gas or oxygen-enriched air, the gas flow of oxidizing gas are controlled in 1~20L/min；
And/or, the catalyst is KMnO4；It is preferred that As is controlled 5 with Mn mol ratios in reaction system:1~50:1；
And/or, the temperature control of catalytic oxidation system control is at 30 DEG C~120 DEG C.
4. method according to claim 1 and 2, it is characterised in that regulating and controlling growth method described in step (3) includes：By institute
Obtain pH of leaching solution and be adjusted to 1.5~3, heavy arsenical ferrous salt solution is added while oxidizing gas are continually fed into, in temperature
75~90 DEG C of 5~24h of reaction, while adding nertralizer regulation and control reaction to be reacted under the conditions of pH value 1.5~3, make Fe3+With
AsO4 3-The solid arsenic mineral of reaction generation high stability；Wherein, oxidizing gas flowrate is 1~20L/min, Fe in reaction system
It is 2~5 with the mol ratio of As:1；The oxidizing gas are oxygen, air or oxygen-enriched air；The ferrous salt solution is sulfuric acid
At least one in ferrous iron solution, solution of ferrous chloride or ferrous nitrate solution, the nertralizer be sodium carbonate, sodium acid carbonate or
At least one in NaOH.
5. method according to claim 1 and 2, it is characterised in that fractional crystallisation method includes described in step (3)：By institute
The initial pH value for obtaining leachate is adjusted to 1.5~3, adds iron salt solutions, and the mol ratio for making Fe and As in the leachate is 1~8:
1, while adding nertralizer regulation and control reaction to be reacted under the conditions of pH value 1.5~3, make Fe3+With AsO4 3-Reaction generation is high steady
Qualitatively consolidate arsenic mineral；Control reaction condition：Temperature be room temperature~120 DEG C, the reaction time be 1~10h, mixing speed 50~
500r/min, the iron salt solutions are at least one in ferrum sulfuricum oxydatum solutum, ferric chloride solution or iron nitrate solution, the neutralization
Agent is at least one in sodium carbonate, sodium acid carbonate or NaOH.
6. method according to claim 1 and 2, it is characterised in that the heavy arsenic method of lime described in step (3) includes：By institute
PH of leaching solution after must aoxidizing is adjusted to 1.5~3, and CaO, Ca (OH) are added in the way of continuous charging2In one or two
Used as heavy arsenical, the mol ratio for making Ca and As in the leachate is 2~8:1, the sedimentation time is 5~100 hours, reaction temperature
It is 10 DEG C~90 DEG C.
7. method according to claim 1 and 2, it is characterised in that precipitation transformation method includes described in step (3)：Xiang Bu
Suddenly iron salt solutions are added in (2) gained reaction system, the mol ratio of Fe and As in reaction system is controlled 1~5:1, while plus
Enter nertralizer regulation and control reaction to be reacted under the conditions of pH value 1.5~3, make Fe3+With AsO4 3-The solid arsenic of reaction generation high stability
Mineral；The iron salt solutions are at least one in ferrum sulfuricum oxydatum solutum, ferric chloride solution or iron nitrate solution, and the nertralizer is
At least one in sodium carbonate, sodium acid carbonate or NaOH.
8. method according to claim 1 and 2, it is characterised in that the control condition of cement solidification is to press in step (3)
Weight according to cement and solid arsenic mineral compares 2:1~10:1 coats solid arsenic mineral with cement；Preferably, the cement and solid arsenic mineral
Weight ratio be 4:1.
9. method according to claim 8, it is characterised in that fine coal is also added with the cement, fine coal addition is
The 20%~60% of cement quality, preferably 40%.
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