CN106834714A - A kind of integrated conduct method of arsenic-containing material - Google Patents

A kind of integrated conduct method of arsenic-containing material Download PDF

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CN106834714A
CN106834714A CN201611192118.4A CN201611192118A CN106834714A CN 106834714 A CN106834714 A CN 106834714A CN 201611192118 A CN201611192118 A CN 201611192118A CN 106834714 A CN106834714 A CN 106834714A
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arsenic
lead
antimony
oxidation
leachate
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CN106834714B (en
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刘智勇
刘志宏
李启厚
周亚明
李玉虎
姚伟
张涛
李思唯
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Central South University
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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
    • A—HUMAN NECESSITIES
    • A62—LIFE-SAVING; FIRE-FIGHTING
    • A62D—CHEMICAL MEANS FOR EXTINGUISHING FIRES OR FOR COMBATING OR PROTECTING AGAINST HARMFUL CHEMICAL AGENTS; CHEMICAL MATERIALS FOR USE IN BREATHING APPARATUS
    • A62D3/00—Processes for making harmful chemical substances harmless or less harmful, by effecting a chemical change in the substances
    • A62D3/30—Processes for making harmful chemical substances harmless or less harmful, by effecting a chemical change in the substances by reacting with chemical agents
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    • 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
    • C22B13/02—Obtaining lead by dry processes
    • C22B13/025—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
    • 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
    • C22B30/00—Obtaining antimony, arsenic or bismuth
    • C22B30/06—Obtaining bismuth
    • 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
    • C22B7/001—Dry processes
    • 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
    • C22B7/008—Wet processes by an alkaline or ammoniacal leaching
    • 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
    • A62D2101/00—Harmful chemical substances made harmless, or less harmful, by effecting chemical change
    • A62D2101/40—Inorganic substances
    • A62D2101/43—Inorganic substances containing heavy metals, in the bonded or free state
    • 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
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    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P10/00—Technologies related to metal processing
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Abstract

The present invention relates to a kind of integrated conduct method of arsenic-containing material, 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.The method that the present invention is provided is soaked by normal pressure alkali, solvable arsenic in removing flue dust, after trivalent arsenic is pentavalent arsenic through catalysis oxidation in leachate, using the solid arsenic mineral of fractional crystallisation method synthesizing stable, then solid arsenic mineral is solidified by the way of storing up, 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

A kind of integrated conduct method of arsenic-containing material
Technical field
The invention belongs to metallurgical technology field, and in particular to a kind of integrated conduct method of arsenic-containing material.
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 material 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 the Leaching way soaked by normal pressure alkali, solvable arsenic in removing flue dust, and with catalysis oxidation Trivalent arsenic is oxidized to pentavalent arsenic by mode, and, through the solid arsenic mineral of fractional crystallisation method synthesizing high-stability, leached mud is through stream for oxidated solution The operations such as state washing, reduction melting, oxidation blowing, make each valuable element be recycled utilization.The method is by arsenic from flue dust Remove and solidify, and antimony, lead, bismuth etc. are stayed in dearsenification slag as far as possible, realize that arsenic is separated and innoxious with valuable metal.This hair Bright comprehensive resource utilization rate is high, raw material wide adaptation range, solves pollution problem in traditional handicraft extraction process, particularly lead zinc The cigarette ash that smelting process is produced, advantage of the invention is more obvious.
A kind of integrated conduct method of arsenic-containing material 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；The valuable element includes antimony, lead, bismuth；
(2) leachate catalysis oxidation
By way of catalysis oxidation, to oxidizing gas and catalyst is added in step (1) gained leachate, will leach The As of the overwhelming majority in liquid3+It is transformed into As5+；Oxidated solution enters into solid arsenic operation；
(3) the solid arsenic of leachate
The initial pH value of the leachate after step (2) gained oxidation is adjusted to 1.5~3, iron salt solutions are added thereto to, made The mol ratio of Fe and As is 1~8 in the leachate:1, solid arsenic reaction is carried out, 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；Control reaction condition:Temperature is room Temperature~120 DEG C, the reaction time is 1~10h, 50~500r/min of mixing speed；The iron salt solutions are ferrum sulfuricum oxydatum solutum, chlorination At least one in ferrous solution or iron nitrate solution, the nertralizer be sodium carbonate, sodium acid carbonate or NaOH at least It is a kind of；
(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 melting or normal pressure alkali leaching step；
Lead is sent to smelt the bubble slag；
The lead-antimony alloy is carried out into oxidation blowing, air (temperature preferably 650~800 is passed through under conditions of muffle DEG C), obtain antimony vapour, blowing slag and lead bullion；By antimony vapour oxidation generation antimony oxide, as stibium trioxide product；By institute State blowing slag and return to 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 (arsenic-containing material) of the present invention includes following main component by percentage to the quality:
Arsenic:1%~60%, antimony:1%~55%, lead:0.1%~35%, zinc:0.1%~30%, copper:0.1%~ 5%, tellurium:0.01%~3%, selenium:0.01%~3%.
The integrated conduct method of the above-mentioned arsenic-containing material of the present invention, wherein
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, the oxidizing gas are oxygen, air or oxygen-enriched air；It is excellent Selection of land, the gas flow of above-mentioned oxidizing gas is controlled in 1~20L/min.
Described in step (2) in the operation of catalysis oxidation, the catalyst is KMnO4；Preferably, in reaction system As with Mn mol ratios are controlled 5:1~50:1.
Described in step (2) in the operation of catalysis oxidation, the reaction temperature that catalytic oxidation system is controlled is 30 DEG C~120 ℃。
The solid arsenic of oxidated solution described in step (3) is using the solid arsenic mineral of fractional crystallization regular way synthesizing high-stability.
The condition of the solid arsenic mineral of fractional crystallisation method synthesizing high-stability described in step (3) is, the initial pH of oxidated solution Value is adjusted to 1.5~3, adds iron salt solutions and nertralizer, makes Fe3+With AsO4 3-The solid arsenic mineral of reaction generation high stability；It is described The mol ratio of Fe and As is 1~8 in leachate:1, reaction temperature is room temperature~120 DEG C, and the reaction time is 1~10h, stirring speed 50~500r/min of degree, the iron salt solutions are at least one in ferrum sulfuricum oxydatum solutum, ferric chloride solution or iron nitrate solution, institute It is at least one in sodium carbonate, sodium acid carbonate or NaOH to state nertralizer.
Preferably, the addition speed control of the iron salt solutions and nertralizer is in 3ml/min~20ml/min.
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+, solve the dysoxidizable problem of trivalent arsenic；
3rd, the present invention on the basis of original technology change feed way, the pH value of precise control building-up process, using point The solid arsenic mineral of cloth crystallisation synthesis stabilization under the conditions of pH scopes 2~11 wide and strong reducing property is stored up, and As is no longer migrated, Also making the As of smelting system has an ideal open circuit, is a kind of technological process simple, resources conservation, environment-friendly Method, and the solid arsenic mineral that fractional crystallisation method is prepared is because its crystallinity is high, BET specific surface area is small, stable region field width, and Possesses high stability, so as to be easy to store up；
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 Full disposal, antimony, lead, bismuth etc. are recycled and effectively utilize, and have reached environmental protection, economy, energy-conservation, the purpose of resource utilization high, Realize the innoxious and maximum resource utilization of arsenic.Use wet processing and avoid fire because arsenic is separated with other elements Massive pollution and utilization of resources problem not high that method is brought, whole technique substantially three-waste free discharge, all resources Obtain maximal efficiency utilization, products therefrom is easy to follow-up treatment and processing, thus the present invention have environmental protection, economy, 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.
The arsenic-containing smoke dust (arsenic-containing material) being below related to includes following main component by percentage to the quality:Arsenic quality percentage Content 1%~60%, antimony weight/mass percentage composition 1%~55%, lead weight/mass percentage composition 0.1%~35%, zinc quality percentage contains Amount 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 material, comprises the following steps:
1st, normal pressure alkali leaching operation, control NaOH concentration for 0.1mol/L~6mol/L, extraction temperature be room temperature~100 DEG C, Time be 30~240min, liquid solid product mass ratio be 3:1~20:1(ml:G), mixing speed is 50~1000r/min.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, catalysis oxidation operation, by way of catalysis oxidation, adds oxidizing gas and catalyst, will be exhausted in leachate Most As3+It is transformed into As5+, oxidated solution enters into solid arsenic operation.Oxidizing gas be oxygen, air or oxygen-enriched 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 condition for controlling is that the initial pH value of oxidated solution is adjusted to 1.5~3, adds molysite Solution, while addition nertralizer makes Fe3+With AsO4 3-The solid arsenic mineral of reaction generation high stability, Fe/As mol ratios are 1~8, Reaction temperature is room temperature~120 DEG C, and the reaction time is 1~10h, and 50~500r/min of mixing speed, the iron salt solutions are sulphur At least one in sour ferrous solution, ferric chloride solution or iron nitrate solution, the nertralizer is sodium carbonate, sodium acid carbonate or hydrogen-oxygen The addition speed control of at least one in change sodium, the iron salt solutions and nertralizer is in 3ml/min~20ml/min.
4th, leached mud washing procedure, at room temperature using fluidization wash tower washing leached mud 2~3 times, makes solvable in washery slag The content ＜ 0.1% of arsenic；Washing lotion can be returned and leach i.e. return to step (1) for alkaline leaching feed liquid used；
5th, washery slag synthetical recovery operation, 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 of the valuable metal such as Sb, Pb, Bi is equally also reduced into simple substance form and enters lead In antimony alloy.Pit ash and a small amount of arsenic, antimony, the oxide of lead and soda ash react light " the bubble slag " of many alveolar substances for being generated, Float over antimony liquid surface.After the completion of reduction, bubble slag is clawed, under conditions of 650 DEG C~800 DEG C muffle of blowing temperature are aoxidized, to antimony Primary air is blasted in liquid, antimony is volatilized and is produced a large amount of antimony vapours, while being passed through auxiliary air to reactor, aoxidize antimony vapour Generation antimony oxide, antimony liquid temperature degree in the big necessary temperature of calorimetric maintenance reaction device produced using antimony oxidation and stove.Due to The concentration of melt body surface metal antimony has comparative advantage, and metallic antimony property is more active than lead, bismuth, the antimony in aluminium alloy is oxidized to three oxygen Change two antimony and be volatized into flue dust, lead, bismuth are then stayed in the lead of reactor bottom, realize that a stove is dual-purpose.Wherein described reduction melting, oxidation Blowing reactor used can be blast furnace, reverberatory furnace, bottom convertor, side-blown converter or top blast stove, preferably reverberatory furnace or bottom convertor.
The following is embodiments of the invention.
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；Measure arsenic leaching rate 72.36%., each element concentration in leachate:Pb 86.00ppm, Se 1.80ppm, Zn 20ppm, Sb 1.36g/L, As 28.69g/L.
By gained leachate using the method for catalysis oxidation by As3+It is oxidized to As5+, the condition for controlling is that oxygen flow is The mol ratio of 5L/min, As and Mn is controlled 10:1, as a result catalytic oxidation system temperature control shows at 90 DEG C, As3+Conversion Rate is 98.45%.
The solid arsenic of oxidated solution uses the solid arsenic mineral of the method synthesizing high-stability of fractional crystallisation method, and control condition is will be initial PH value is adjusted to 1.5, adds iron nitrate solution and sodium carbonate, and 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 8ml/min, and the addition speed of sodium carbonate is 8ml/min. The solid arsenic mineral of synthesis meets GB5085.3-2007 (solid waste judging standard-leaching characteristic identification) regulations, can safe heap Deposit.
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 lead-antimony alloy, while to reactor Auxiliary air is passed through, antimony vapour is aoxidized generation antimony oxide.
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.Pb contains 3.08% containing 24.38%, Sb containing 70.46%, As wherein in lead-antimony alloy；The stibium trioxide powder symbol of generation It is Sb to close the trade mark specified in GB/T 4062-20132O399.00 stibium trioxide powder；Contain Pb97.21% in lead bullion, contain 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:Pb 10.39%, As 34.59%, Sn 1.45%, Sb 20.54%, Zn 0.11%, Se 0.24%.
The high-arsenic antimony flue dust of certain mass is weighed in 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, the condition of extraction time 4h carry out leaching experiment.Leach knot Shu Hou, removes slurry filtration and separates；Arsenic leaching rate 52.06%. is measured, each element concentration Pb 87ppm, Se in leachate 0.52ppm, Zn 71ppm, Sb 1.24g/L, As 18.01g/L.
Leachate is using the method for catalysis oxidation by As3+It is oxidized to As5+, the condition for controlling is that oxygen flow is 10L/ The mol ratio of min, As and Mn is controlled 40:1, as a result catalytic oxidation system temperature control shows at 30 DEG C, As3+Conversion ratio It is 92.31%.
The solid arsenic of oxidated solution uses the solid arsenic mineral of the method synthesizing high-stability of fractional crystallisation method, and control condition is will be initial PH value is adjusted to 2, adds iron nitrate solution and sodium carbonate, and Fe/As mol ratios are 6, and reaction temperature is 120 DEG C, and the reaction time is 4h, Mixing speed 350r/min, the addition speed of iron nitrate solution is 5ml/min, and the addition speed of sodium carbonate is 5ml/min.Synthesis Solid arsenic mineral meet GB5085.3-2007 (solid waste judging standard-leaching characteristic identification) regulation, can store up safely.
Leached mud 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 antimony oxide.
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.Pb contains 4.67% containing 29.36%, Sb containing 63.89%, As wherein in lead-antimony alloy；The stibium trioxide powder symbol of generation It is Sb to close the trade mark specified in GB/T 4062-20132O399.00 stibium trioxide powder；Contain Pb96.14% in lead bullion, contain 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, the condition of extraction time 2h carry out leaching experiment.Leaching terminates Afterwards, slurry filtration is removed to separate；Arsenic leaching rate 42.26%. is measured, each element concentration Pb 124ppm in leachate, Se0.67ppm, Zn 107ppm, Sb 2.02g/L, As 10.25g/L.
By gained leachate using the method for catalysis oxidation by As3+It is oxidized to As5+, the condition for controlling is that oxygen flow is The mol ratio of 1L/min, As and Mn is controlled 20:1, as a result catalytic oxidation system temperature control shows at 120 DEG C, As3+Turn Rate is 89.36%.
The solid arsenic of oxidated solution uses the solid arsenic mineral of the method synthesizing high-stability of fractional crystallisation method, and control condition is will be initial PH value is adjusted to 2, adds iron nitrate solution and sodium carbonate, and Fe/As mol ratios are 8, and reaction temperature is 120 DEG C, and the reaction time is 4h, Mixing speed 200r/min, the addition speed of iron nitrate solution is 10ml/min, and the addition speed of sodium carbonate is 10ml/min.Close Into solid arsenic mineral meet GB5085.3-2007 (solid waste judging standard-leaching characteristic identification) regulation, can store up safely.
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 antimony oxide.
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.Pb contains 4.21% containing 27.89%, Sb containing 66.96%, As wherein in lead-antimony alloy；The stibium trioxide powder symbol of generation It is Sb to close the trade mark specified in GB/T 4062-20132O399.00 stibium trioxide powder；Contain Pb96.69% in lead bullion, contain Sb2.12%, containing As 0.49%.
Although above the present invention is described in detail with a general description of the specific embodiments, On the basis of the present invention, it can be made some modifications or improvements, this will be apparent to those skilled in the art.Cause This, these modifications or improvements, belong to the scope of protection of present invention without departing from theon the basis of the spirit of the present invention.

Claims (7)

1. a kind of integrated conduct method of arsenic-containing material, 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；The valuable element includes antimony, lead, bismuth；
(2) leachate catalysis oxidation
By way of catalysis oxidation, to oxidizing gas and catalyst is added in step (1) gained leachate, by leachate The As of the overwhelming majority3+It is transformed into As5+；Oxidated solution enters into solid arsenic operation；
(3) the solid arsenic of leachate
The initial pH value of the leachate after step (2) gained oxidation is adjusted to 1.5~3, iron salt solutions are added thereto to, made described The mol ratio of Fe and As is 1~8 in leachate:1, carry out solid arsenic reaction, while add nertralizer regulation and control reaction 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；Control reaction condition:Temperature be room temperature~ 120 DEG C, the reaction time is 1~10h, 50~500r/min of mixing speed；The iron salt solutions are ferrum sulfuricum oxydatum solutum, iron chloride is molten At least one in liquid or iron nitrate solution, the nertralizer is at least one in sodium carbonate, sodium acid carbonate or NaOH；
(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. the integrated conduct method of arsenic-containing material according to claim 1, it is characterised in that:The arsenic-containing smoke dust is with quality Percentages include 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%.
3. the integrated conduct method of arsenic-containing material according to claim 1 and 2, it is characterised in that oxygen described in step (2) The property changed gas is oxygen, air or oxygen-enriched air；Preferably, the gas flow of the oxidizing gas is controlled in 1~20L/ min。
4. the integrated conduct method of arsenic-containing material according to claim 1 and 2, it is characterised in that step is urged described in (2) Agent is KMnO4；Preferably, the mol ratio of As and Mn is controlled 5:1~50:1.
5. the integrated conduct method of arsenic-containing material according to claim 1 and 2, it is characterised in that step is urged described in (2) The temperature that change oxidation system is controlled is 30 DEG C~120 DEG C.
6. the integrated conduct method of arsenic-containing material according to claim 1 and 2, it is characterised in that soaked described in step (4) Washing slag tap using the washing of fluidization wash tower.
7. the integrated conduct method of arsenic-containing material according to claim 1 and 2, it is characterised in that described in step (5) also It is blast furnace, reverberatory furnace, bottom convertor, side-blown converter or top blast stove that former melting, oxidation are blown reactor used.
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