CN106834717B - A method of recycling valuable metal and arsenic safe disposal from arsenic-containing smoke dust - Google Patents
A method of recycling valuable metal and arsenic safe disposal from arsenic-containing smoke dust Download PDFInfo
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- CN106834717B CN106834717B CN201611192959.5A CN201611192959A CN106834717B CN 106834717 B CN106834717 B CN 106834717B CN 201611192959 A CN201611192959 A CN 201611192959A CN 106834717 B CN106834717 B CN 106834717B
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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
-
- 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
-
- 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
The present invention relates to a kind of methods recycling valuable metal and arsenic safe disposal from arsenic-containing smoke dust, include the following steps：Normal pressure water logging；Leachate catalysis oxidation；Oxidated solution consolidates arsenic；Leached mud washs；Washery slag recycles valuable metal.The method removes solvable arsenic in flue dust by normal pressure water logging, and for leachate through catalysis oxidation process, the arsenic of trivalent is oxidized to the arsenic of pentavalent, and oxidated solution sinks arsenic method synthesizing high-stability through lime and consolidate arsenic mineral, and cement solidification later is handled.The processes such as leached mud is washed, reduction melting, oxidation blowing make each valuable element be recycled utilization.Arsenic is removed and is cured from flue dust by the method, and the valuable elements such as antimony, lead, bismuth is made to stay in as far as possible in leached mud, and the separation of realization arsenic and valuable metal is simultaneously innoxious.Comprehensive resource utilization rate of the present invention is high, and raw material wide adaptation range solves the flue dust generated in pollution problem in traditional handicraft extraction process, especially Lead-Zinc Sintering Process, and the advantage of this method is more obvious.
Description
Technical field
The invention belongs to metallurgical technology fields, and in particular to a kind of harmless from arsenic-containing smoke dust comprehensively recovering valuable metal and arsenic
Change the method for disposition.
Background technology
In nature, arsenic is usually with mispickel (FeAsS), arsenic magnetic iron ore (FeAsS2), symplesite (FeAs2), sulphur arsenical copper
Mine (Cu3AsS3), realgar (As2S3), orpiment (As2S3) etc. mineral, be enriched in the non-ferrous metals such as copper, lead, zinc, nickel, cobalt, gold and silver
In ore；In Nonferrous Metallurgical Process, many high arsenic solid materials of output, such as roasting and melting flue dust.These materials are high containing arsenic
Up to 5~50%, also contain a large amount of valuable metal, directly returns and smelt flow, lead to the circulative accumulation of arsenic in systems, because
This, usually should individually handle dearsenification.Arsenic belongs to severe toxicity, carcinogenic elements, applies gradually atrophy, in face of increasingly stringent environmental protection mark
How standard handles various high-arsenic materials, it has also become threatens the significant problem of nonferrous metallurgy industry existence.
The method of processing arsenic-containing smoke dust is mainly two classes at present, when fire concentrate, second is that wet separation.Pyrogenic process produces
In, the difference of the oxide and other elements oxide boiling point of arsenic is mainly utilized, arsenic is made to be detached with other elements.
CN103602835A discloses a kind of displacement reduction method and obtains crude arsenic and needle antimony, and CN103602834A discloses a kind of selective oxygen
Change-reduction obtains the not high As of purity2O3And needle antimony, CN104294053A disclose a kind of side of arsenic-containing smoke dust reduction volatilization arsenic
Method obtains arsenic trioxide purity and reaches 97.0% or more.But if contain the metal close with arsenic element property in flue dust
(such as antimony), then the arsenic trioxide purity obtained is not high.Mainly there are water logging, acidleach, alkali to soak three kinds of techniques in wet production, still
The products such as the not high arsenic trioxide of purity, natrium arsenicum can only be obtained, and the recycling of valuable metal powder is not made further research.
CN105567983A discloses a kind for the treatment of process of Copper making flue dust water logging-alkali leaching, so that arsenic is detached with metal, the arsenic production of preparation
Product are at a discount, still higher containing arsenic in leached mud.CN104357668A discloses a kind of waste acid leaching flue dust, electrodeposition dearsenification, acid
Leaching and electrolytic deposition process easy to produce arsenic hydride.CN105648226A and CN105648227A discloses a kind of oxygen pressure alkali leaching realization arsenic
The method of antimony separation, more thoroughly, but the natrium arsenicum obtained in process is untreated, the valuable gold such as tellurium, antimony for the ratio of arsenic antimony separation
Belong to unrecovered.
There are many dearsenification, the research paper for extracting valuable metal and related patents report from flue dust, but there are valuable elements
Comprehensive recovery is low, and arsenic product market is limited, and there are potential security risks.Therefore, the prior art could be improved and develop.
Invention content
In order to solve the problems, such as arsenic-containing smoke dust dearsenification and containing comprehensively recovering valuable metal, the present invention proposes a kind of arsenic-containing smoke dust
The method of dearsenification and valuable element comprehensive reutilization.The present invention has the advantages that environmentally friendly, economical, energy saving, resource utilization is high,
Realize the innoxious of arsenic.
The scheme of the invention is by normal pressure water logging, solvable arsenic in flue dust is removed, and will leaching by way of catalysis oxidation
The trivalent arsenic gone out in liquid is oxidized to pentavalent arsenic, then synthesizing high-stability consolidates arsenic mineral, and leached mud is molten through fluidization wash, reduction
The processes such as refining, oxidation blowing, maximize and recycle each valuable element.Arsenic is removed and is cured from flue dust by the method, and is made
Antimony, lead, bismuth etc. are stayed in as far as possible in dearsenification slag, and the separation of realization arsenic and valuable metal is simultaneously innoxious.Resource comprehensive profit of the present invention
With rate height, raw material wide adaptation range is solved and is produced in pollution problem in traditional handicraft extraction process, especially Lead-Zinc Sintering Process
The advantage of raw flue dust, this method is more obvious.
Specifically, method provided by the invention includes the following steps：
(1) normal pressure water logging：Water logging is carried out to arsenic-containing smoke dust in atmospheric conditions, the liquid solid product mass ratio of water and flue dust is
3：1~20:1, mixing speed is 50r/min~1000r/min, and the temperature of water logging is room temperature~100 DEG C, and extraction time is
30min~240min makes arsenical be completely dissolved in water；After filtering, leachate and leached mud are obtained；
(2) leachate catalysis oxidation：Oxidizing gas is added in the leachate and catalyst progress catalysis oxidation is anti-
It answers, the arsenic in arsenical is made to be oxidizing to pentavalent, obtain oxidated solution；
(3) oxidated solution consolidates arsenic：Use lime sink arsenic method by the arsenical in the oxidated solution with scorodite shape
Formula cures, and obtains solid arsenic mineral；Cement solidification mode is used further to cure the solid arsenic mineral again；
(4) leached mud washs：Leached mud obtained by step (1) is passed through into fluidization wash, makes the Soluble Arsenic in leached mud
Content is down to 0.1% or less；After filtering, washing lotion and washery slag are obtained；It is molten for preparing that the washing lotion returns to the dipped journey of water at atmospheric pressure
Liquid；
(5) washery slag recycles valuable metal：After the washery slag is dried, is mixed with charcoal, coal and soda ash and carries out reduction melting,
Generate flue dust, bubble slag and lead-antimony alloy；
The flue dust is returned into the reduction melting or normal pressure water logging；
Lead is sent to smelt the bubble slag；
The lead-antimony alloy is subjected to oxidation blowing, is passed through under conditions of aoxidizing 650 DEG C of blowing temperature~800 DEG C of muffle
Air obtains antimony vapour, blowing slag and lead bullion；The antimony vapour is aoxidized and generates antimony oxide, as stibium trioxide product；By institute
It states blowing slag and returns to reduction melting process dispensing；Lead is sent to refine the lead bullion.
It include following element in arsenic-containing smoke dust of the present invention：Arsenic, antimony, lead, zinc, copper, tellurium, selenium, bismuth, tin；Preferably, with
Mass percent meter, including：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%, bismuth 0.01%~3%, tin 0.01%~1%.
Step (1) of the present invention can be such that arsenic and a small amount of antimony is dissolved into water logging leachate, and most of antimony, lead, bismuth etc. have
Valence metal stays in leached mud.The water that the water logging uses is preferably industrial water.The preferably described water logging stir process of the step
Temperature be room temperature~100 DEG C；It is preferred that the mixing time is 30min~240min, the preferably described leachate consolidates volume mass
Than 5:1~20:1, preferably described 300~550r/min of mixing speed.The liquid solid product of step (1) water and flue dust of the present invention
Quality is ml than unit：g.
In step (2) of the present invention, in order to further ensure that the catalytic oxidation can be carried out fully, make the abundant oxygen of arsenic
To change to pentavalent, the oxidizing gas is oxygen, air or oxygen-enriched air, the flow of the preferably described oxidizing gas is 1~
20L/min；The catalyst is KMnO4, the preferably molar ratio of arsenic element and manganese element is 5:1~50:1；The catalysis oxidation
Temperature be preferably 30 DEG C~120 DEG C.
Step (3) the of the present invention lime sink arsenic method be specially：The pH value of the oxidated solution is adjusted to 1.5~3, continuously
CaO, Ca (OH) is added2One or both of as sink arsenical, under the conditions of 10 DEG C~90 DEG C settle 5h~100h；It is preferred that
Ground, the molar ratio of arsenic element is 2~8 in the calcium constituent and oxidated solution in the heavy arsenical.
In the processing procedure of the heavy arsenic method of above-mentioned lime, certain density antalkali, the antalkali can be added
Sodium carbonate, sodium bicarbonate or sodium hydroxide solution can be selected.The addition speed of the antalkali can generate H according to reaction+
Speed be added, for maintaining the pH value of system in reaction process constant.
Step (3) of the present invention can be used cement solidification mode and further cure the solid arsenic mineral.The cement solidification
Specially：By cement with the solid arsenic mineral with weight ratio 2:1~10:1, preferably with weight ratio 4:1 mixing, makes cement coat institute
State solid arsenic mineral.In order to reinforce the effect of cement solidification, preferably fine coal is added in the cement；The fine coal additive amount is preferred
For cement weight 20~60%, more preferably cement weight 40%.
Step (4) the of the present invention fluidization wash can be used fluidization wash tower and be washed；It is preferred that the washing
Number is 2~3 times.
Step (5) the of the present invention reduction melting can carry out in the reactor, and blast furnace, reverberatory furnace, bottom specifically can be selected
Blown converter, side-blown converter or top blast stove.In the step, supplying charcoal, coal and a small amount of soda ash (Na after washery slag drying2CO3), 900~
1200 DEG C and have under the conditionings such as C, CO, the oxides such as Sb, Pb, Bi are equally also reduced into simple substance form and enter lead-antimony alloy
In；Pit ash and a small amount of arsenic, antimony, lead oxide light " the bubble slag " of the more alveolar substances generated is reacted with soda ash, float on antimony
Liquid surface；After the completion of reduction, bubble slag is clawed, under conditions of aoxidizing 650 DEG C of blowing temperature~800 DEG C of muffle, the drum into antimony liquid
Enter primary air, so that antimony volatilization is generated a large amount of antimony vapours, while auxiliary air is passed through to reactor, antimony vapour oxidation is made to generate three
Two antimony are aoxidized, the big calorimetric generated using antimony oxidation maintains antimony liquid temperature in the necessary temperature of reactor and stove；Due to melt body table
The concentration of face metallic antimony has comparative advantage, and metallic antimony property is more active than lead, bismuth, and the antimony in aluminium alloy is made to be oxidized to antimony oxide
It is volatized into flue dust, lead, bismuth then stay in the lead of reactor bottom, realize that a stove is dual-purpose.
As a kind of specific implementation mode of the present invention, in the arsenic-containing smoke dust mainly mass percentage containing arsenic 1%~
60%, antimony mass percentage 1%~55%, lead mass percentage 0.1%~35%, zinc mass percentage 0.1%~
30%, copper mass percentage composition 0.1~5%, tellurium mass percentage 0.01%~3%, selenium mass percentage 0.01%~
3%, bismuth mass percentage 0.01%~3%, tin mass percentage 0.01%~1%；Specifically comprise the following steps (flow
It can refer to shown in Fig. 1)：
(1) normal pressure water logging：Water logging is carried out to arsenic-containing smoke dust in atmospheric conditions, the liquid solid product mass ratio of water and flue dust is
3：1~20:1, mixing speed is 50r/min~1000r/min, and the temperature of water logging is room temperature~100 DEG C, and extraction time is
30min~240min makes arsenical be completely dissolved in water；After filtering, leachate and leached mud are obtained；
(2) leachate catalysis oxidation process：By way of catalysis oxidation, oxidizing gas and catalyst is added, will soak
Go out As most in liquid3+It is transformed into As5+, oxidated solution enters solid arsenic process；Oxidizing gas be oxygen, air or
Oxygen-enriched air, catalyst KMnO4；The gas flow control of oxidizing gas exists in 1~20L/min, the control of As/Mn molar ratios
5：1~50:1, the temperature of catalytic oxidation system control is controlled at 30 DEG C~120 DEG C；
(3) oxidated solution consolidates arsenic process：The pH value of oxidated solution is adjusted to 1.5~3, is added in a manner of continuous charging
CaO and Ca (OH)2One or both of as sink arsenical, Ca/As molar ratios be 2~15, the sedimentation time be 5~100 hours,
Reaction temperature is 10 DEG C~90 DEG C, obtains solid arsenic mineral；According to the weight ratio 2 of cement and the solid arsenic mineral：1~10：1, it uses
The solid arsenic mineral of cement cladding, preferably 4：1.Fine coal is added in cement can strengthen solidification effect, and fine coal additive amount is cement
The 20%~60% of curing agent quality, preferably 40%；
(4) leached mud washing procedure：Leached mud is passed through into fluidization wash 2~3 times, the solvable arsenic in leached mud is down to
0.1% hereinafter, washing lotion returns to leaching process for preparing solution；
(5) washery slag recycles valuable metal process, supplying charcoal, coal and a small amount of soda ash (Na after washery slag drying2CO3), 900
~1200 DEG C and have under the conditionings such as C, CO, the oxides such as Sb, Pb, Bi are equally also reduced into simple substance form and enter the conjunction of lead antimony
Jin Zhong；Pit ash and a small amount of arsenic, antimony, lead oxide light " the bubble slag " of the more alveolar substances generated is reacted with soda ash, float on
Antimony liquid surface；After the completion of reduction, bubble slag is clawed, under conditions of aoxidizing 650 DEG C of blowing temperature~800 DEG C of muffle, into antimony liquid
Primary air is blasted, so that antimony volatilization is generated a large amount of antimony vapours, while auxiliary air is passed through to reactor, antimony vapour oxidation is made to generate
Antimony oxide, the big calorimetric generated using antimony oxidation maintain antimony liquid temperature in the necessary temperature of reactor and stove；Due to melt body
The concentration of surface metal antimony has comparative advantage, and metallic antimony property is more active than lead, bismuth, and the antimony in aluminium alloy is made to be oxidized to three oxidations two
Antimony is volatized into flue dust, and lead, bismuth then stay in the lead of reactor bottom, realizes that a stove is dual-purpose.
Compared with prior art, method provided by the invention has following significant advantage：
The first, the present invention is removed solvable arsenic most in arsenic flue dust, by the way of normal pressure water logging after dearsenification
Raw material arsenic content is low, can the valuable metals such as synthetical recovery antimony, lead, bismuth, reduce the content of arsenic in product；
The second, the present invention is by the way of catalysis oxidation, by As3+It is oxidized to As5+, solve the dysoxidizable difficulty of trivalent arsenic
Topic；
The pH value that third, the present invention change feed way on the basis of original technology, accurately control building-up process, uses
The calcium arsenate of the heavy arsenic method synthesis of lime, uses cement solidification, the solid arsenic mineral after solidification is gone back in wide pH ranges 2~11 and by force later
Stablize stockpiling under the conditions of originality, so that As is no longer migrated, the As of smelting system is also made to have an ideal open circuit, is a kind of
Simple, resource-effective, the environmental-friendly method of technological process；
4th, for the present invention using the heavy solid arsenic mineral of arsenic method synthesis of lime, flow is simple, easy to operate, pollutes small, cost
It is low, it is as a result easily up to standard, and the arsenic acid calcium stability generated is good, and stable region field width facilitates stockpiling, so at the sewage of factory
Using very extensive in reason.
5th, arsenic-containing material can be coated, so that object containing arsenic by the way of cement solidification in the present invention
Material can stablize stockpiling.By solidification and stabilization treated product, such as meet Leaching standard or recycling mark
Standard can enter common landfill yard and carry out landfill stabilization or carry out recycling.
6th, the present invention uses fluidization wash, further decreases the content of arsenic in leached mud, and recycling product matter can be improved
Amount；
7th, the present invention recycles valuable metal using reduction melting, realizes that metal comprehensive reutilization maximizes.
In short, the rational process of the present invention is arranged in pairs or groups, by strictly controlling the conditional parameter in each process, arsenic is enable to pacify
Full disposition, antimony, lead, bismuth etc. are recycled and efficiently use, and have achieved the purpose that environmentally friendly, economic, energy saving, high resource utilization,
Realize the innoxious and maximum resource utilization of arsenic.Since the separation of arsenic and other elements avoids fire using wet processing
The not high problem of massive pollution and the utilization of resources caused by method, entire technique substantially three-waste free discharge, all resources
Obtain maximal efficiency utilization, products therefrom be convenient for subsequent processing and processing, so the present invention have it is environmentally friendly, economical, energy saving,
The advantage of high resource utilization.
Description of the drawings
Fig. 1 is the flow diagram of the method for the invention.
Specific implementation mode
The following examples are used to illustrate the present invention, but are not intended to limit the scope of the present invention..
Embodiment 1：
By certain domestic Lead And Zinc Smelter containing for arsenic smoke dust, raw material main component is Pb 1.57%, As 48.56%, Sn
0.51%, Sb 21.24%, Zn 0.73%, Te 0.35%, Se 0.25%.
It is handled in accordance with the following methods：
(1) the high-arsenic antimony flue dust of certain mass is weighed in reaction kettle, and mass ratio 5 is accumulated by liquid solid:1, mixing speed
100r/min, 70 DEG C of extraction temperature, extraction time 4h carry out leaching experiment.After leaching, slurry filtration separation, arsenic leaching are removed
Extracting rate 41.53%, each element concentration Pb 709.60ppm, Se 31.02ppm, Sb 1.26g/L, Te in leachate
123.28ppm As 20.17g/L.
(2) leachate using the method for catalysis oxidation by As3+It is oxidized to As5+, the condition of control is oxygen flow 5L/
Min, As/Mn molar ratio are controlled 10：1, catalytic oxidation system temperature is controlled at 90 DEG C.The result shows that As3+Conversion ratio be
95.87%.
(3) pH value of oxidated solution is adjusted to 1.5, CaO and Ca (OH) is added in a manner of continuous charging2As heavy arsenic
Agent, Ca/As molar ratios are 5, and the sedimentation time is 50 hours, and reaction temperature is 60 DEG C.According to the weight ratio of cement and solid arsenic mineral
4：1, coat solid arsenic mineral with cement.Fine coal is added in cement, fine coal additive amount is the 40% of cement hardener.
(4) leached mud accumulates mass ratio 5 according to liquid solid:1 washes leached mud 2 times using fluidization wash tower, and washing lotion contains arsenic
9.62g/L, washery slag contain solvable arsenic 0.1%.
(5) supplying charcoal, coal and soda ash after washery slag drying, carry out reduction melting, melting generates in 1150 DEG C of reverberatory furnaces
Steep slag, lead-antimony alloy and flue dust.Bubble slag send lead to smelt, and flue dust returns to reduction melting or normal pressure water logging, lead-antimony alloy enter oxidation
Blow process.Under conditions of muffle and 700 DEG C of blowing temperature of oxidation, primary air is blasted into alloy, while to reactor
It is passed through auxiliary air, so that antimony vapour oxidation is generated antimony oxide, the antimony oxide of generation is as stibium trioxide product.Blowing slag returns
Reduction melting system, and the lead bullion aoxidized after blowing send lead rectification systems.Wherein Pb contains containing 18.96%, Sb in lead-antimony alloy
75.67%, As contain 3.76%；It is Sb that the stibium trioxide powder of generation, which meets the trade mark specified in GB/T 4062-2013,2O399.00 antimony
White powder；Contain Pb 97.65% in lead bullion, contain Sb 1.85%, contains As 0.52%.
Embodiment 2：
By certain domestic Lead And Zinc Smelter containing for arsenic smoke dust, raw material main component is Pb 6.88%, As 36.51%, Sn
1.11%, Sb 29.77%, Zn 0.54%, Te 0.24%, Se 0.05%.
It is handled in accordance with the following methods：
(1) the high-arsenic antimony flue dust of certain mass is weighed in reaction kettle, and mass ratio 20 is accumulated by liquid solid:1, mixing speed
300r/min, 40 DEG C of extraction temperature, extraction time 2h carry out leaching experiment.After leaching, slurry filtration separation, arsenic leaching are removed
Extracting rate 41.29%, each element concentration Pb 515.20ppm, Se 31.56ppm, Sb 0.88g/L, Te in leachate
122.26ppm As 15.07g/L.
(2) leachate using the method for catalysis oxidation by As3+It is oxidized to As5+, the condition of control is that oxygen flow is
10L/min, As/Mn molar ratio are controlled 40：1, catalytic oxidation system temperature is controlled at 30 DEG C.The result shows that As3+Conversion ratio
It is 87.69%.
(3) pH value of oxidated solution is adjusted to 2, CaO and Ca (OH) is added in a manner of continuous charging2As heavy arsenical,
Ca/As molar ratios are 10, and the sedimentation time is 20 hours, and reaction temperature is 60 DEG C.According to the weight ratio 6 of cement and solid arsenic mineral：
1, coat solid arsenic mineral with cement.Fine coal is added in cement, fine coal additive amount is the 60% of cement hardener.
(4) leached mud accumulates mass ratio 5 according to liquid solid:1 washes leached mud 2 times using fluidization wash tower, and washing lotion contains arsenic
8.45g/L, washery slag contain solvable arsenic 0.1%.
(5) supplying charcoal, coal and soda ash after washery slag drying, carry out reduction melting, melting generates in 1100 DEG C of reverberatory furnaces
Steep slag, lead-antimony alloy and flue dust.Bubble slag send lead to smelt, and flue dust returns to reduction melting or normal pressure water logging, lead-antimony alloy enter oxidation
Blow process.Under conditions of muffle and 800 DEG C of blowing temperature of oxidation, primary air is blasted into alloy, while to reactor
It is passed through auxiliary air, so that antimony vapour oxidation is generated antimony oxide, the antimony oxide of generation is as stibium trioxide product.Blowing slag returns
Reduction melting system, and the lead bullion aoxidized after blowing send lead rectification systems.Wherein Pb contains containing 28.27%, Sb in lead-antimony alloy
64.98%, As contain 5.58%；It is Sb that the stibium trioxide powder of generation, which meets the trade mark specified in GB/T 4062-2013,2O399.00 antimony
White powder；Contain Pb 95.25% in lead bullion, contain Sb 2.75%, contains As 0.67%.
Embodiment 3：
By certain domestic Lead And Zinc Smelter containing for arsenic smoke dust, raw material main component is Pb 5.46%, As 30.29%, Sn
0.98%, Sb 29.58%, Zn 0.68%, Te 0.26%, Se 0.07%.
It is handled in accordance with the following methods：
(1) the high-arsenic antimony flue dust of certain mass is weighed in reaction kettle, and mass ratio 15 is accumulated by liquid solid:1, mixing speed
50r/min, 90 DEG C of extraction temperature, extraction time 3h carry out leaching experiment.After leaching, slurry filtration separation, arsenic leaching are removed
Extracting rate 44.52%, each element concentration Pb 956.35ppm, Se 18.91ppm, Sb 0.93g/L, Te in leachate
144.92ppm As 13.48g/L.
(2) leachate using the method for catalysis oxidation by As3+It is oxidized to As5+, the condition of control is oxygen flow 1L/
Min, As/Mn molar ratio are controlled 20：1, catalytic oxidation system temperature is controlled at 120 DEG C.The result shows that As3+Conversion ratio be
93.48%.
(3) pH value of oxidated solution is adjusted to 1.5, CaO and Ca (OH) is added in a manner of continuous charging2As heavy arsenic
Agent, Ca/As molar ratios are 10, and the sedimentation time is 100 hours, and reaction temperature is 90 DEG C.According to the weight of cement and solid arsenic mineral
Than 4：1, coat solid arsenic mineral with cement.Fine coal is added in cement, fine coal additive amount is the 20% of cement hardener.
(4) leached mud accumulates mass ratio 5 according to liquid solid:1 washes leached mud 2 times using fluidization wash tower, and washing lotion contains arsenic
5.46g/L, washery slag contain solvable arsenic 0.1%.
(5) supplying charcoal, coal and soda ash after washery slag drying, carry out reduction melting, melting generates in 1200 DEG C of reverberatory furnaces
Steep slag, lead-antimony alloy and flue dust.Bubble slag send lead to smelt, and flue dust returns to reduction melting or normal pressure water logging, lead-antimony alloy enter oxidation
Blow process.Under conditions of muffle and 650 DEG C of blowing temperature of oxidation, primary air is blasted into alloy, while to reactor
It is passed through auxiliary air, so that antimony vapour oxidation is generated antimony oxide, the antimony oxide of generation is as stibium trioxide product.Blowing slag returns
Reduction melting system, and the lead bullion aoxidized after blowing send lead rectification systems.Wherein Pb contains containing 26.67%, Sb in lead-antimony alloy
65.27%, As contain 6.45%；It is Sb that the stibium trioxide powder of generation, which meets the trade mark specified in GB/T 4062-2013,2O399.00 antimony
White powder；Contain Pb 95.89% in lead bullion, contain Sb 2.98%, contains As 0.64%.
Although above having used general explanation, specific implementation mode and experiment, the present invention is made to retouch in detail
It states, but on the basis of the present invention, it can be made some modifications or improvements, this is apparent to those skilled in the art
's.Therefore, these modifications or improvements without departing from theon the basis of the spirit of the present invention, belong to claimed
Range.
Claims (12)
1. a kind of method recycling valuable metal and arsenic safe disposal from arsenic-containing smoke dust, which is characterized in that in the arsenic-containing smoke dust
By percentage to the quality, including：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%, bismuth 0.01%~3%, tin 0.01%~1%；The method packet
Include following steps：
(1) normal pressure water logging：Water logging is carried out to arsenic-containing smoke dust in atmospheric conditions, the liquid solid product mass ratio of water and flue dust is 3：1
~20:1, mixing speed is 50r/min~1000r/min, and the temperature of water logging is room temperature~100 DEG C, extraction time be 30min~
240min makes arsenical be completely dissolved in water；After filtering, leachate and leached mud are obtained；
(2) leachate catalysis oxidation：Oxidizing gas is added in the leachate and catalyst carries out catalytic oxidation, makes
Arsenic in arsenical is oxidizing to pentavalent, obtains oxidated solution；
(3) oxidated solution consolidates arsenic：It uses lime to sink arsenic method to consolidate the arsenical in the oxidated solution with scorodite form
Change, obtains solid arsenic mineral；Cement solidification mode is used further to cure the solid arsenic mineral again；
The lime sink arsenic method be specially：The pH value of the oxidated solution is adjusted to 1.5~3, is continuously added to CaO, Ca (OH)2In
It is one or two kinds of as arsenical is sunk, 5h~100h is settled under the conditions of 10 DEG C~90 DEG C；
(4) leached mud washs：Leached mud obtained by step (1) is passed through into fluidization wash, makes the Soluble Arsenic content in leached mud
It is down to 0.1% or less；After filtering, washing lotion and washery slag are obtained；The washing lotion returns to the dipped journey of water at atmospheric pressure；
(5) washery slag recycles valuable metal：It after the washery slag is dried, is mixed with charcoal, coal and soda ash and carries out reduction melting, generated
Flue dust, bubble slag and lead-antimony alloy；
The flue dust is returned into the reduction melting or normal pressure water logging；
Lead is sent to smelt the bubble slag；
The lead-antimony alloy is subjected to oxidation blowing, is passed through air under conditions of muffle, obtains antimony vapour, blowing slag and thick
Lead；The antimony vapour is aoxidized and generates antimony oxide, as stibium trioxide product；Blowing slag return reduction melting process is matched
Material；Lead is sent to refine the lead bullion.
2. according to the method described in claim 1, it is characterized in that, step (2) described oxidizing gas is oxygen, air or richness
Oxygen air；And/or the catalyst is KMnO4。
3. according to the method described in claim 2, it is characterized in that, the flow of step (2) described oxidizing gas is 1~20L/
min；And/or the molar ratio of arsenic element and the manganese element in catalyst is 5:1~50:1.
4. according to the method in claim 2 or 3, which is characterized in that the temperature of the catalysis oxidation is 30 DEG C~120 DEG C.
5. according to the method described in claim 1, it is characterized in that, arsenogen in calcium constituent and oxidated solution in the heavy arsenical
The molar ratio of element is 2~8.
6. method according to claim 1 or 5, which is characterized in that step (3) described cement solidification is specially：By cement
With the solid arsenic mineral with weight ratio 2:1~10:1 mixing makes the cement cladding solid arsenic mineral.
7. according to the method described in claim 6, it is characterized in that, step (3) described cement solidification is specially：By cement and institute
Solid arsenic mineral is stated with weight ratio 4:1 mixing makes the cement cladding solid arsenic mineral.
8. according to the method described in claim 6, it is characterized in that, adding fine coal in the cement.
9. according to the method described in claim 8, it is characterized in that, the fine coal additive amount is the 20~60% of cement weight.
10. according to the method described in claim 8, it is characterized in that, the fine coal additive amount is the 40% of cement weight.
11. according to the method described in claim 1, it is characterized in that, step (4) described fluidization wash uses fluidization wash
Tower is washed.
12. according to the method for claim 11, which is characterized in that the number of the washing is 2~3 times.
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