CN106834717A - A kind of method that valuable metal and arsenic safe disposal are reclaimed from arsenic-containing smoke dust - Google Patents
A kind of method that valuable metal and arsenic safe disposal are reclaimed from arsenic-containing smoke dust Download PDFInfo
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- CN106834717A CN106834717A CN201611192959.5A CN201611192959A CN106834717A CN 106834717 A CN106834717 A CN 106834717A CN 201611192959 A CN201611192959 A CN 201611192959A CN 106834717 A CN106834717 A CN 106834717A
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
- C22B7/02—Working-up flue dust
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B13/00—Obtaining lead
- C22B13/04—Obtaining lead by wet processes
- C22B13/045—Recovery from waste materials
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B30/00—Obtaining antimony, arsenic or bismuth
- C22B30/02—Obtaining antimony
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B30/00—Obtaining antimony, arsenic or bismuth
- C22B30/04—Obtaining arsenic
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
- C22B7/006—Wet processes
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- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
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Abstract
The present invention relates to a kind of method that valuable metal and arsenic safe disposal are reclaimed from arsenic-containing smoke dust, comprise the following steps:Normal pressure water logging;Leachate catalysis oxidation;The solid arsenic of oxidated solution;Leached mud is washed;Washery slag reclaims valuable metal.Methods described is oxidized to the arsenic of pentavalent, and oxidated solution through the lime solid arsenic mineral of heavy arsenic method synthesizing high-stability by normal pressure water logging, solvable arsenic in removing flue dust, leachate through catalysis oxidation operation, the arsenic of trivalent, and cement solidification afterwards is processed.The operations such as leached mud is scrubbed, reduction melting, oxidation blowing make each valuable element be recycled utilization.Arsenic is removed and solidified by the method from flue dust, and the valuable elements such as antimony, lead, bismuth is stayed in as far as possible in leached mud, realizes that arsenic is separated and innoxious with valuable metal.Comprehensive resource utilization rate of the present invention is high, raw material wide adaptation range, solves the flue dust 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 harmless from arsenic-containing smoke dust comprehensively recovering valuable metal and arsenic
The method for changing disposal.
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
Dearsenification and the method for valuable element comprehensive reutilization.The present invention has the advantages that environmental protection, economy, energy-conservation, resource utilization are high,
Realize the innoxious of arsenic.
The solution of the present invention is, by normal pressure water logging, to remove solvable arsenic in flue dust, and will leaching by way of catalysis oxidation
The trivalent arsenic gone out in liquid is oxidized to pentavalent arsenic, then the solid arsenic mineral of synthesizing high-stability, and leached mud is molten through fluidization wash, reduction
The operations such as refining, oxidation blowing, maximize and recycle each valuable element.Arsenic is removed and solidified by the method from flue dust, and is made
Antimony, lead, bismuth etc. are stayed in dearsenification slag as far as possible, realize that arsenic is separated and innoxious with valuable metal.Resource comprehensive profit of the present invention
High with rate, raw material wide adaptation range solves product in pollution problem in traditional handicraft extraction process, particularly Lead-Zinc Sintering Process
Raw flue dust, the advantage of this method is more obvious.
Specifically, the method that the present invention is provided comprises the following steps:
(1) normal pressure water logging:Water logging is carried out to arsenic-containing smoke dust in atmospheric conditions, water is with the liquid solid product mass ratio of flue dust
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 and catalyst is added to carry out catalysis oxidation in the leachate anti-
Should, the arsenic in arsenical is oxidizing to pentavalent, obtain oxidated solution;
(3) the solid arsenic of oxidated solution:Use the heavy arsenic method of lime by the arsenical in the oxidated solution with scorodite shape
Formula solidifies, and obtains solid arsenic mineral;The solid arsenic mineral is further solidified using cement solidification mode again;
(4) leached mud washing:By step (1) gained leached mud by fluidization wash, make the Soluble Arsenic in leached mud
Content is down to less than 0.1%;After filtering, washing lotion and washery slag are obtained;The washing lotion returns to the dipped journey of water at atmospheric pressure to be used to prepare molten
Liquid;
(5) washery slag reclaims valuable metal:After the washery slag is dried, mixing with charcoal, coal and soda ash carries out reduction melting,
Generation flue dust, bubble slag and lead-antimony alloy;
The flue dust is returned into the reduction melting or normal pressure water logging;
Lead is sent to smelt the bubble slag;
The lead-antimony alloy is carried out into oxidation blowing, is passed through under conditions of 650 DEG C~800 DEG C muffle of blowing temperature are aoxidized
Air, obtains 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 dispensing;Lead is sent to refine the lead bullion.
Following element is included in arsenic-containing smoke dust of the present invention:Arsenic, antimony, lead, zinc, copper, tellurium, selenium, bismuth, tin;Preferably, with
Mass percent meter, comprising: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
Valency metal is stayed in leached mud.The water that the water logging is used preferably industrial water.The step preferably water logging stir process
Temperature be room temperature~100 DEG C;It is preferred that the mixing time is 30min~240min, the solid volume mass of preferably described leachate
Than 5:1~20:1, preferably described 300~550r/min of mixing speed.Step (1) the of the present invention water is accumulated with the liquid solid of flue dust
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
Change to pentavalent, the oxidizing gas are oxygen, air or oxygen-enriched air, the flow of preferably described oxidizing gas for 1~
20L/min;The catalyst is KMnO4, preferably arsenic element and the mol ratio of manganese element is 5:1~50:1;The catalysis oxidation
Temperature be preferably 30 DEG C~120 DEG C.
The heavy arsenic method of step (3) the of the present invention lime is specially:The pH value of the oxidated solution is adjusted to 1.5~3, continuously
Add CaO, Ca (OH)2In one or two as heavy arsenical, under the conditions of 10 DEG C~90 DEG C settle 5h~100h;It is preferred that
Ground, calcium constituent and the mol ratio of arsenic element in oxidated solution in the heavy arsenical are 2~8.
In the processing procedure of the heavy arsenic method of above-mentioned lime, certain density antalkali, the antalkali can be added
Can select sodium carbonate, sodium acid carbonate or sodium hydroxide solution.The addition speed of the antalkali can be according to reaction generation H+
Speed add, the pH value for system during maintenance reaction is constant.
Step (3) of the present invention can further be solidified the solid arsenic mineral using cement solidification mode.The cement solidification
Specially:Cement is compared 2 with the solid arsenic mineral with weight:1~10:1st, preferably 4 are compared with weight:1 mixing, makes cement coat institute
State solid arsenic mineral.In order to strengthen the effect of cement solidification, preferably fine coal is added in the cement;The fine coal addition is preferred
For cement weight 20~60%, more preferably cement weight 40%.
Step (4) the of the present invention fluidization wash can be washed using fluidization wash tower;It is preferred that the washing
Number of times is 2~3 times.
Step (5) the of the present invention reduction melting can be carried out in the reactor, specifically can select blast furnace, reverberatory furnace, bottom
Blown converter, side-blown converter or top blast stove.In the step, 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 DEG C~800 DEG C muffle of blowing temperature are aoxidized, to drum in antimony liquid
Enter primary air, antimony is volatilized and produce a large amount of antimony vapours, while being passed through auxiliary air to reactor, antimony vapour is aoxidized generation three
Two antimony are aoxidized, antimony liquid temperature degree in the big necessary temperature of calorimetric maintenance reaction device and stove produced using antimony oxidation;Due to melt body table
The concentration of face 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
Flue dust is volatized into, lead, bismuth are then stayed in the lead of reactor bottom, realize that a stove is dual-purpose.
As a kind of specific embodiment of the invention, main weight/mass percentage composition containing arsenic 1% in the arsenic-containing smoke dust~
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%, bismuth weight/mass percentage composition 0.01%~3%, tin weight/mass percentage composition 0.01%~1%;Specifically include following steps (flow
Refer to shown in Fig. 1):
(1) normal pressure water logging:Water logging is carried out to arsenic-containing smoke dust in atmospheric conditions, water is with the liquid solid product mass ratio of flue dust
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 operation:By way of catalysis oxidation, oxidizing gas and catalyst are added, will soaked
Go out the As of the overwhelming majority in liquid3+It is transformed into As5+, oxidated solution enters into solid arsenic operation;Oxidizing gas be oxygen, air or
Oxygen-enriched air, catalyst is KMnO4;The gas flow control of oxidizing gas exists in 1~20L/min, the control of As/Mn mol ratios
5:1~50:1, the temperature control of catalytic oxidation system control is at 30 DEG C~120 DEG C;
(3) the solid arsenic operation of oxidated solution:The pH value of oxidated solution is adjusted to 1.5~3, is added in the way of continuous charging
CaO and Ca (OH)2In one or two as heavy arsenical, Ca/As mol ratios are 2~15, and the sedimentation time is 5~100 hours,
Reaction temperature is 10 DEG C~90 DEG C, obtains solid arsenic mineral;Weight according to cement and the solid arsenic mineral compares 2:1~10:1, use
The solid arsenic mineral of cement cladding, preferably 4:1.Fine coal is added in cement can strengthen solidification effect, and fine coal addition is cement
The 20%~60% of curing agent quality, preferably 40%;
(4) leached mud washing procedure:By leached mud by fluidization wash 2~3 times, the solvable arsenic in leached mud is down to
Less than 0.1%, washing lotion returns to leaching process to be used to prepare solution;
(5) 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 into lead antimony conjunction
Jin Zhong;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 DEG C~800 DEG C muffle of blowing temperature are aoxidized, in antimony liquid
Primary air is blasted, antimony is volatilized and is produced a large amount of antimony vapours, while being passed through auxiliary air to reactor, antimony vapour is aoxidized 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 melt body
The concentration of 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 oxidations two
Antimony is volatized into flue dust, and lead, bismuth are then stayed in the lead of reactor bottom, realize that a stove is dual-purpose.
Compared with prior art, the method that the present invention is provided has following significant advantage:
Firstth, the present invention is removed the solvable arsenic of the overwhelming majority in arsenic flue dust, after dearsenification by the way of normal pressure water logging
Raw material arsenic content is low, can the valuable metal such as synthetical recovery antimony, lead, bismuth, reduce the content of arsenic in product;
Secondth, it is of the invention by the way of catalysis oxidation, by As3+It is oxidized to As5+, solve the dysoxidizable difficulty of trivalent arsenic
Topic;
3rd, the present invention changes feed way, the pH value of precise control building-up process on the basis of original technology, uses
The calcium arsenate of the heavy arsenic method synthesis of lime, afterwards with cement solidification, the solid arsenic mineral after solidification is gone back in pH scopes 2~11 wide and by force
Stabilization is stored up under the conditions of originality, As is no longer migrated, and also making the As of smelting system has an ideal open circuit, is a kind of
Technological process is simple, resources conservation, environment-friendly method;
4th, using the heavy solid arsenic mineral of arsenic method synthesis of lime, flow is simple, and small, cost is polluted in easily operation for the present invention
It is low, it is as a result easily up to standard, and the calcium arsenate good stability for generating, stable region field width is conveniently stored up, so at the sewage of factory
Using quite varied in reason.
5th, arsenic-containing material can be coated, so that thing containing arsenic by the way of cement solidification in the present invention
Material can be stablized to be stored up.Product after solidification and stabilization treatment, such as meets Leaching standard or recycling mark
Standard, into common landfill yard can carry out landfill stabilization or carry out recycling.
6th, the present invention uses fluidization wash, further reduces the content of arsenic in leached mud, can improve recovery product matter
Amount;
7th, 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 schematic flow sheet of the method for the invention.
Specific embodiment
Following examples are used to illustrate the present invention, but are not limited to the scope of the present invention.
Embodiment 1:
So that domestic certain Lead And Zinc Smelter is containing arsenic smoke dust as an example, raw material main component is Pb 1.57%, As 48.56%, Sn
0.51%, Sb 21.24%, Zn 0.73%, Te 0.35%, Se 0.25%.
Processed in accordance with the following methods:
(1) the high-arsenic antimony flue dust of certain mass is weighed in reactor, and mass ratio 5 is accumulated by liquid solid:1st, mixing speed
100r/min, 70 DEG C of extraction temperature, extraction time 4h carry out leaching experiment.After leaching terminates, remove slurry filtration and separate, arsenic leaching
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 for controlling is that oxygen flow is 5L/
Min, As/Mn mol ratio are controlled 10:1, catalytic oxidation system temperature control is at 90 DEG C.Result shows, As3+Conversion ratio be
95.87%.
(3) pH value of oxidated solution is adjusted to 1.5, CaO and Ca (OH) is added in the way of continuous charging2As heavy arsenic
Agent, Ca/As mol ratios are 5, and the sedimentation time is 50 hours, and reaction temperature is 60 DEG C.According to cement and the weight ratio of solid arsenic mineral
4:1, coat solid arsenic mineral with cement.Fine coal is added in cement, fine coal addition 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 contains solvable arsenic 0.1%.
(5) washery slag allocates charcoal, coal and soda ash into after drying, and reduction melting, melting generation are carried out in 1150 DEG C of reverberatory furnaces
Bubble 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, and lead-antimony alloy enters oxidation
Blowing operation.Under conditions of muffle and 700 DEG C of blowing temperature of oxidation, to primary air is blasted in 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 is returned
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%;The stibium trioxide powder of generation meets the trade mark specified in GB/T 4062-2013 for Sb2O399.00 antimony
White powder;Contain Pb 97.65% in lead bullion, containing Sb 1.85%, containing As 0.52%.
Embodiment 2:
So that domestic certain Lead And Zinc Smelter is containing arsenic smoke dust as an example, raw material main component is Pb 6.88%, As 36.51%, Sn
1.11%, Sb 29.77%, Zn 0.54%, Te 0.24%, Se 0.05%.
Processed in accordance with the following methods:
(1) the high-arsenic antimony flue dust of certain mass is weighed in reactor, and mass ratio 20 is accumulated by liquid solid:1st, mixing speed
300r/min, 40 DEG C of extraction temperature, extraction time 2h carry out leaching experiment.After leaching terminates, remove slurry filtration and separate, arsenic leaching
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 for controlling is that oxygen flow is
10L/min, As/Mn mol ratio are controlled 40:1, catalytic oxidation system temperature control is at 30 DEG C.Result shows, As3+Conversion ratio
It is 87.69%.
(3) pH value of oxidated solution is adjusted to 2, CaO and Ca (OH) is added in the way of continuous charging2As heavy arsenical,
Ca/As mol ratios are 10, and the sedimentation time is 20 hours, and reaction temperature is 60 DEG C.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 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 contains solvable arsenic 0.1%.
(5) washery slag allocates charcoal, coal and soda ash into after drying, and reduction melting, melting generation are carried out in 1100 DEG C of reverberatory furnaces
Bubble 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, and lead-antimony alloy enters oxidation
Blowing operation.Under conditions of muffle and 800 DEG C of blowing temperature of oxidation, to primary air is blasted in 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 is returned
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%;The stibium trioxide powder of generation meets the trade mark specified in GB/T 4062-2013 for Sb2O399.00 antimony
White powder;Contain Pb 95.25% in lead bullion, containing Sb 2.75%, containing As 0.67%.
Embodiment 3:
So that domestic certain Lead And Zinc Smelter is containing arsenic smoke dust as an example, raw material main component is Pb 5.46%, As 30.29%, Sn
0.98%, Sb 29.58%, Zn 0.68%, Te 0.26%, Se 0.07%.
Processed in accordance with the following methods:
(1) the high-arsenic antimony flue dust of certain mass is weighed in reactor, and mass ratio 15 is accumulated by liquid solid:1st, mixing speed
50r/min, 90 DEG C of extraction temperature, extraction time 3h carry out leaching experiment.After leaching terminates, remove slurry filtration and separate, arsenic leaching
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 for controlling is that oxygen flow is 1L/
Min, As/Mn mol ratio are controlled 20:1, catalytic oxidation system temperature control is at 120 DEG C.Result shows, As3+Conversion ratio be
93.48%.
(3) pH value of oxidated solution is adjusted to 1.5, CaO and Ca (OH) is added in the way of continuous charging2As heavy arsenic
Agent, Ca/As mol ratios are 10, and the sedimentation time is 100 hours, and reaction temperature is 90 DEG C.According to cement and the weight of solid arsenic mineral
Than 4:1, coat solid arsenic mineral with cement.Fine coal is added in cement, fine coal addition 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 contains solvable arsenic 0.1%.
(5) washery slag allocates charcoal, coal and soda ash into after drying, and reduction melting, melting generation are carried out in 1200 DEG C of reverberatory furnaces
Bubble 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, and lead-antimony alloy enters oxidation
Blowing operation.Under conditions of muffle and 650 DEG C of blowing temperature of oxidation, to primary air is blasted in 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 is returned
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%;The stibium trioxide powder of generation meets the trade mark specified in GB/T 4062-2013 for Sb2O399.00 antimony
White powder;Contain Pb 95.89% in lead bullion, containing Sb 2.98%, containing As 0.64%.
Although above having used general explanation, specific embodiment and experiment, the present invention is made to retouch in detail
State, but on the basis of the present invention, it can be made some modifications or improvements, this is to those skilled in the art apparent
's.Therefore, these modifications or improvements without departing from theon the basis of the spirit of the present invention, belong to claimed
Scope.
Claims (10)
1. a kind of method that valuable metal and arsenic safe disposal are reclaimed from arsenic-containing smoke dust, it is characterised in that in the arsenic-containing smoke dust
Contain arsenic, antimony and lead;The described method comprises the following steps:
(1) normal pressure water logging:Water logging is carried out to arsenic-containing smoke dust in atmospheric conditions, water is 3 with the liquid solid product mass ratio of flue dust: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 and catalyst are added in the leachate carries out catalytic oxidation, makes
Arsenic in arsenical is oxidizing to pentavalent, obtains oxidated solution;
(3) the solid arsenic of oxidated solution:The heavy arsenic method of lime is used to consolidate the arsenical in the oxidated solution with scorodite form
Change, obtain solid arsenic mineral;The solid arsenic mineral is further solidified using cement solidification mode again;
(4) leached mud washing:By step (1) gained leached mud by fluidization wash, make the Soluble Arsenic content in leached mud
It is down to less than 0.1%;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 reclaims valuable metal:After the washery slag is dried, mixing with charcoal, coal and soda ash carries out reduction melting, generation
Flue dust, bubble slag and lead-antimony alloy;
The flue dust is returned into the reduction melting or normal pressure water logging;
Lead is sent to smelt the bubble slag;
The lead-antimony alloy is carried out into oxidation blowing, air is passed through under conditions of muffle, antimony vapour, blowing slag and thick is obtained
Lead;By antimony vapour oxidation generation antimony oxide, as stibium trioxide product;The blowing slag is returned into reduction melting operation to match somebody with somebody
Material;Lead is sent to refine the lead bullion.
2. method according to claim 1, it is characterised in that following element is included in the arsenic-containing smoke dust:Arsenic, antimony, lead,
Zinc, copper, tellurium, selenium, bismuth, tin;
Preferably, by percentage to the quality, comprising: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%.
3. method according to claim 1 and 2, it is characterised in that the control condition of step (1) described water logging is, water with
The liquid solid product mass ratio of 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 is 30min~240min.
4. the method according to claims 1 to 3 any one, it is characterised in that step (2) described oxidizing gas are oxygen
Gas, air or oxygen-enriched air, the flow of preferably described oxidizing gas is 1~20L/min;
And/or, the catalyst is KMnO4, preferably arsenic element and the mol ratio of manganese element is 5:1~50:1.
5. method according to claim 4, it is characterised in that the temperature of the catalysis oxidation is 30 DEG C~120 DEG C.
6. method according to claim 1, it is characterised in that the heavy arsenic method of step (3) described lime is specially:By the oxygen
The pH value of liquid is adjusted to 1.5~3 after change, is continuously added to CaO, Ca (OH)2In one or two as heavy arsenical, 10 DEG C~90
5h~100h is settled under the conditions of DEG C.
7. method according to claim 6, it is characterised in that the calcium constituent in the heavy arsenical and arsenogen in oxidated solution
The mol ratio of element is 2~8.
8. the method according to claim 1,6 or 7, it is characterised in that step (3) described cement solidification is specially:By water
Mud compares 2 with the solid arsenic mineral with weight:1~10:1st, preferably 4 are compared with weight:1 mixing, makes cement coat the solid arsenic mineral.
9. method according to claim 8, it is characterised in that add fine coal in the cement;The fine coal addition
Preferably cement weight 20~60%, more preferably cement weight 40%.
10. method according to claim 1, it is characterised in that step (4) described fluidization wash uses fluidization wash
Tower is washed;It is preferred that the number of times of the washing is 2~3 times.
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Cited By (3)
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CN108265177A (en) * | 2018-01-08 | 2018-07-10 | 昆明理工大学 | A kind of zinc hydrometallurgy kiln slag and the method for waste acid comprehensive utilization |
CN112063858A (en) * | 2020-09-08 | 2020-12-11 | 龙岩市宇恒环保科技有限公司 | Process for producing qualified arsenic oxide from arsenic-containing material by full-wet method |
CN113526563A (en) * | 2021-09-14 | 2021-10-22 | 赛恩斯环保股份有限公司 | Long-term stabilization treatment method for arsenic in arsenic-containing waste liquid |
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2016
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Cited By (5)
Publication number | Priority date | Publication date | Assignee | Title |
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CN108265177A (en) * | 2018-01-08 | 2018-07-10 | 昆明理工大学 | A kind of zinc hydrometallurgy kiln slag and the method for waste acid comprehensive utilization |
CN108265177B (en) * | 2018-01-08 | 2019-04-12 | 昆明理工大学 | A kind of method of zinc hydrometallurgy kiln slag and waste acid comprehensive utilization |
CN112063858A (en) * | 2020-09-08 | 2020-12-11 | 龙岩市宇恒环保科技有限公司 | Process for producing qualified arsenic oxide from arsenic-containing material by full-wet method |
CN113526563A (en) * | 2021-09-14 | 2021-10-22 | 赛恩斯环保股份有限公司 | Long-term stabilization treatment method for arsenic in arsenic-containing waste liquid |
CN113526563B (en) * | 2021-09-14 | 2021-12-03 | 赛恩斯环保股份有限公司 | Long-term stabilization treatment method for arsenic in arsenic-containing waste liquid |
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