CN106834709B - The method that a kind of comprehensive utilization of arsenic-containing smoke dust and precipitation transformation method synthesize solid arsenic mineral - Google Patents
The method that a kind of comprehensive utilization of arsenic-containing smoke dust and precipitation transformation method synthesize solid arsenic mineral Download PDFInfo
- Publication number
- CN106834709B CN106834709B CN201611191082.8A CN201611191082A CN106834709B CN 106834709 B CN106834709 B CN 106834709B CN 201611191082 A CN201611191082 A CN 201611191082A CN 106834709 B CN106834709 B CN 106834709B
- Authority
- CN
- China
- Prior art keywords
- arsenic
- antimony
- lead
- oxygen
- solid
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Classifications
-
- 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
- A62D3/33—Processes for making harmful chemical substances harmless or less harmful, by effecting a chemical change in the substances by reacting with chemical agents by chemical fixing the harmful substance, e.g. by chelation or complexation
-
- 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
- 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
-
- 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
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Geology (AREA)
- Environmental & Geological Engineering (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Health & Medical Sciences (AREA)
- General Health & Medical Sciences (AREA)
- Toxicology (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Business, Economics & Management (AREA)
- Emergency Management (AREA)
- Manufacture And Refinement Of Metals (AREA)
- Processing Of Solid Wastes (AREA)
Abstract
The present invention relates to the method that metallurgical technology field more particularly to a kind of comprehensive utilization of arsenic-containing smoke dust and precipitation transformation method synthesize solid arsenic mineral, this method includes that oxygen presses water logging, leachate to consolidate arsenic, precipitating conversion, leached mud washing and washery slag recycling 5 steps of valuable metal.Water logging is pressed by oxygen, removes solvable arsenic in flue dust, leachate sinks the stable solid arsenic mineral of arsenic-precipitating Synthesis through lime, then using solidifying solid arsenic mineral by the way of storing up.Leached mud is washed, reduction melting, aoxidizes the processes such as blowing, maximizes and recycles each valuable element.Arsenic is removed from flue dust and synthesize stable solid arsenic mineral, and make antimony, lead, bismuth etc. by the method to be stayed in as far as possible in leached mud, realizes that the separation of arsenic and valuable metal is simultaneously innoxious.Comprehensive resource utilization rate of the present invention is high, raw material wide adaptation range, solves the flue dust that pollution problem in traditional handicraft extraction process, especially Lead-Zinc Sintering Process generate, 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 comprehensive utilization of arsenic-containing smoke dust and precipitation transformation method synthesis are solid
The method of arsenic mineral.
Background technique
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 process, 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, first is that fire concentrate, second is that wet separation.Pyrogenic process production
In, mainly using the difference of the oxide of arsenic and other elements oxide boiling point, separate arsenic with other elements.
CN103602835A discloses a kind of method that displacement reduction method obtains crude arsenic and needle antimony, and CN103602834A discloses a kind of choosing
Selecting property oxidationreduction obtains the not high As of purity2O3With the method for needle antimony, CN104294053A discloses a kind of arsenic-containing smoke dust also
The method of former volatilized arsenic obtains arsenic trioxide purity and reaches 97.0% or more.But if contain and arsenogen disposition in flue dust
The close metal of matter (such as antimony), then the arsenic trioxide purity obtained is not high.Mainly there are water logging, acidleach, alkali leaching in wet production
Three kinds of techniques, but the products such as the not high arsenic trioxide of purity, natrium arsenicum can only be obtained, and not to the recycling of valuable metal powder
It makes further research.CN105567983A discloses a kind for the treatment of process of Copper making flue dust water logging-alkali leaching, makes arsenic and metal point
From the arsenic product of preparation is at a discount, still higher containing arsenic in leached mud.CN104357668A discloses a kind of waste acid leaching cigarette
Dirt, electrodeposition dearsenification, acidleach and electrolytic deposition process are easy to produce arsenic hydride.CN105648226A and CN105648227A discloses oxygen pressure
The method that the separation of arsenic antimony is realized in alkali leaching, more thoroughly, but the natrium arsenicum obtained in process is untreated for the ratio of arsenic antimony separation, tellurium,
The valuable metals such as antimony are unrecovered.
In conclusion dearsenification, the research paper for extracting valuable metal and related patents report are many but existing from flue dust
For technology there are still valuable metal comprehensive recovery is low, arsenic product market is limited, there are problems that potential security risk.Cause
This, the existing technology has yet to be improved and developed.
Summary of the invention
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 from cigarette containing arsenic
The method of valuable metal and arsenic harmlessness disposing is recycled in dirt.The present invention has environmental protection, economic, energy conservation, resource utilization high
Advantage realizes the harmless treatment of arsenic, specifically adopts the following technical scheme that
The method that a kind of comprehensive utilization of arsenic-containing smoke dust and precipitation transformation method synthesize solid arsenic mineral, comprising the following steps:
(1) oxygen presses water logging: taking arsenic-containing smoke dust in reaction kettle, water is added thereto, oxidisability gas is passed through into reaction kettle
Body, carries out oxygen leaching under 120~300 DEG C, 0.1~3.5MPa, after oxygen leaching, through solid-liquor separation, obtains containing arsenic
Leachate and leached mud；
(2) leachate consolidates arsenic: the pH value of leachate obtained by regulating step (1) to 1.5~3, in a manner of continuous charging to
CaO and Ca (OH) is added in leachate2One or both of solid arsenic, obtain arsenic acid calcium precipitate；
(3) precipitating is converted into scorodite: iron salt solutions are added into the system of step (2), while being continuously added neutralizer,
Regulation reaction carries out under the conditions of pH value 1.5~3, makes Fe3+With AsO4 3-Reaction generates the solid arsenic mineral of high stability, final to obtain
To solid arsenic mineral；
(4) leached mud washs: washing to step (1) resulting leached mud, obtains washing lotion and washery slag, controls in washery slag
Arsenic content is less than 0.1%, wherein the washing lotion return step (1) carries out oxygen and presses water logging；
(5) washery slag recycles valuable metal: after the washery slag that step (4) obtains is dry, mixing and is gone back with charcoal, coal and soda ash
Former melting generates 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, obtain antimony vapour, blowing slag and
Lead bullion；The antimony vapour is aoxidized and generates antimony oxide, as stibium trioxide product；The blowing slag is returned into reduction melting process
Ingredient；Lead is sent to refine the lead bullion.
The particularly suitable following arsenic-containing smoke dust of processing of method of the invention, by percentage to the quality, the arsenic-containing smoke dust includes
Following main component: arsenic: 1%~60%, antimony: 1%~55%, lead: 0.1%~35%, zinc: 0.1%~30%, copper: 0.1%
~5%, tellurium: 0.01%~3%, selenium: 0.01%~3%.
Preferably, in step (1), extraction temperature is 150~260 DEG C.
Preferably, in step (1), leaching pressure is 1.5~2MPa.
Preferably, in step (1), the liquid solid product mass ratio of water and arsenic-containing smoke dust is 3:1~20:1 (ml:g), optimal to be
10:1。
Preferably, step (1) carries out under stiring, and the speed of the stirring is 50r/min~500r/min.
Preferably, in step (1), extraction time is 30~240min, and optimal is 120~200min.
Preferably, in step (1), the oxidizing gas is selected from least one of oxygen, air, oxygen-enriched air.
As the preferable technical solution of the present invention, the operation of step (1) specifically: take arsenic-containing smoke dust in reaction kettle, press
It is 3:1~20:1 (ml:g) meter according to the liquid solid of water and arsenic-containing smoke dust product mass ratio, water is added thereto, is passed through into reaction kettle
Oxidizing gas, carries out oxygen leaching under 150~260 DEG C, 1.5~2MPa, 50~500r/min, and control extraction time is
120~200min.Such condition can realize the abundant leaching of arsenic, and realization arsenic is sufficiently separated with other metals.
Leachate described in step (2) consolidates arsenic using the heavy arsenic method of lime.
Preferably, it in step (2), Gu arsenic carries out under the conditions of 10~90 DEG C, is further preferably carried out at 40~90 DEG C.
Preferably, in step (2), CaO and Ca (OH)2In Ca and leachate in As molar ratio (i.e. Ca/As) be 2~
8, further preferably 3~5.
Preferably, in step (2), in step (3), in molysite in Fe and leachate the molar ratio (i.e. Fe/As) of As be 1~
5, further preferably 2-3.
Preferably, in step (3), the iron salt solutions are in ferrum sulfuricum oxydatum solutum, ferric chloride solution, iron nitrate solution
At least one, the neutralizer are selected from least one of sodium carbonate, sodium bicarbonate, sodium hydroxide.
Preferably, in step (4), the leached mud washing uses fluidization wash tower, and generally washing 2~3 times can make
The content of arsenic is less than 0.1% in gained washery slag.
In step (5), antimonial is reduced to metallic antimony in reactor, and the impurity such as Pb, Bi, Sn are also reduced into list
Matter enters in needle antimony alloy, pit ash and a small amount of arsenic, antimony, lead oxide that generated more alveolar substances are reacted with soda ash is light
" bubble slag ", floats on antimony liquid surface.After the completion of reduction, bubble slag is clawed, under conditions of muffle, blasts primary air into antimony liquid,
So that antimony volatilization is generated a large amount of antimony vapours, while being passed through auxiliary air to reactor, antimony vapour oxidation is made to generate antimony oxide, benefit
Antimony liquid temperature in the necessary temperature of reactor and furnace is maintained with the big calorimetric that antimony oxidation generates.It is dense due to melt body surface metal antimony
Degree has comparative advantage, and metallic antimony property is more active than lead, bismuth, tin, make the antimony in aluminium alloy be oxidized to antimony oxide volatilize into
Enter flue dust, lead, bismuth, tin etc. then stays in the lead of reactor bottom, realizes that a furnace is dual-purpose.
Preferably, in step (5), the temperature of the reduction melting is 900~1200 DEG C.
Preferably, in step (5), the temperature of the oxidation blowing is 650~800 DEG C.
Preferably, in step (5), the reduction melting and oxidation blowing are using blast furnace, reverberatory furnace, bottom convertor, side-blown
Any one in furnace, top blast furnace.
The scheme of the invention is pressing water logging by oxygen, solvable arsenic in flue dust is removed, and trivalent arsenic is oxidized to pentavalent arsenic, soaked
Liquid through lime sinks arsenic method out and precipitation transformation method synthesizing high-stability consolidates arsenic mineral, leached mud through fluidization wash, reduction melting,
The processes such as oxidation blowing, recycle each valuable element.Arsenic is removed and is solidified from flue dust by the method, and antimony, lead,
Bismuth etc. is stayed in as far as possible in dearsenification slag, and the separation of realization arsenic and valuable metal is simultaneously innoxious.Comprehensive resource utilization rate of the present invention is high,
Raw material wide adaptation range solves the cigarette ash that pollution problem in traditional handicraft extraction process, especially Lead-Zinc Sintering Process generate,
The advantage of this method is more obvious.
The advantages of the method for the present invention and good effect:
1, the present invention the solvable arsenic in arsenic flue dust is totally removed, the raw material arsenic after dearsenification in such a way that oxygen presses water logging
Content is low, can the valuable metals such as synthetical recovery antimony, lead, reduce the content of arsenic in product；
2, the present invention presses water logging using oxygen, by As3+It is oxidized to As5+, solve the dysoxidizable problem of trivalent arsenic；
3, the present invention changes the pH value of feed way, accurate control synthesis process on the basis of original technology, using stone
The heavy arsenic method of ash and the solid arsenic mineral of precipitation transformation method synthesis stablize stockpiling under the conditions of wide pH range 2~11 and strong reducing property,
It migrates As no longer, the As of smelting system is also made to have an ideal open circuit, be that a kind of process flow is simple, resource section
About, environmental-friendly method, and it is that the scorodite stability of preparation is good the advantages of precipitation transformation method, stable region field width, side
Just it stores up, and process costs are low, it is easy to operate.
4, the present invention uses fluidization wash, further decreases the content of arsenic in leached mud, recycling product quality can be improved；
5, the present invention recycles valuable metal using reduction melting, realizes that metal comprehensive reutilization maximizes.
6, the reasonable process collocation of the present invention, enables arsenic safe disposal, and antimony, lead, bismuth etc. are recycled and efficiently used,
Achieve the purpose that environmental protection, economic, energy conservation, high resource utilization, realizes the innoxious and maximum resource utilization of arsenic.Due to arsenic
It is not high that separation with other elements using wet processing avoids massive pollution and the utilization of resources brought by pyrogenic process
The problem of, entire technique substantially three-waste free discharge, all resources obtain maximal efficiency utilization, and products therefrom is convenient for subsequent
Processing and processing, so the present invention has the advantage of environmentally friendly, economic, energy conservation, high resource utilization.
Detailed description of the invention
Fig. 1 is process flow chart of the invention.
Specific embodiment
Technical solution of the present invention is described in detail below, the process flow of embodiment please refers to Fig. 1.The wherein percentage
Content is mass number.
Embodiment 1:
By taking certain domestic Lead And Zinc Smelter is containing arsenic smoke dust as an example, raw material main component is Pb 1.57%, As 48.56%, Sn
0.51%, Sb 21.24%, Zn 0.73%, Te 0.35%, Se 0.25%, is handled using following steps:
(1) oxygen presses water logging: weighing the high-arsenic antimony flue dust of certain mass in reaction kettle, control condition is that liquid consolidates volume mass
Than 10:1, mixing speed 300r/min, 160 DEG C of extraction temperature, partial pressure of oxygen 2Mpa, extraction time 2h, after leaching, material is removed
Slurry is separated by filtration, and obtains leachate and leached mud；
Through detecting: arsenic leaching rate 64.53%, each element concentration Pb 709.60ppm, Se 31.02ppm, Sb in leachate
1.26g/L, Te 123.28ppm, As 29.88g/L.
(2) leachate consolidates arsenic: the pH value of leachate being adjusted to 1.5, oxygen is added into leachate in a manner of continuous charging
Change calcium, control Ca/As molar ratio is 6, arsenic 40 hours solid in 40 DEG C；
(3) precipitating is converted into scorodite: iron nitrate solution being added into the solution of step (2), the control of Fe/As molar ratio exists
5, while sodium carbonate is added as neutralizer, regulation reaction is stablized under being 1.5 in pH value to be carried out, and consolidating for high stability is ultimately generated
Arsenic mineral, the addition speed of iron nitrate solution are 5ml/min, and the addition speed of sodium carbonate is 5ml/min.
Through detecting, the solid arsenic mineral of synthesis meets GB5085.3-2007 (solid waste judging standard-leaching characteristic identification)
Regulation, can store up safely.
(4) leached mud washs: the leached mud of step (1) uses fluidization wash tower water according to liquid solid product mass ratio 5:1
It washes leached mud 2 times, obtains washing lotion and washery slag；
Through detecting: washing lotion 9.62g/L containing arsenic, washery slag contain solvable arsenic 0.1%.
(5) washery slag recycles valuable metal: being incorporated charcoal, coal and soda ash after the washery slag of step (3) is dry, reflects at 1150 DEG C
Reduction melting is carried out in furnace, melting generates bubble slag, lead-antimony alloy and flue dust.Bubble slag send lead to smelt, flue dust return reduction melting or
Oxygen presses water logging, and lead-antimony alloy enters oxidation blowing process.Oxidation blowing operation are as follows: in muffle and 700 DEG C of blowing temperature of oxidation
Under the conditions of, primary air is blasted into lead-antimony alloy, while being passed through auxiliary air to reactor, antimony vapour oxidation is made to generate three oxygen
Change two antimony, the antimony oxide of generation is as stibium trioxide product.The slag that blows returns former smelting system, and the lead bullion aoxidized after blowing is sent
Lead rectification systems.
Through detecting: Pb contains 3.76% containing 75.67%, As containing 18.96%, Sb in lead-antimony alloy；The stibium trioxide powder of generation meets
The trade mark specified in GB/T 4062-2013 is Sb2O399.00 stibium trioxide powder；Contain Pb 97.65% in lead bullion, contains Sb
1.85%, contain As 0.52%.
Embodiment 2:
By taking certain domestic Lead And Zinc Smelter is containing arsenic smoke dust as an example, raw material main component is Pb 6.88%, As 36.51%, Sn
1.11%, Sb 29.77%, Zn 0.54%, Te 0.24%, Se 0.05%, is handled using following steps:
(1) oxygen presses water logging: weighing the high-arsenic antimony flue dust of certain mass in reaction kettle, control condition is that liquid consolidates volume mass
Than 20:1, mixing speed 300r/min, 160 DEG C of extraction temperature, partial pressure of oxygen 0.5Mpa, extraction time 2h, after leaching, remove
Slurry filtration separation, obtains leachate and leached mud；
Through detecting: arsenic leaching rate 51.29%, each element concentration Pb 515.20ppm, Se 31.56ppm, Sb in leachate
0.88g/L, Te 122.26ppm, As 9.36g/L.
(2) leachate consolidates arsenic: the pH value of leachate being adjusted to 2, oxidation is added into leachate in a manner of continuous charging
Calcium, control Ca/As molar ratio are 10, arsenic 100 hours solid in 40 DEG C；
(3) precipitating is converted into scorodite: iron nitrate solution being added into the solution of step (2), the control of Fe/As molar ratio exists
5, while sodium hydroxide solution is added as neutralizer, regulation reaction is stablized under being 2 in pH value to be carried out, and high stability is ultimately generated
Solid arsenic mineral, the addition speed of iron nitrate solution is 5ml/min, and the addition speed of sodium carbonate is 5ml/min.
Through detecting, the solid arsenic mineral of synthesis meets GB5085.3-2007 (solid waste judging standard-leaching characteristic identification)
Regulation, can store up safely.
(4) leached mud washs: the leached mud of step (1) uses fluidization wash tower water according to liquid solid product mass ratio 5:1
It washes leached mud 2 times, obtains washing lotion and washery slag；
Through detecting: washing lotion 8.45g/L containing arsenic, washery slag contain solvable arsenic 0.1%.
(5) washery slag recycles valuable metal: being incorporated charcoal, coal and soda ash after the washery slag of step (3) is dry, reflects at 1150 DEG C
Reduction melting is carried out in furnace, melting generates bubble slag, lead-antimony alloy and flue dust.Bubble slag send lead to smelt, flue dust return reduction melting or
Oxygen presses water logging, and lead-antimony alloy enters oxidation blowing process.Oxidation blowing operation are as follows: in muffle and 800 DEG C of blowing temperature of oxidation
Under the conditions of, primary air is blasted into lead-antimony alloy, while being passed through auxiliary air to reactor, antimony vapour oxidation is made to generate three oxygen
Change two antimony, the antimony oxide of generation is as stibium trioxide product.The slag that blows returns former smelting system, and the lead bullion aoxidized after blowing is sent
Lead rectification systems.
Through detecting: Pb contains 5.58% containing 64.98%, As containing 28.27%, Sb in lead-antimony alloy；The stibium trioxide powder of generation meets
The trade mark specified in GB/T 4062-2013 is Sb2O399.00 stibium trioxide powder；Contain Pb 95.25% in lead bullion, contains Sb
2.75%, contain As 0.67%.
Embodiment 3:
By taking certain domestic Lead And Zinc Smelter is containing arsenic smoke dust as an example, raw material main component is Pb 5.46%, As 30.29%, Sn
0.98%, Sb 29.58%, Zn 0.68%, Te 0.26%, Se 0.07%, is handled using following steps:
(1) oxygen presses water logging: weighing the high-arsenic antimony flue dust of certain mass in reaction kettle, control condition is that liquid consolidates volume mass
Than 10:1, mixing speed 300r/min, 200 DEG C of extraction temperature, partial pressure of oxygen 2.5Mpa, extraction time 4h, after leaching, remove
Slurry filtration separation, obtains leachate and leached mud；
Through detecting: arsenic leaching rate 64.52%, each element concentration Pb 956.35ppm, Se 18.91ppm, Sb in leachate
0.93g/L, Te 144.92ppm, As 19.54g/L.
(2) leachate consolidates arsenic: the pH value of leachate being adjusted to 3, oxidation is added into leachate in a manner of continuous charging
Calcium, control Ca/As molar ratio are 6, arsenic 40 hours solid in 90 DEG C；
(3) precipitating is converted into scorodite: iron nitrate solution being added into the solution of step (2), the control of Fe/As molar ratio exists
5, while sodium carbonate is added as neutralizer, regulation reaction is stablized under being 3 in pH value to be carried out, and the solid arsenic of high stability is ultimately generated
Mineral, the addition speed of iron nitrate solution are 5ml/min, and the addition speed of sodium carbonate is 5ml/min.
Through detecting, the solid arsenic mineral of synthesis meets GB5085.3-2007 (solid waste judging standard-leaching characteristic identification)
Regulation, can store up safely.
(4) leached mud washs: the leached mud of step (1) uses fluidization wash tower water according to liquid solid product mass ratio 5:1
It washes leached mud 2 times, obtains washing lotion and washery slag；
Through detecting: washing lotion 5.46g/L containing arsenic, washery slag contain solvable arsenic 0.1%.
(5) washery slag recycles valuable metal: being incorporated charcoal, coal and soda ash after the washery slag of step (3) is dry, reflects at 1150 DEG C
Reduction melting is carried out in furnace, melting generates bubble slag, lead-antimony alloy and flue dust.Bubble slag send lead to smelt, flue dust return reduction melting or
Oxygen presses water logging, and lead-antimony alloy enters oxidation blowing process.Oxidation blowing operation are as follows: in muffle and 650 DEG C of blowing temperature of oxidation
Under the conditions of, primary air is blasted into lead-antimony alloy, while being passed through auxiliary air to reactor, antimony vapour oxidation is made to generate three oxygen
Change two antimony, the antimony oxide of generation is as stibium trioxide product.The slag that blows returns former smelting system, and the lead bullion aoxidized after blowing is sent
Lead rectification systems.
Through detecting: Pb contains 6.45% containing 65.27%, As containing 26.67%, Sb in lead-antimony alloy；The stibium trioxide powder of generation meets
The trade mark specified in GB/T 4062-2013 is Sb2O399.00 stibium trioxide powder；Contain Pb 95.89% in lead bullion, contains Sb
2.98%, contain As 0.64%.
Although above having used general explanation, specific embodiment and test, 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 (9)
1. a kind of method that arsenic-containing smoke dust comprehensive utilization and precipitation transformation method synthesize solid arsenic mineral, which is characterized in that including following
Step:
(1) oxygen presses water logging: it takes arsenic-containing smoke dust in reaction kettle, water is added thereto, oxidizing gas is passed through into reaction kettle, in
120 ~ 300 DEG C, carry out oxygen leaching under 0.1 ~ 3.5MPa, after oxygen leaching, through solid-liquor separation, obtain arsenic leaching solution and
Leached mud；In terms of ml/g, the liquid solid product mass ratio of water and arsenic-containing smoke dust is 3:1 ~ 20:1；The water logging of oxygen pressure under stiring into
Row, the speed of the stirring are 50r/min ~ 500r/min；Extraction time is 30 ~ 240min；
(2) leachate consolidates arsenic: the pH value of leachate obtained by regulating step (1) is to 1.5 ~ 3, to leachate in a manner of continuous charging
Middle addition CaO and Ca (OH)2One or both of solid arsenic, obtain arsenic acid calcium precipitate；CaO and Ca (OH)2In Ca and leachate in
The molar ratio of As is 2 ~ 8；The solid arsenic carries out under the conditions of 10 ~ 90 DEG C；
(3) precipitating is converted into solid arsenic mineral: iron salt solutions being added into the system of step (2), while being continuously added neutralizer, adjust
Control reaction carries out under the conditions of pH value 1.5 ~ 3, makes Fe3+With AsO4 3-Reaction generates the solid arsenic mineral of high stability, and final synthesis is steady
Fixed solid arsenic mineral；
The iron salt solutions are selected from least one of ferrum sulfuricum oxydatum solutum, ferric chloride solution, iron nitrate solution, the neutralizer choosing
From at least one of sodium carbonate, sodium bicarbonate, sodium hydroxide；
The molar ratio of Fe and As in leachate is 1 ~ 5 in iron salt solutions；
(4) leached mud washs: washing to step (1) resulting leached mud, obtains washing lotion and washery slag, controls arsenic in washery slag and contain
Amount is less than 0.1%, wherein the washing lotion return step (1) carries out oxygen and presses water logging；
(5) washery slag recycles valuable metal: after the washery slag that step (4) obtains is dry, mixing restore with charcoal, coal and soda ash and melt
Refining generates 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 by: by percentage to the quality, the flue dust includes following main
Ingredient: 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. according to the method described in claim 1, it is characterized by: the operation of step (1) specifically: take arsenic-containing smoke dust in reaction
In kettle, accumulating mass ratio according to the liquid solid of water and arsenic-containing smoke dust in terms of ml/g is 3:1 ~ 20:1, and water, Xiang Fanying are added thereto
It is passed through oxidizing gas in kettle, oxygen leaching, control leaching are carried out under 150 ~ 260 DEG C, 1.5 ~ 2Mpa, 50r/min ~ 500r/min
The time is 120 ~ 200min out.
4. according to the method described in claim 1, it is characterized by: extraction temperature is 150 ~ 260 DEG C, and leaching is pressed in step (1)
Power is 1.5 ~ 2MPa.
5. according to the method described in claim 1, it is characterized by: the oxidizing gas is oxygen, air in step (1)
Or oxygen-enriched air.
6. -3,5 described in any item methods according to claim 1, it is characterised in that: in step (5), the behaviour of the oxidation blowing
As: under conditions of muffle, primary air is blasted into lead-antimony alloy, antimony volatilization is made to generate a large amount of antimony vapours, while to anti-
It answers device to be passed through auxiliary air, antimony vapour oxidation is made to generate antimony oxide.
7. according to the method described in claim 6, it is characterized by: step (5) the oxidation blowing is under the conditions of 650 ~ 800 DEG C
It carries out.
8. according to the method described in claim 1, it is characterized by: in step (5), the temperature of the reduction melting is 900 ~
1200℃。
9. -3,5,7 described in any item methods according to claim 1, it is characterised in that: in step (4), the leached mud washing
Using fluidization wash tower；And/or in step (5), the reduction melting and oxidation blowing use blast furnace, reverberatory furnace, bottom blowing
Furnace, side-blown converter, any one in top blast furnace.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201611191082.8A CN106834709B (en) | 2016-12-21 | 2016-12-21 | The method that a kind of comprehensive utilization of arsenic-containing smoke dust and precipitation transformation method synthesize solid arsenic mineral |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201611191082.8A CN106834709B (en) | 2016-12-21 | 2016-12-21 | The method that a kind of comprehensive utilization of arsenic-containing smoke dust and precipitation transformation method synthesize solid arsenic mineral |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN106834709A CN106834709A (en) | 2017-06-13 |
| CN106834709B true CN106834709B (en) | 2019-03-05 |
Family
ID=59135124
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201611191082.8A Active CN106834709B (en) | 2016-12-21 | 2016-12-21 | The method that a kind of comprehensive utilization of arsenic-containing smoke dust and precipitation transformation method synthesize solid arsenic mineral |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN106834709B (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108950222A (en) * | 2018-07-27 | 2018-12-07 | 昆明冶金研究院 | A kind of high arsenic tin flue dust mineralizes the method for solid arsenic collaboration recycling tin |
| CN112047811B (en) * | 2020-08-24 | 2023-10-27 | 锡矿山闪星锑业有限责任公司 | Arsenic removal method for arsenic-containing ethylene glycol mother liquor |
| CN113444886B (en) * | 2021-07-21 | 2022-12-06 | 东北大学 | Valuable element leaching and recycling method for copper smelting smoke dust |
| CN113684368A (en) * | 2021-08-29 | 2021-11-23 | 中南大学 | Method for co-processing arsenic sulfide slag and arsenic-containing smoke dust in copper smelting |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4244734A (en) * | 1979-07-19 | 1981-01-13 | Hazen Research, Inc. | Process for recovering metal values from materials containing arsenic |
| CN101200776A (en) * | 2006-12-14 | 2008-06-18 | 中南大学 | Method for removing arsenic from smoke containing arsenic trioxide |
| CN101508479A (en) * | 2009-02-13 | 2009-08-19 | 中南大学 | Oxidation method for trivalent arsenic in solution |
| CN102634666A (en) * | 2012-04-24 | 2012-08-15 | 葫芦岛锌业股份有限公司 | Method for dearsenicating fresh high-arsenium lead anode slime under oxygen pressure |
| CN102674526A (en) * | 2012-05-14 | 2012-09-19 | 中南大学 | Method for precipitating and stabilizing As from As-containing solution |
| CN104911364A (en) * | 2015-06-26 | 2015-09-16 | 郴州市金贵银业股份有限公司 | Environment-friendly and high-efficiency production method of antimony white by using Sb and As-containing ash |
-
2016
- 2016-12-21 CN CN201611191082.8A patent/CN106834709B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4244734A (en) * | 1979-07-19 | 1981-01-13 | Hazen Research, Inc. | Process for recovering metal values from materials containing arsenic |
| CN101200776A (en) * | 2006-12-14 | 2008-06-18 | 中南大学 | Method for removing arsenic from smoke containing arsenic trioxide |
| CN101508479A (en) * | 2009-02-13 | 2009-08-19 | 中南大学 | Oxidation method for trivalent arsenic in solution |
| CN102634666A (en) * | 2012-04-24 | 2012-08-15 | 葫芦岛锌业股份有限公司 | Method for dearsenicating fresh high-arsenium lead anode slime under oxygen pressure |
| CN102674526A (en) * | 2012-05-14 | 2012-09-19 | 中南大学 | Method for precipitating and stabilizing As from As-containing solution |
| CN104911364A (en) * | 2015-06-26 | 2015-09-16 | 郴州市金贵银业股份有限公司 | Environment-friendly and high-efficiency production method of antimony white by using Sb and As-containing ash |
Also Published As
| Publication number | Publication date |
|---|---|
| CN106834709A (en) | 2017-06-13 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN100462453C (en) | Comprehensive extraction of valent metal from bismuth-containing polymetallic material | |
| CN106834708B (en) | A kind of integrated conduct method of arsenic-containing smoke dust | |
| CN106834720B (en) | A kind of method that arsenic-containing smoke dust integrated treatment and regulation growth method synthesize solid arsenic mineral | |
| CN106834707B (en) | A kind of method that arsenic-containing material synthetical recovery and arsenic resource utilize | |
| CN106834709B (en) | The method that a kind of comprehensive utilization of arsenic-containing smoke dust and precipitation transformation method synthesize solid arsenic mineral | |
| CN106801145B (en) | One kind dearsenification and its cured method from arsenic-containing smoke dust | |
| CN106834715B (en) | A kind of method of comprehensive utilization of arsenic-containing material | |
| CN106834716B (en) | A kind of method of arsenic-containing smoke dust dearsenification and valuable element comprehensive reutilization | |
| CN106756058B (en) | One kind dearsenification and its cured method from arsenic-containing smoke dust | |
| CN103266225A (en) | Side-blown furnace reduction smelting technology for lead anode mud | |
| CN101328539A (en) | Oxidation oven ash hydrometallurgical leaching process | |
| CN102061395A (en) | Smelting and separating method of noble lead | |
| CN106834718B (en) | A kind of arsenic-containing smoke dust comprehensive utilization and the method for arsenic harmlessness disposing | |
| CN104451188A (en) | Method for separating lead and antimony of jamesonite concentrate by virtue of vacuum treatment | |
| CN106756059B (en) | A method of valuable metal is recycled from arsenic-containing smoke dust and precipitation transformation method synthesizes solid arsenic mineral | |
| CN106834714B (en) | A kind of integrated conduct method of arsenic-containing material | |
| CN101565780A (en) | Smelting method of polymetallic lead-zinc sulfide ore | |
| CN102586584A (en) | Method for selectively separating valuable metals from complex lead-containing precious metal material | |
| CN106834717B (en) | A method of recycling valuable metal and arsenic safe disposal from arsenic-containing smoke dust | |
| CN106834676B (en) | A kind of method that valuable metal and arsenic recycling harmlessness disposing are reclaimed from arsenic-containing smoke dust | |
| CN110284005A (en) | A method of the enriching and recovering lead from lead bullion | |
| CN106834712B (en) | A kind of method that arsenic-containing smoke dust dearsenification and distribution crystallisation synthesize solid arsenic mineral | |
| CN106834719B (en) | A method of from arsenic-containing smoke dust comprehensively recovering valuable metal and arsenic safe disposal | |
| CN106756057B (en) | A method of recycling valuable metal and arsenic harmlessness disposing from arsenic-containing smoke dust | |
| CN106834710B (en) | A method of from arsenic-containing smoke dust comprehensively recovering valuable metal and arsenic recycling |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |