CN106834709A - A kind of arsenic-containing smoke dust comprehensive utilization and the method for the solid arsenic mineral of precipitation transformation method synthesis - Google Patents
A kind of arsenic-containing smoke dust comprehensive utilization and the method for the solid arsenic mineral of precipitation transformation method synthesis Download PDFInfo
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- CN106834709A CN106834709A CN201611191082.8A CN201611191082A CN106834709A CN 106834709 A CN106834709 A CN 106834709A CN 201611191082 A CN201611191082 A CN 201611191082A CN 106834709 A CN106834709 A CN 106834709A
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
- C22B7/02—Working-up flue dust
-
- A—HUMAN NECESSITIES
- A62—LIFE-SAVING; FIRE-FIGHTING
- A62D—CHEMICAL MEANS FOR EXTINGUISHING FIRES OR FOR COMBATING OR PROTECTING AGAINST HARMFUL CHEMICAL AGENTS; CHEMICAL MATERIALS FOR USE IN BREATHING APPARATUS
- A62D3/00—Processes for making harmful chemical substances harmless or less harmful, by effecting a chemical change in the substances
- A62D3/30—Processes for making harmful chemical substances harmless or less harmful, by effecting a chemical change in the substances by reacting with chemical agents
- A62D3/33—Processes for making harmful chemical substances harmless or less harmful, by effecting a chemical change in the substances by reacting with chemical agents by chemical fixing the harmful substance, e.g. by chelation or complexation
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- 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
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- 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 metallurgical technology field, more particularly to the method that a kind of comprehensive utilization of arsenic-containing smoke dust and precipitation transformation method synthesize solid arsenic mineral, the method includes that oxygen presses the solid arsenic of water logging, leachate, precipitates conversion, leached mud washing and washery slag recovery 5 steps of valuable metal.Water logging is pressed by oxygen, then solvable arsenic in removing flue dust, leachate solidifies solid arsenic mineral through the solid arsenic mineral of the heavy arsenic precipitation Synthesis stabilization of lime by the way of storing up.The operations such as leached mud is scrubbed, reduction melting, oxidation blowing, maximize and recycle each valuable element.Arsenic is removed the method the solid arsenic mineral of simultaneously synthesizing stable from flue dust, and antimony, lead, bismuth etc. 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 that pollution problem in traditional handicraft extraction process, particularly Lead-Zinc Sintering Process are produced, 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 arsenic-containing smoke dust comprehensive utilization and precipitation transformation method synthesis are solid
The method of arsenic mineral.
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 method for replacing reducing process acquisition crude arsenic and needle antimony, and CN103602834A discloses a kind of choosing
Selecting property oxidationreduction obtains purity As not high2O3With 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 more than 97.0%.But if contain and arsenogen disposition in flue dust
The close metal of matter (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 valuable metal powder is reclaimed not
Make further research.CN105567983A discloses a kind of handling process of Copper making flue dust water logging-alkali leaching, makes arsenic with metal point
From the arsenic product of preparation is at a discount, still higher containing arsenic in leached mud.CN104357668A discloses one kind waste acid and leaches cigarette
Dirt, electrodeposition dearsenification, acidleach and electrolytic deposition process easily produce arsenic hydride.CN105648226A and CN105648227A disclose oxygen pressure
Alkali leaching realize arsenic antimony separate method, arsenic antimony separate ratio more thoroughly, but the natrium arsenicum for obtaining in process is untreated, tellurium,
The valuable metals such as antimony are unrecovered.
In sum, dearsenification, the research paper of extraction valuable metal and Patents report are many but existing from flue dust
Technology is low there are still valuable metal comprehensive recovery, and arsenic product market is limited, there is a problem of potential potential safety hazard.Cause
This, 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 from cigarette containing arsenic
The method that valuable metal and arsenic harmlessness disposing are reclaimed in dirt.The present invention has environmental protection, economy, energy-conservation, resource utilization high
Advantage, realizes the harmless treatment of arsenic, specifically adopts the following technical scheme that：
A kind of arsenic-containing smoke dust comprehensive utilization and the method for the solid arsenic mineral of precipitation transformation method synthesis, comprise the following steps：
(1) oxygen pressure water logging：Arsenic-containing smoke dust is taken in reactor, water is added thereto to, to being passed through oxidisability gas in reactor
Body, in 120~300 DEG C, carries out oxygen leaching under 0.1~3.5MPa, after oxygen leaching terminates, through solid-liquor separation, obtain containing arsenic
Leachate and leached mud；
(2) the solid arsenic of leachate：Regulating step (1) gained leachate pH value to 1.5~3, in the way of continuous charging to
CaO and Ca (OH) is added in leachate2In one or two solid arsenic, obtain arsenic acid calcium precipitate；
(3) precipitation is converted into scorodite：Iron salt solutions are added in system to step (2), while nertralizer is continuously added,
Regulation and control reaction is carried out under the conditions of pH value 1.5~3, makes Fe3+With AsO4 3-The solid arsenic mineral of reaction generation high stability, final
To solid arsenic mineral；
(4) leached mud washing：Leached mud obtained by step (1) is washed, washing lotion and washery slag is obtained, in control washery slag
Arsenic content is less than 0.1%, wherein, the washing lotion return to step (1) carries out oxygen pressure water logging；
(5) washery slag reclaims valuable metal：After the washery slag that step (4) is obtained is dried, mix with charcoal, coal and soda ash and gone back
Former 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, obtain antimony vapour, blowing slag and
Lead bullion；By antimony vapour oxidation generation antimony oxide, as stibium trioxide product；The blowing slag is returned into reduction melting operation
Dispensing；Lead is sent to refine the lead bullion.
The particularly suitable following arsenic-containing smoke dust for the treatment of of the method for the present 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), water is 3 with the liquid solid product mass ratio of arsenic-containing smoke dust:1~20:1(ml:G), it is optimal to be
10:1。
Preferably, step (1) is carried out under agitation, 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 are selected from least one in oxygen, air, oxygen-enriched air.
Used as the present invention preferably technical scheme, the operation of step (1) is specially：Arsenic-containing smoke dust is taken in reactor, is pressed
Liquid solid product mass ratio according to water and arsenic-containing smoke dust is 3:1~20:1(ml:G) count, be added thereto to water, to being passed through in reactor
Oxidizing gas, in 150~260 DEG C, carry out oxygen leaching under 1.5~2MPa, 50~500r/min, control the extraction time to be
120~200min.This kind of condition can realize the abundant leaching of arsenic, realize being sufficiently separated for arsenic and other metals.
The solid arsenic of leachate described in step (2) is using the heavy arsenic method of lime.
Preferably, in step (2), Gu arsenic is carried out under the conditions of 10~90 DEG C, further preferably carried out at 40~90 DEG C.
Preferably, in step (2), CaO and Ca (OH)2In Ca and leachate in As mol ratio (i.e. Ca/As) for 2~
8, more preferably 3~5.
Preferably, in step (2), in step (3), in molysite in Fe and leachate the mol ratio (i.e. Fe/As) of As for 1~
5, more preferably 2-3.
Preferably, in step (3), the iron salt solutions are selected from ferrum sulfuricum oxydatum solutum, ferric chloride solution, iron nitrate solution
At least one, the nertralizer is selected from least one in sodium carbonate, sodium acid carbonate, NaOH.
Preferably, in step (4), the leached mud washing uses fluidization wash tower, and typically 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 the impurity such as metallic antimony, Pb, Bi, Sn and is also reduced into list in reactor
Matter enters in needle antimony alloy, and pit ash and a small amount of arsenic, antimony, the oxide of lead react that to generate many alveolar substances light with soda ash
" bubble slag ", floats over antimony liquid surface.After the completion of reduction, bubble slag is clawed, under conditions of muffle, to blasting primary air in antimony liquid,
Antimony is volatilized and produce a large amount of antimony vapours, while being passed through auxiliary air to reactor, antimony vapour is aoxidized generation antimony oxide, profit
Antimony liquid temperature degree in the big necessary temperature of calorimetric maintenance reaction device and stove for producing is aoxidized with antimony.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 to stay in the lead of reactor bottom, realize that a stove 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 stove, top blast stove.
The solution of the present invention is to press water logging, solvable arsenic in removing flue dust by oxygen, and trivalent arsenic is oxidized into pentavalent arsenic, is soaked
Go out liquid through the heavy arsenic method of lime and the solid arsenic mineral of precipitation transformation method synthesizing high-stability, leached mud through fluidization wash, reduction melting,
The operations such as oxidation blowing, make each valuable element be recycled utilization.Arsenic is removed and solidified by the method from flue dust, and antimony, lead,
Bismuth etc. is stayed in dearsenification slag as far as possible, 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 cigarette ash that pollution problem in traditional handicraft extraction process, particularly Lead-Zinc Sintering Process are produced,
The advantage of this method is more obvious.
The advantage and good effect of the inventive method：
1st, the present invention is all removed the solvable arsenic in arsenic flue dust, the raw material arsenic after dearsenification by the way of oxygen pressure water logging
Content is low, can the valuable metal such as synthetical recovery antimony, lead, reduce the content of arsenic in product；
2nd, the present invention presses water logging using oxygen, by As3+It is oxidized to As5+, solve the dysoxidizable problem of trivalent arsenic；
3rd, the present invention changes feed way, the pH value of precise control building-up process on the basis of original technology, using stone
The heavy arsenic method of ash and the solid arsenic mineral of precipitation transformation method the synthesis stabilization under the conditions of pH scopes 2~11 wide and strong reducing property are stored up,
As is no longer migrated, also making the As of smelting system has an ideal open circuit, be that a kind of technological process is simple, resource section
The advantage of about, environment-friendly method, and precipitation transformation method is the scorodite good stability for preparing, stable region field width, side
Just store up, and process costs are low, it is easy to operate.
4th, the present invention uses fluidization wash, further reduces the content of arsenic in leached mud, can improve recovery product quality；
5th, the present invention reclaims valuable metal using reduction melting, realizes that metal comprehensive reutilization is maximized.
6th, the rational operation collocation of the present invention, enables arsenic safe disposal, antimony, lead, bismuth etc. to be recycled and effectively utilize,
Environmental protection, economy, energy-conservation, the purpose of resource utilization high have been reached, the innoxious and maximum resource utilization of arsenic has been realized.Due to arsenic
Separated with other elements and use that wet processing avoids massive pollution that pyrogenic process brought and the utilization of resources is not high
Problem, whole technique substantially three-waste free discharge, all resources obtain maximal efficiency utilization, products therefrom is easy to follow-up
Treatment and processing, so the present invention has environmental protection, economy, energy-conservation, the advantage of resource utilization high.
Brief description of the drawings
Fig. 1 is process chart of the invention.
Specific embodiment
Below to the detailed narration of technical scheme, the technological process of embodiment refer to Fig. 1.Wherein described percentage
Content is mass number.
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%, is processed using following steps：
(1) oxygen pressure water logging：The high-arsenic antimony flue dust of certain mass is weighed in reactor, control condition is the solid volume mass of liquid
Than 10:1, mixing speed 300r/min, 160 DEG C of extraction temperature, partial pressure of oxygen 2Mpa, extraction time 2h after leaching terminates, remove material
Slurry is separated by filtration, and obtains leachate and leached mud；
After testing：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) the solid arsenic of leachate：The pH value of leachate is adjusted to 1.5, to adding oxygen in leachate in the way of continuous charging
Change calcium, it is 6 to control Ca/As mol ratios, and arsenic is consolidated 40 hours in 40 DEG C；
(3) precipitation is converted into scorodite：Iron nitrate solution is added in solution to step (2), the control of Fe/As mol ratios exists
5, while adding sodium carbonate as nertralizer, regulation and control reaction is that 1.5 times stabilizations are carried out in pH value, ultimately generates consolidating for high stability
Arsenic mineral, the addition speed of iron nitrate solution is 5ml/min, and the addition speed of sodium carbonate is 5ml/min.
After testing, 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 washing：The leached mud of step (1) accumulates mass ratio 5 according to liquid solid:1 uses fluidization wash tower water
Wash leached mud 2 times, obtain washing lotion and washery slag；
After testing：Washing lotion 9.62g/L containing arsenic, washery slag contains solvable arsenic 0.1%.
(5) washery slag reclaims valuable metal：The washery slag of step (3) allocates charcoal, coal and soda ash into after drying, in 1150 DEG C of reflections
Reduction melting, melting generation bubble slag, lead-antimony alloy and flue dust are carried out in stove.Bubble slag send lead to smelt, flue dust return reduction melting or
Oxygen presses water logging, and lead-antimony alloy enters oxidation blowing operation.Aoxidizing blowing operation is：In muffle and 700 DEG C of blowing temperature of oxidation
Under the conditions of, to primary air is blasted in lead-antimony alloy, while being passed through auxiliary air to reactor, antimony vapour is aoxidized three oxygen of generation
Change two antimony, the antimony oxide of generation is used as stibium trioxide product.Blowing slag returns former smelting system, and the lead bullion aoxidized after blowing send
Lead rectification systems.
After testing：Pb contains 3.76% containing 18.96%, Sb containing 75.67%, As 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, 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%, is processed using following steps：
(1) oxygen pressure water logging：The high-arsenic antimony flue dust of certain mass is weighed in reactor, control condition is the solid volume mass of liquid
Than 20:1, mixing speed 300r/min, 160 DEG C of extraction temperature, partial pressure of oxygen 0.5Mpa, extraction time 2h after leaching terminates, are removed
Slurry filtration is separated, and obtains leachate and leached mud；
After testing：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) the solid arsenic of leachate：The pH value of leachate is adjusted to 2, to addition oxidation in leachate in the way of continuous charging
Calcium, it is 10 to control Ca/As mol ratios, and arsenic is consolidated 100 hours in 40 DEG C；
(3) precipitation is converted into scorodite：Iron nitrate solution is added in solution to step (2), the control of Fe/As mol ratios exists
5, while adding sodium hydroxide solution as nertralizer, regulation and control reaction is that 2 times stabilizations are carried out in pH value, ultimately generates high stability
Solid arsenic mineral, the addition speed of iron nitrate solution is 5ml/min, and the addition speed of sodium carbonate is 5ml/min.
After testing, 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 washing：The leached mud of step (1) accumulates mass ratio 5 according to liquid solid:1 uses fluidization wash tower water
Wash leached mud 2 times, obtain washing lotion and washery slag；
After testing：Washing lotion 8.45g/L containing arsenic, washery slag contains solvable arsenic 0.1%.
(5) washery slag reclaims valuable metal：The washery slag of step (3) allocates charcoal, coal and soda ash into after drying, in 1150 DEG C of reflections
Reduction melting, melting generation bubble slag, lead-antimony alloy and flue dust are carried out in stove.Bubble slag send lead to smelt, flue dust return reduction melting or
Oxygen presses water logging, and lead-antimony alloy enters oxidation blowing operation.Aoxidizing blowing operation is：In muffle and 800 DEG C of blowing temperature of oxidation
Under the conditions of, to primary air is blasted in lead-antimony alloy, while being passed through auxiliary air to reactor, antimony vapour is aoxidized three oxygen of generation
Change two antimony, the antimony oxide of generation is used as stibium trioxide product.Blowing slag returns former smelting system, and the lead bullion aoxidized after blowing send
Lead rectification systems.
After testing：Pb contains 5.58% containing 28.27%, Sb containing 64.98%, As 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, 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%, is processed using following steps：
(1) oxygen pressure water logging：The high-arsenic antimony flue dust of certain mass is weighed in reactor, control condition is the solid volume mass of liquid
Than 10:1, mixing speed 300r/min, 200 DEG C of extraction temperature, partial pressure of oxygen 2.5Mpa, extraction time 4h after leaching terminates, are removed
Slurry filtration is separated, and obtains leachate and leached mud；
After testing：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) the solid arsenic of leachate：The pH value of leachate is adjusted to 3, to addition oxidation in leachate in the way of continuous charging
Calcium, it is 6 to control Ca/As mol ratios, and arsenic is consolidated 40 hours in 90 DEG C；
(3) precipitation is converted into scorodite：Iron nitrate solution is added in solution to step (2), the control of Fe/As mol ratios exists
5, while adding sodium carbonate as nertralizer, regulation and control reaction is that 3 times stabilizations are carried out in pH value, ultimately generates the solid arsenic of high stability
Mineral, the addition speed of iron nitrate solution is 5ml/min, and the addition speed of sodium carbonate is 5ml/min.
After testing, 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 washing：The leached mud of step (1) accumulates mass ratio 5 according to liquid solid:1 uses fluidization wash tower water
Wash leached mud 2 times, obtain washing lotion and washery slag；
After testing：Washing lotion 5.46g/L containing arsenic, washery slag contains solvable arsenic 0.1%.
(5) washery slag reclaims valuable metal：The washery slag of step (3) allocates charcoal, coal and soda ash into after drying, in 1150 DEG C of reflections
Reduction melting, melting generation bubble slag, lead-antimony alloy and flue dust are carried out in stove.Bubble slag send lead to smelt, flue dust return reduction melting or
Oxygen presses water logging, and lead-antimony alloy enters oxidation blowing operation.Aoxidizing blowing operation is：In muffle and 650 DEG C of blowing temperature of oxidation
Under the conditions of, to primary air is blasted in lead-antimony alloy, while being passed through auxiliary air to reactor, antimony vapour is aoxidized three oxygen of generation
Change two antimony, the antimony oxide of generation is used as stibium trioxide product.Blowing slag returns former smelting system, and the lead bullion aoxidized after blowing send
Lead rectification systems.
After testing：Pb contains 6.45% containing 26.67%, Sb containing 65.27%, As 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, 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 arsenic-containing smoke dust comprehensive utilization and precipitation transformation method synthesize solid arsenic mineral, it is characterised in that including following
Step：
(1) oxygen pressure water logging：Arsenic-containing smoke dust is taken in reactor, water is added thereto to, to being passed through oxidizing gas in reactor, in
120~300 DEG C, oxygen leaching is carried out under 0.1~3.5MPa, after oxygen leaching terminates, through solid-liquor separation, obtain arsenic leaching solution
And leached mud；
(2) the solid arsenic of leachate：Regulating step (1) gained leachate pH value to 1.5~3, to leaching in the way of continuous charging
CaO and Ca (OH) is added in liquid2In one or two solid arsenic, obtain arsenic acid calcium precipitate；
(3) precipitation is converted into solid arsenic mineral：Iron salt solutions are added in system to step (2), while being continuously added nertralizer, is adjusted
Control reaction is carried out under the conditions of pH value 1.5~3, makes Fe3+With AsO4 3-The solid arsenic mineral of reaction generation high stability, final synthesis
The solid arsenic mineral of stabilization；
(4) leached mud washing：Leached mud obtained by step (1) is washed, washing lotion and washery slag is obtained, arsenic contains in control washery slag
Amount is less than 0.1%, wherein, the washing lotion return to step (1) carries out oxygen pressure water logging；
(5) washery slag reclaims valuable metal：After the washery slag that step (4) is obtained is dried, mix reduce with charcoal, coal and soda ash and melt
Refining, 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：By percentage to the quality, the flue dust includes following main
Composition：Arsenic：1%~60%, antimony：1%~55%, lead：0.1%~35%, zinc：0.1%~30%, copper：0.1%~5%,
Tellurium：0.01%~3%, selenium：0.01%~3%.
3. method according to claim 1, it is characterised in that：In step (1), the solid volume mass of liquid of water and arsenic-containing smoke dust
Than being 3：1~20：1(ml：g).
4. the method according to claim 1 or 3, it is characterised in that：In step (1), extraction temperature is 150~260 DEG C, leaching
Go out pressure for 1.5~2MPa；And/or, oxygen pressure water logging is carried out under agitation, the speed of the stirring for 50r/min~
500r/min。
5. method according to claim 1, it is characterised in that：In step (2), CaO and Ca (OH)2In Ca and leachate
The mol ratio of middle As is 2~8；And/or, in step (3), the mol ratio of Fe and As in leachate is 1~5 in iron salt solutions.
6. the method according to any one of claim 1-3 or 5, it is characterised in that：In step (3), the iron salt solutions choosing
At least one from ferrum sulfuricum oxydatum solutum, ferric chloride solution, iron nitrate solution, the nertralizer be selected from sodium carbonate, sodium acid carbonate,
At least one in NaOH.
7. method according to claim 6, it is characterised in that：In step (1), the oxidizing gas are oxygen, air
Or oxygen-enriched air.
8. the method according to any one of claim 1-3 or 5 or 7, it is characterised in that：In step (5), the oxidation blowing
Operation be：Under conditions of muffle, to primary air is blasted in lead-antimony alloy, antimony is volatilized and produce a large amount of antimony vapours, while
Auxiliary air is passed through to reactor, antimony vapour is aoxidized generation antimony oxide；Preferably, the oxidation blowing is 650~800
Carried out under the conditions of DEG C.
9. method according to claim 1, it is characterised in that：In step (5), the temperature of the reduction melting for 900~
1200℃。
10. the method according to any one of claim 1-3 or 5 or 7, it is characterised in that：In step (4), the leached mud
Washing uses fluidization wash tower；And/or, in step (5), the reduction melting and oxidation blowing using blast furnace, reverberatory furnace,
Any one in bottom convertor, side-blown converter, top blast stove.
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