CN106636678B - A kind of method that arsenic-containing material direct-reduction roasting prepares arsenic - Google Patents
A kind of method that arsenic-containing material direct-reduction roasting prepares arsenic Download PDFInfo
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- CN106636678B CN106636678B CN201611001156.7A CN201611001156A CN106636678B CN 106636678 B CN106636678 B CN 106636678B CN 201611001156 A CN201611001156 A CN 201611001156A CN 106636678 B CN106636678 B CN 106636678B
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- arsenic
- arsenate
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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
Abstract
The invention discloses the methods that a kind of direct-reduction roasting of arsenic-containing material prepares arsenic, and this method is using arsenate as raw material, and arsenate material and carbonaceous reducing agent are after mixing, it is placed in inertia or reducing atmosphere, under condition of negative pressure, carries out reduction roasting, baking flue gas is collected to get arsenic product.This method makes the common arsenic-containing material based on arsenate in metallurgical process be reduced to chemically stable elemental arsenic, elemental arsenic is not only nontoxic and can be as the raw material of semiconductor and alloy industry, with certain market value, reduction process realizes the minimizing of toxic arsenic-containing material, innoxious and recycling, it is that arsenic the most reasonably moves towards, great popularization.
Description
Technical field
The present invention relates to a kind of method preparing arsenic by arsenic-containing material, more particularly to a kind of material containing arsenate directly passes through
The method that reduction roasting prepares arsenic belongs to non-ferrous metallurgy technology field.
Technical background
Contain arsenic in the materials such as alkaline residue, cigarette ash and the earth of positive pole generated during nonferrous smelting, when using wet process more
When being handled and being purified, dearsenicating technology is essential.It is leached using alkaline condition, then it is a kind of to be crystallized or precipitated separation
Effectively and common arsenic removing method, but the process generates a large amount of arsenate, these arsenates are toxic and unstable chemcial property,
It is easy to threaten to environmental and human health impacts, it is therefore desirable to find a kind of economic and environment-friendly method and subsequently locate arsenate
Reason.
Processing for this kind of arsenate, at present mainly use cured method, common curing have cement solidification,
Lime solidification, plastics solidification, bitumen solidification, melting and solidification etc., although the fixation of arsenic can be realized to a certain extent, these
There is the problems such as front and back increase-volume of solidification needs a large amount of soil stockpilings and landfill than the big, later stage in curing.
Currently, the production of metallic arsenic is typically all that the ore containing arsenic is first passed through the oxide that arsenic is recycled in oxidizing roasting, then
Using the oxide of arsenic as raw material, carries out reduction reaction using hydrogen, carbon etc. as reducing agent and obtain, there are no direct-reduction arsenic acid
The report of salt.
Invention content
To solve existing arsenic-containing material, the especially intractable problem of arsenate material, the purpose of the present invention is be intended to carry
For a kind of cleaning, the method for efficiently directly recycling high-purity arsenic from arsenic-containing material, the method achieve subtracting for arsenic-containing waste residue
Quantization, innoxious and recycling.
In order to achieve the above technical purposes, the present invention provides the sides that a kind of direct-reduction roasting of arsenic-containing material prepares arsenic
Method after arsenate material is mixed with carbonaceous reducing agent, is placed in inertia or reducing atmosphere, in negative pressure and >=600 DEG C of temperature conditions
Lower carry out reduction roasting collects baking flue gas to get arsenic product.
The ratio of preferred scheme, the arsenate material and the carbonaceous reducing agent is with the molar ratio of arsenic and carbon for 1:
(0.5~5) it measures.
More preferably scheme, arsenate material include natrium arsenicum, calcium arsenate, lead arsenate, barium arsenate, magnesium arsenate, ferric arsenate
At least one of.
More preferably scheme, carbonaceous reducing agent include stone tar powder, coke blacking, active powdered carbon, carbon black powder, graphite powder and wood
At least one of powdered carbon.
The vacuum degree of preferred scheme, the negative pressure is 0.1~101325Pa.
Preferred scheme, reduction roasting temperature more preferably be 700~1200 DEG C, more preferable reduction roasting temperature be 700~
900℃。
Preferred scheme, reduction roasting time are 1~8h；The preferred reduction roasting time is 2~4h.
Preferred scheme, arsenic product grade are more than 90%；More preferably grade is more than 94%.
The reducing atmosphere used in technical scheme of the present invention is mainly inert gas and/or nitrogen and hydrogen and/or one
The mixed atmosphere of carbonoxide etc..
The basic principle of technical solution of the present invention, and the advantage brought compared with the prior art：
Technical scheme of the present invention key is to pass through inventor to the control of the conditions such as temperature, pressure in reduction roasting
Largely studies have shown that under conditions of technical solution of the present invention controls, arsenate material mainly occurs in carbonaceous reducing agent
Following reduction reaction is specifically described by taking natrium arsenicum, calcium arsenate and ferric arsenate as an example, reaction such as equation (1)~(7) of generation
It is shown：
4Na3AsO4+ 5C=5Na2CO3+As4(g)+Na2O (1)
4Na3AsO4+5C+H2O=5Na2CO3+As4(g)+2NaOH (2)
4Na3AsO4+10C+6H2O (g)=12NaOH+10CO (g)+As4(g) (3)
2Ca3(AsO4)2+ 5C=6CaO+5CO2(g)+As4(g) (4)
2Ca3(AsO4)2+ 10C=6CaO+10CO (g)+As4(g) (5)
4FeAsO4+ 8C=4Fe+8CO2(g)+As4(g) (6)
4FeAsO4+ 16C=4Fe+16CO (g)+As4(g) (7)
The relationship of the gibbs free energy change value and temperature of reacting (1)~(7) is as shown in Figure 1.By that can be seen in Fig. 1
Go out, under the process conditions of the present invention, these reactions can smoothly occur.
Compared with prior art, the beneficial effects of the invention are as follows：
1) one step of arsenate material is restored and prepares high-purity by technical scheme of the present invention first passage reduction roasting method
Arsenic product.
2) technical solution through the invention can be by a large amount of existing toxic arsenates of existing nonferrous metallurgy industry also
Originally it was nontoxic elemental arsenic, arsenic yield>95%, elemental arsenic purity>90%, it can be sold directly as product, before simultaneous reactions
The volume of matter containing arsenic reduces afterwards, is conducive to landfill and stockpiling disposition；The minimizing of arsenic, innoxious and disposal of resources are realized,
With promotional value.
3) technical scheme of the present invention process conditions are mild, environmentally protective, easy to operate, are conducive to industrialized production.
Description of the drawings
【Fig. 1】For the relationship of reaction (1)~(7) gibbs free energy change and temperature in atmospheric conditions；
Specific implementation mode
The content of present invention is further illustrated with reference to specific example, but not limits the claims in the present invention and protects model
It encloses.
Embodiment 1
The calcium arsenate obtained using Yunnan Bellamya aeruginosa alkali leaching-lime precipitation takes raw material 100Kg to be mixed with carbon dust as raw material
It is put into vacuum arc furnace ignition (carbon dust addition is the 15% of material quality) after uniformly, opens vacuum pump, is opened as pressure 1000Pa
Begin to heat up, be warming up to 700 DEG C and reducing environment is kept to stop heating after 3 hours, so that arsenic steam is condensed, after reduction, work as temperature
Degree is reduced to room temperature, closes vacuum drying oven, obtains metallic arsenic from condensation pipeline section, after testing purity>95%, restore slag specimen main component
For CaO.
Embodiment 2
As raw material, which contains the arsenic acid sodium crystal obtained using Yunnan tin electrolysis anode sludge high pressure base leaching-crystallisation by cooling
As 30.13%, Pb 0.58%, Sb 0.42% and Sn 0.07%.Take the 100Kg arsenic acid sodium crystals and carbon dust after mixing
It is put into vacuum arc furnace ignition (carbon dust addition is the 20% of material quality), vacuum pump is opened, is started to warm up as pressure 1Pa, risen
Temperature is to 700 DEG C and reducing environment is kept to stop heating after 4 hours, so that arsenic steam is condensed, after reduction, when temperature is reduced to room
Temperature closes vacuum drying oven, obtains metallic arsenic from condensation pipeline section, after testing purity>94%, reduction slag specimen main component is Na2CO3。
Embodiment 3
The ferric arsenate obtained using Yunnan the anode mud of copper electroplating high pressure base leaching-molysite deposition as raw material, take 100Kg raw materials with
Carbon dust is put into electric reduction furnace (carbon dust addition is the 20% of material quality) after mixing, is warming up to 900 DEG C and keeps restoring
Environment stops heating after 2 hours, arsenic steam is made to condense, and after reduction, when temperature is reduced to room temperature, closes reduction furnace, from cold
Solidifying pipeline section obtains metallic arsenic, after testing purity>96%, the oxide that reduction slag specimen main component is Fe.
Comparative example 1
As raw material, which contains the arsenic acid sodium crystal obtained using Yunnan tin electrolysis anode sludge high pressure base leaching-crystallisation by cooling
As 30.13%, Pb 0.58%, Sb 0.42% and Sn 0.07%.Take the 100Kg arsenic acid sodium crystals and carbon dust after mixing
It is put into vacuum arc furnace ignition (carbon dust addition is the 20% of material quality), vacuum pump is opened, is started to warm up as pressure 1Pa, risen
Temperature is to 550 DEG C and reducing environment is kept to stop heating after 4 hours, and arsenic is mainly present in reducing slag in the form of simple substance and natrium arsenicum
In sample, condensation pipeline section is hardly obtained metallic arsenic.
Claims (6)
1. a kind of method that arsenic-containing material direct-reduction roasting prepares arsenic, it is characterised in that：Arsenate material and carbonaceous reducing agent
It after mixing, is placed in inertia or reducing atmosphere, reduction roasting is carried out under negative pressure and >=600 DEG C of temperature conditions, collect roasting cigarette
Gas is to get arsenic product；
The ratio of the arsenate material and the carbonaceous reducing agent is with the molar ratio of arsenic and carbon for 1:(0.5~5) it measures.
2. the method that arsenic-containing material direct-reduction roasting according to claim 1 prepares arsenic, it is characterised in that：The arsenic
Aluminate materials include at least one of natrium arsenicum, calcium arsenate, lead arsenate, barium arsenate, magnesium arsenate, ferric arsenate.
3. the method that arsenic-containing material direct-reduction roasting according to claim 1 prepares arsenic, it is characterised in that：The carbon
Matter reducing agent includes at least one of stone tar powder, coke blacking, active powdered carbon, carbon black powder, graphite powder and charcoal powder.
4. the method that arsenic-containing material direct-reduction roasting according to claim 1 prepares arsenic, it is characterised in that：The negative pressure
Vacuum degree be 0.1~101325Pa.
5. the method that arsenic-containing material direct-reduction roasting according to claim 1 prepares arsenic, it is characterised in that：Described goes back
Former roasting time is 1~8h.
6. the method that arsenic-containing material direct-reduction roasting according to claim 1 prepares arsenic, it is characterised in that：The arsenic
Product grade is more than 90%.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN109913657A (en) * | 2019-03-12 | 2019-06-21 | 济源市中亿科技有限公司 | A method of recycling lead bronze arsenic from white cigarette dirt |
| CN109881018A (en) * | 2019-03-12 | 2019-06-14 | 济源市中亿科技有限公司 | A method of recycling arsenic iron calcium from arsenic iron calcium slag |
| CN110144463A (en) * | 2019-05-21 | 2019-08-20 | 铜仁学院 | A method of processing arsenic calcium slag resource utilization |
| CN110229962A (en) * | 2019-05-21 | 2019-09-13 | 铜仁学院 | A kind of method of arsenic scum resource utilization |
| CN110184450A (en) * | 2019-05-21 | 2019-08-30 | 铜仁学院 | A method of processing arsenic scum |
| CN111334673B (en) * | 2020-03-13 | 2022-06-07 | 江西理工大学 | Method for selectively recovering antimony, arsenic and alkali from arsenic-alkali residue |
| CN113462907A (en) * | 2021-06-30 | 2021-10-01 | 林西金易来砷业有限公司 | Process for producing arsenic by using arsenic-containing material |
| CN114836635B (en) * | 2022-03-25 | 2023-05-16 | 中南大学 | Method for preparing high-purity metal arsenic by nonferrous smelting arsenic-containing solid waste short process |
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| CN102965517A (en) * | 2012-12-03 | 2013-03-13 | 中南大学 | Treatment method for vitrifying arsenic-alkali residue |
| CN103555931A (en) * | 2013-11-15 | 2014-02-05 | 湖南省环境保护科学研究院 | Method for comprehensive utilization of removed arsenium of high-arsenium-sulfur-iron watercourse tailings |
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