CN109911869A - A kind of method that selenium is extracted in the cleaning of selenic acid scum reduction decomposition - Google Patents
A kind of method that selenium is extracted in the cleaning of selenic acid scum reduction decomposition Download PDFInfo
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Abstract
The invention belongs to non-ferrous metallurgy technology fields, specifically disclose a kind of method that selenium is extracted in the cleaning of selenic acid scum reduction decomposition.This method is using selenic acid scum as raw material, reducing agent is added, reduction decomposition roasting is carried out within the temperature range of 400~900 DEG C after mix, product of roasting is flue gas containing selenium and fired slags, the flue gas containing selenium obtains liquid and tail gas after the atomization containing elemental selenium by short chain organic aqueous solution atomization absorption and after restoring, liquid obtains elemental selenium after separating the atomization, and tail washings produced by separation process returns to atomization absorption and reduction process, and the tail gas can direct emission.The method of the present invention has the characteristics that easy to operate, process cleans, direct products, realizes that efficient reduction decomposition selenic acid scum extracts selenium and former slag and has valence component complete utilization, is easy to carry out industrialized production.
Description
Technical field
The invention belongs to non-ferrous metallurgy technology fields, clean more particularly, to a kind of selenic acid scum reduction decomposition
The method for extracting selenium.
Background technique
Selenium is a kind of important strategic rare metal, is widely applied in the industry such as chemistry, petroleum, pharmacy, electronics, metallurgy.
The main association of selenium in non-ferrous metal slag copper, nickel, lead, zinc primary slag in, and rare independent slag object, mainly in the electrolysis of cupro-nickel lead
It is recycled in the earth of positive pole, wherein the by-product selenium amount of cupper smelting has accounted for 60% or more of total selenium yield.It is recycled from selenium waste material
The method of selenium has high-temperature oxydation volatility process and solution chemical method two major classes.
In the method for various high-temperature oxydation volatility process recycling selenium, sulfating roasting is most common method, and such as China is special
Sharp CN106379870 " a method of selenium is recycled from copper anode mud ", a kind of Chinese patent CN108502852A " microwave sulfuric acid
Change the method for selenium in roasting recycling copper anode mud " and a kind of Chinese patent CN107574300A " mixed processing of copper, lead anode slurry
Technique ", method involved by above-mentioned patent are used as roasting additive using sulfuric acid, mix it is sour environmental pollution is serious with roasting process,
Volatilizing SeO2When mostly use SO2As reducing agent, the environmental hazard of sour gas is big.Chinese patent CN108559850 is public
A kind of method for having opened sour sludge recycling selen-tellurjum, this method essence are that elemental selenium is volatilized in an inert atmosphere, recycle form
It is single, the selenium of compound state and alloy state is not recycled very well.
In terms of the solution chemical method of wet separation recycles selenium, Chinese patent CN108609587A is " a kind of to extract impure selenium
Method " and Chinese patent CN101775498A " a kind of preprocess method of copper anode mud " be all made of pressure leaching make selenium enter it is molten
Liquid is restored using sulfur dioxide or sulphite.A kind of Chinese patent CN104944388 " normal pressure nitric-sulfuric acid recycling copper
The method of selenium in the earth of positive pole ", using sulfonitric as leaching agent, enters selenium in solution in the form of selenic acid.Chinese patent
CN108342580A discloses a kind of method that selenium copper is extracted in the earth of positive pole, selenium of this method mainly for alloy state and elemental
Raw material.The characteristics of solution chemical method is that wastewater flow rate is big, production efficiency is low, there is no large-scale industrial application at present.
In conclusion the recovery process of selenium is mainly directed towards elemental selenium and alloy selenium in selenium waste material at present, to compound state
There are selenic acid iron [Fe2(SeO3)3、Fe2(Se2O5)3] without good recovery method, sulfur dioxide is used after simultaneous oxidation volatilization
Or sulphite etc. is used as reducing agent, easily causes the problem of environmental pollutions such as atmosphere and waste water.
Summary of the invention
The technical problem to be solved by the present invention is to utilize method and selenium dioxide two without fine for existing selenic acid scum
Problem of environmental pollution present in the harmfulness reducing agent reduction process such as sulfur oxide, it is clear to provide a kind of selenic acid scum reduction decomposition
The method of clean extraction selenium, this method are roasted by reduction rotating decomposition and are realized under conditions of not introducing increment flux, completion pair
Ferroselenium slag efficiently separates, and analytical product can be used for preparing simple substance pure selenium and as iron-smelting raw material, realizes that former slag has valence component complete
It utilizes, no other waste residue and liquids generate, and process is short, is easy to carry out industrialized production.
The purpose of the present invention is achieved by the following technical programs:
A kind of method that selenium is extracted in the cleaning of selenic acid scum reduction decomposition, using selenic acid scum as raw material, addition reducing agent, through mixed
Close ingredient after within the temperature range of 400~900 DEG C carry out reduction decomposition roasting, product of roasting be flue gas containing selenium and fired slags,
The flue gas containing selenium obtains liquid and tail gas after the atomization containing elemental selenium by short chain organic aqueous solution atomization absorption and after restoring,
Liquid obtains elemental selenium and tail washings after separating the atomization, and the tail washings returns to atomization absorption and reduction process, and the tail gas can be direct
Discharge.
Scientific design production technology of the present invention and use ingredient, first to raw material carry out reduction decomposition roasting, make selenic acid iron
Slag is through reduction decomposition at iron oxide and selenium oxide, and the two is separated because of the difference of saturated vapor pressure, and selenium oxide is volatized into flue gas.
The flue gas containing selenium is only absorbed by the water generation by the synchronous progress atomization absorption of short chain organic aqueous solution and reduction, i.e. selenium dioxide
Selenic acid, and elemental selenium is further reduced by alcohol liquid, organic matter is decomposed into carbon dioxide and water.The elemental selenium that is generated after reaction and
Water droplet sinks to collector bottom, is separated by natural subsidence, elemental selenium, that is, final products, and separates aqueous by supplementing short chain
The main component that can return to after organic matter and be made into absorbing liquid, and decompose slag is iron oxide, can be used as the raw material of ironmaking.The present invention exists
It does not introduce under conditions of increment flux, realizes that efficiently separating for ferroselenium slag prepares with selenium product short route, product is oxidation scum
And elemental selenium, no other waste residue and liquids generate.
Preferably, the selenic acid iron processes purification section, concrete composition are as follows: Se > from the sour sludge of smelting and selenium material
30%, Fe 5~30%, Si 1~10%, Sn 0.5~5%, Cu 0.5~5%, S 0.5~5%.
Preferably, the carbonaceous reductant is one of coal dust, broken coal and coke powder or a variety of, and the carbonaceous reductant adds
Dosage is 5~25%, further preferably the 10~20% of selenic acid scum quality.
Preferably, the short chain organic aqueous solution be methanol solution, ethanol solution, propanol solution, ethylene glycol solution and
One of oxalic acid solution is a variety of, and the volumetric concentration of the short chain organic aqueous solution is 20~60%；The short chain is organic
Object aqueous solution is more preferably ethyl alcohol or oxalic acid solution, cheap and easy to get, asepsis environment-protecting.
The present invention it is a kind of preferably by selenic acid scum reduction decomposition clean extract selenium method specifically includes the following steps:
S1. it by selenic acid scum and the uniform mixing and ball milling of carbonaceous reductant, is gone back under the conditions of 400~900 DEG C of temperature
Original roasting, the fired slags for obtaining flue gas containing selenium and being made of a large amount of iron oxide；
S2. flue gas containing selenium obtained by step S1 is passed through absorption chamber, the short chain organic matter after atomization is sprayed into absorption chamber is water-soluble
Liquid is absorbed, while the aquation that selenium oxide occurs absorbs and aqueous solution reduction, reaction obtain after the atomization containing elemental selenium liquid and
Innoxious tail gas；
S3. liquid placement after the atomization containing elemental selenium obtained by step S2 is settled, is separated by filtration after selenium settles completely
Elemental selenium and sedimentation liquid are obtained, the sedimentation liquid return step S2 atomization absorption and reduction process are recycled.
Elemental selenium obtained in technical solution of the present invention is final products, and reduction decomposition slag main component is iron oxide, is
Good iron-smelting raw material.Auxiliary material preferably use carbonaceous reductant to restore after for carbon dioxide, short chain organic solution restore after be
Carbon dioxide and water, therefore the object that is safe from harm in the whole process uses and pollutant generates, sanitary characteristics are obvious.
Selenic acid under the reaction temperature that the present invention is set, especially when temperature within the scope of 400~900 DEG C, in raw material
Following reduction roasting reaction mainly occurs for iron and carbonaceous reductant:
Fe2(SeO3)3=Fe2O3+3SeO2 (1)
Fe2(SeO3)3+ 0.5C (g)=2FeO+3SeO2+0.5CO2(g) (2)
Fe2(Se2O5)3]=Fe2O3+6SeO2 (3)
Fe2(Se2O5)3]+0.5CO (g)=Fe2O3+6SeO2+0.5CO2(g) (4)
SeO2+ C=Se+CO (5)
SeO2+ 2CO (g)=Se+2CO2(g) (6)
Fe2O3(s) (7)+C=2FeO (s)+CO (g)
Fe3O4(s) (8)+C=3FeO (s)+CO (g)
Selenic acid iron, which is reduced, in above-mentioned reaction process resolves into selenium dioxide and iron oxide, while releasing oxycarbide gas
Body, selenium oxide volatilization and carbon dioxide etc. enter flue gas together, and decomposing slag is mainly ferriferous oxide, including ferroso-ferric oxide, three
Two iron and ferrous oxide are aoxidized, ferrous oxide is oxidized to ferroso-ferric oxide or di-iron trioxide during cooling, can make
For the raw material of ironmaking.
In step s 2, flue gas atomization organic liquor absorbs reduction process and mainly occurs to react as follows:
SeO2+H2O=H2SeO3 (9)
H2O (g)=H2O(l) (10)
3H2SeO3+CH3CH2OH=3Se+2CO2(g)+6H2O (11)
3H2SeO3+2CH3OH=3Se+2CO2(g)+7H2O (12)
9H2SeO3+2CH3CH2CH2OH=9Se+6CO2(g)+17H2O (13)
H2SeO3+2C2H2O4=Se+4CO2(g)+3H2O (14)
3H2SeO3+2C2H6O4=3Se+4CO2(g)+9H2O (15)
Preferably, after step S1 mixing and ball milling, mixed material granularity is 300 μm or less.
Preferably, reducing roasting process described in step S1 carries out in revolving burner, the preferably described furnace body rotation speed be 5~
30 turns/min.
Preferably, reduction roasting temperature described in step S1 is 600~800 DEG C, and calcining time is 0.5~5h；It is further excellent
Selecting the calcining time is 1~3h.
Preferably, atomized liquid temperature described in step S2 is 50~80 DEG C, penetrating speed is 1.0~10m/s.
Preferably, sedimentation process described in step S3 is natural subsidence, and the sedimentation time is 5~20h.Enter without external force circle, selenium
Density be up to 4.81g/cm3, it is easy to it is separated from water, is mixed with water in infall process and also ensure that selenium is not oxidized, thus
Obtain pure simple substance selenium powder.
Preferably, sedimentation liquid described in step S3 is made by return step S2 atomization circulation after supplementing short chain organic solution
With.After analytical solution ingredient, supplementing fresh short chain organic solution thereto makes needed for restoring up to atomization, so that circulation makes
With elimination discharge of wastewater.
Compared with the prior art, the beneficial effects of the present invention are:
(1) present invention proposes reduction rotating decomposition roasting-organic liquor atomization absorption reduction for selenic acid scum creativeness
Process combination.It is realized under conditions of not introducing increment flux, is completed to selenic acid scum by reduction rotating decomposition roasting
It efficiently separates and is prepared with selenium product short route.Analytical product can be used for preparing simple substance pure selenium and as iron-smelting raw material, realize efficient
Reduction decomposition selenic acid scum, which extracts selenium and former slag, valence component complete utilization；The direct yield of its elemental selenium may be up to 99.17%, and iron is straight
Yield has no the generation of other waste residue and liquids up to 99.48%, and process is short, is easy to carry out industrialized production.
(2) present invention creatively uses reducing agent of the short chain organic matter as selenium dioxide, instead of existing common two
Sulfur oxide, not only process cleans, but also discharge that harmless, environment access is low, and improve absorption efficiency in atomization absorption process.
The purity and direct yield for keeping higher elemental selenium simultaneously, have the characteristics that easy to operate, process cleans, direct products.
Detailed description of the invention
Attached drawing 1 is the process flow chart for the method that selenium is extracted in a kind of selenic acid scum reduction decomposition cleaning of the present invention.
Attached drawing 2 is the XRD analysis map of selenic acid scum raw material in the embodiment of the present invention 1~5.
Attached drawing 3 is the XRD analysis map of elemental selenium obtained by 1 step S3 of the embodiment of the present invention.
Attached drawing 4 is the XRD analysis map that slag is decomposed obtained by 1 step S1 of the embodiment of the present invention.
Specific embodiment
To facilitate the understanding of the present invention, the present invention is made below in conjunction with Figure of description and preferred embodiment more complete
Face meticulously describes, but the protection scope of the present invention is not limited to the following specific embodiments.
Unless otherwise defined, all technical terms used hereinafter and the normally understood meaning of those skilled in the art
It is identical.Technical term used herein is intended merely to the purpose of description specific embodiment, it is no intended to limit of the invention
Protection scope.
Unless otherwise specified, various raw material, reagent, the instrument and equipment etc. used in the present invention can pass through city
Field is commercially available or can be prepared by existing method.
As the Main chemical component (wt.%) of the selenic acid scum of test raw material in the embodiment of the present invention are as follows: Se 50.36,
Fe 17.30, Si 3.29, Sn 2.16, Cu 1.02, S 1.18, Al 0.81, Cr 0.50, Mo 0.28, Ni 0.25, the selenium
The XRD analysis of sour scum is as shown in Fig. 2, it can be seen from the figure that the main component of the selenic acid scum is Fe2(Se2O5)3.Reduction
The chemical constituent (wt.%) of coal dust are as follows: C 82.33, S 2.01, SiO2 6.66、CaO 0.83、Al2O34.81,MgO 0.23；
The chemical constituent (wt.%) for restoring coke powder is C 85.73, S 2.23, ash content 11.03.
Embodiment 1
The present embodiment provides a kind of selenic acid scum reduction decompositions to clean the method for extracting selenium, process flow chart such as attached drawing 1
It is shown, specifically includes the following steps:
S1. ferroselenium slag 1000g, the coal dust 150g for weighing mentioned component respectively, are finely ground to whole granularities 250 after mixing
μm or less.It is fitted into rotation electric furnace, during which keeping furnace body revolving speed is 10rpm, and 2.0h is roasted at 700 DEG C, is contained after reaction
Selenium flue gas and the decomposition slag being made of a large amount of iron oxide, weighing and decomposing the weight of slag is 304.52g, and wherein iron content is for analysis
56.32%, calculating iron direct yield is 99.13%, and XRD analysis is as shown in figure 4, as can be seen from the figure main component is
Fe2O3, i.e. the grade of the main ingredient of bloodstone, bloodstone obtained by the present embodiment is higher than general bloodstone, can directly send to ironmaking
Technique；
S2. exhausting and atomising device are opened simultaneously, flue gas containing selenium obtained by step S1 is passed through absorption chamber, while with 5m/s's
Speed sprays into the ethanol solution that volumetric concentration is 35%, solution temperature is 70 DEG C into absorption chamber and is absorbed, same in absorption chamber
The aquation of Shi Fasheng selenium oxide absorbs and aqueous solution reduction, reaction obtain liquid and innoxious tail gas after the atomization containing elemental selenium, nothing
Evilization tail gas is directly discharged without processing；
S3. after liquid after the atomization containing elemental selenium obtained by step S2 being placed cooling, natural subsidence 10h is carried out, it is complete to selenium
It is separated by filtration to obtain elemental selenium and sedimentation liquid after sedimentation, the sedimentation liquid return step S2 atomization absorption and reduction process circulation make
With, after separation weigh gained elemental selenium quality be 485.32g, to gained elemental selenium carry out XRD analysis, as a result as shown in figure 3, from
As can be seen that the diffraction maximum of essentially selenium, illustrates to have obtained more pure elemental selenium in figure.XRF spectrum is carried out to it to divide entirely
The content that analysis measures Se is 98.76%, and calculating its direct yield is 95.18%,
Embodiment 2
The present embodiment provides a kind of selenic acid scum reduction decompositions to clean the method for extracting selenium, process flow chart such as attached drawing 1
It is shown, wherein atomized liquid of the present invention is liquid after the heavy selenium of embodiment 1, and new ethyl alcohol, which is added, makes its concentration reach 30%.Specific packet
Include following steps:
S1. ferroselenium slag 1000g, the coal dust 200g for weighing mentioned component respectively, are finely ground to whole granularities 150 after mixing
μm or less.It is fitted into rotation electric furnace, during which keeping furnace body revolving speed is 20rpm, and 3.0h is roasted at 900 DEG C, is contained after reaction
Selenium flue gas and the decomposition slag being made of a large amount of iron oxide, weighing and decomposing the weight of slag is 297.12g, and wherein iron content is for analysis
57.43%, calculating iron direct yield is 98.64%；
S2. exhausting and atomising device are opened simultaneously, flue gas containing selenium obtained by step S1 is passed through absorption chamber, while with 8m/s's
Speed is sprayed into absorption chamber selenium is sunk as obtained by embodiment 1 after the volumetric concentration that configures of liquid be 30%, temperature is 80 DEG C
Circulation ethanol solution is absorbed, and the aquation that selenium oxide occurs in absorption chamber simultaneously absorbs and aqueous solution reduction, reaction are contained
Liquid and innoxious tail gas after the atomization of elemental selenium, innoxious tail gas are directly discharged without processing；
S3. after liquid after the atomization containing elemental selenium obtained by step S2 being placed cooling, natural subsidence 15h is carried out, it is complete to selenium
It is separated by filtration to obtain elemental selenium and sedimentation liquid after sedimentation, the sedimentation liquid return step S2 atomization absorption and reduction process circulation make
With, it is 489.35g that gained elemental selenium quality is weighed after separation, XRF spectrum complete analysis carried out to it measure the content of Se be
99.10%, calculating its direct yield is 96.30%.
Embodiment 3
The present embodiment provides a kind of selenic acid scum reduction decompositions to clean the method for extracting selenium, process flow chart such as attached drawing 1
It is shown, specifically includes the following steps:
S1. ferroselenium slag 1000g, the coal dust 60g of mentioned component are weighed respectively, it is finely ground to whole 74 μ of granularity after mixing
M or less.It is fitted into rotation electric furnace, during which keeping furnace body revolving speed is 30rpm, and 5.0h is roasted at 500 DEG C, is obtained after reaction containing selenium
Flue gas and the decomposition slag being made of a large amount of iron oxide, weighing and decomposing the weight of slag is 313.28g, and wherein iron content is for analysis
54.94%, calculating iron direct yield is 99.48%；
S2. exhausting and atomising device are opened simultaneously, flue gas containing selenium obtained by step S1 is passed through absorption chamber, while with 3m/s's
Speed sprays into the methanol solution that volumetric concentration is 25%, solution temperature is 60 DEG C into absorption chamber and is absorbed, same in absorption chamber
The aquation of Shi Fasheng selenium oxide absorbs and aqueous solution reduction, reaction obtain liquid and innoxious tail gas after the atomization containing elemental selenium, nothing
Evilization tail gas is directly discharged without processing；
S3. after liquid after the atomization containing elemental selenium obtained by step S2 being placed cooling, natural subsidence 5h is carried out, it is completely heavy to selenium
It is separated by filtration to obtain elemental selenium and sedimentation liquid after drop, the sedimentation liquid return step S2 atomization absorption and reduction process circulation make
With, it is 481.59g that gained elemental selenium quality is weighed after separation, XRF spectrum complete analysis carried out to it measure the content of Se be
98.27%, calculating its direct yield is 93.98%.
Embodiment 4
The present embodiment provides a kind of selenic acid scum reduction decompositions to clean the method for extracting selenium, process flow chart such as attached drawing 1
It is shown, specifically includes the following steps:
S1. ferroselenium slag 1000g, the coal dust 160g for weighing mentioned component respectively, are finely ground to whole granularities 125 after mixing
μm or less.It is fitted into rotation electric furnace, during which keeping furnace body revolving speed is 15rpm, and 3.0h is roasted at 800 DEG C, is contained after reaction
Selenium flue gas and the decomposition slag being made of a large amount of iron oxide, weighing and decomposing the weight of slag is 297.14g, and wherein iron content is for analysis
57.17%, calculating iron direct yield is 98.20%；
S2. exhausting and atomising device are opened simultaneously, flue gas containing selenium obtained by step S1 is passed through absorption chamber, while with 6m/s's
Speed sprays into the oxalic acid solution that volumetric concentration is 35%, solution temperature is 80 DEG C into absorption chamber and is absorbed, same in absorption chamber
The aquation of Shi Fasheng selenium oxide absorbs and aqueous solution reduction, reaction obtain liquid and innoxious tail gas after the atomization containing elemental selenium, nothing
Evilization tail gas is directly discharged without processing；
S3. after liquid after the atomization containing elemental selenium obtained by step S2 being placed cooling, natural subsidence 8h is carried out, it is completely heavy to selenium
It is separated by filtration to obtain elemental selenium and sedimentation liquid after drop, the sedimentation liquid return step S2 atomization absorption and reduction process circulation make
With, it is 499.42g that gained elemental selenium quality is weighed after separation, XRF spectrum complete analysis carried out to it measure the content of Se be
98.63%, calculating its direct yield is 97.81%.
Embodiment 5
The present embodiment provides a kind of selenic acid scum reduction decompositions to clean the method for extracting selenium, process flow chart such as attached drawing 1
It is shown, specifically includes the following steps:
S1. ferroselenium slag 5000g, the coal dust 500g for weighing mentioned component respectively are finely ground to whole 74 μ of granularity after mixing
M or less.It is fitted into rotation electric furnace, during which keeping furnace body revolving speed is 20rpm, and 4.0h is roasted at 800 DEG C, is obtained after reaction containing selenium
Flue gas and the decomposition slag being made of a large amount of iron oxide, weighing and decomposing the weight of slag is 1548.72g, and wherein iron content is for analysis
54.86%, calculating iron direct yield is 98.22%；
S2. exhausting and atomising device are opened simultaneously, flue gas containing selenium obtained by step S1 is passed through absorption chamber, while with 10m/s
Speed spray into the ethylene glycol solution that volumetric concentration is 40%, solution temperature is 70 DEG C into absorption chamber and absorbed, absorption chamber
Aquation interior while that selenium oxide occurs absorbs and aqueous solution reduction, reaction obtain liquid and innoxious tail after the atomization containing elemental selenium
Gas, innoxious tail gas are directly discharged without processing；
S3. after liquid after the atomization containing elemental selenium obtained by step S2 being placed cooling, natural subsidence 10h is carried out, it is complete to selenium
It is separated by filtration to obtain elemental selenium and sedimentation liquid after sedimentation, the sedimentation liquid return step S2 atomization absorption and reduction process circulation make
With, it is 2448.76g that gained elemental selenium quality is weighed after separation, XRF spectrum complete analysis carried out to it measure the content of Se be
97.75%, calculating its direct yield is 95.06%.
Claims (10)
1. a kind of method that selenium is extracted in the cleaning of selenic acid scum reduction decomposition, which is characterized in that using selenic acid scum as raw material, be added also
Former agent, carries out reduction decomposition roasting after mix within the temperature range of 400~900 DEG C, and product of roasting is flue gas containing selenium
And fired slags, after the flue gas containing selenium is by obtaining the atomization containing elemental selenium after short chain organic aqueous solution atomization absorption and reduction
Liquid and tail gas, liquid obtains elemental selenium and tail washings after separating the atomization, and the tail washings returns to atomization absorption and reduction process, the tail
Gas can direct emission.
2. the method that selenium is extracted in selenic acid scum reduction decomposition cleaning according to claim 1, which is characterized in that the selenic acid
Iron processes purification section, concrete composition from the sour sludge of smelting and selenium material are as follows: and Se > 30%, Fe 5~30%, Si 1~
10%, Sn 0.5~5%, Cu 0.5~5%, S 0.5~5%.
3. the method that selenium is extracted in selenic acid scum reduction decomposition cleaning according to claim 1, which is characterized in that the carbonaceous
Reducing agent is one of coal dust, broken coal and coke powder or a variety of, and the preferably described carbonaceous reductant additive amount is selenic acid scum quality
5~25%.
4. the method that selenium is extracted in selenic acid scum reduction decomposition cleaning according to claim 1, which is characterized in that the short chain
Organic aqueous solution is one of methanol solution, ethanol solution, propanol solution, ethylene glycol solution and oxalic acid solution or a variety of,
It is preferred that the volumetric concentration of the short chain organic aqueous solution is 20~60%.
5. the method that selenium is extracted in selenic acid scum reduction decomposition cleaning according to any one of claims 1 to 4, feature exist
In, comprising the following steps:
S1. by selenic acid scum and the uniform mixing and ball milling of carbonaceous reductant, reduction roasting is carried out under the conditions of 400~900 DEG C of temperature
It burns, the fired slags for obtaining flue gas containing selenium and being made of a large amount of iron oxide；
S2. flue gas containing selenium obtained by step S1 is passed through absorption chamber, sprayed into absorption chamber the short chain organic aqueous solution after being atomized into
Row absorbs, while the aquation that selenium oxide occurs absorbs and aqueous solution reduction, and reaction obtains after the atomization containing elemental selenium liquid and harmless
Change tail gas；
S3. liquid placement after the atomization containing elemental selenium obtained by step S2 is settled, is separated by filtration to obtain after selenium settles completely
Elemental selenium and sedimentation liquid, the sedimentation liquid return step S2 atomization absorption and reduction process are recycled.
6. the method that selenium is extracted in selenic acid scum reduction decomposition cleaning according to claim 5, which is characterized in that step S1 institute
It states reducing roasting process to carry out in revolving burner, the preferably described furnace body rotation speed is 5~30 turns/min.
7. the method that selenium is extracted in selenic acid scum reduction decomposition cleaning according to claim 5, which is characterized in that step S1 institute
Stating reduction roasting temperature is 600~800 DEG C, and calcining time is 0.5~5h；It is preferred that the calcining time is 1~3h.
8. the method that selenium is extracted in selenic acid scum reduction decomposition cleaning according to claim 5, which is characterized in that step S2 institute
State that atomized liquid temperature is 50~80 DEG C, to spray into speed be 1.0~10m/s.
9. selenic acid scum reduction decomposition according to claim 5 proposes the method that cleaning takes selenium, which is characterized in that step S3 institute
Stating sedimentation process is natural subsidence, and the sedimentation time is 5~20h.
10. the method that selenium is extracted in selenic acid scum reduction decomposition cleaning according to claim 5, which is characterized in that step S3
The sedimentation liquid is recycled by return step S2 atomization after supplementing short chain organic solution.
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| CN108588430A (en) * | 2018-06-13 | 2018-09-28 | 汉能新材料科技有限公司 | A kind of recovery method of the material containing copper indium gallium selenide |
| CN109231175A (en) * | 2018-11-14 | 2019-01-18 | 昆明理工大学 | A method of impure selenium is purified with dehydrated alcohol |
| CN109371228A (en) * | 2018-11-14 | 2019-02-22 | 昆明理工大学 | A method of recycling selenium, tellurium, copper and noble metal from copper anode mud |
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2019
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Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1669913A (en) * | 2005-02-25 | 2005-09-21 | 中国科学院上海硅酸盐研究所 | Non-template liquid phase reduction method for preparing elemental selenium nanotube |
| CN1721321A (en) * | 2005-05-13 | 2006-01-18 | 中国科学院上海硅酸盐研究所 | A kind of method for preparing the simple substance nano powder with the reductive agent reduced oxide |
| CN103964402A (en) * | 2013-02-06 | 2014-08-06 | 安徽省思达新材料科技有限公司 | Method for utilizing solid industrial waste containing trace selenium to extract high-purity selenium for new materials |
| CN108588430A (en) * | 2018-06-13 | 2018-09-28 | 汉能新材料科技有限公司 | A kind of recovery method of the material containing copper indium gallium selenide |
| CN109231175A (en) * | 2018-11-14 | 2019-01-18 | 昆明理工大学 | A method of impure selenium is purified with dehydrated alcohol |
| CN109371228A (en) * | 2018-11-14 | 2019-02-22 | 昆明理工大学 | A method of recycling selenium, tellurium, copper and noble metal from copper anode mud |
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