CN104276845B - A kind of gas mud basal granule sub-electrode and preparation method thereof - Google Patents
A kind of gas mud basal granule sub-electrode and preparation method thereof Download PDFInfo
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- CN104276845B CN104276845B CN201310275597.6A CN201310275597A CN104276845B CN 104276845 B CN104276845 B CN 104276845B CN 201310275597 A CN201310275597 A CN 201310275597A CN 104276845 B CN104276845 B CN 104276845B
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- shale
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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
- Y02P40/00—Technologies relating to the processing of minerals
- Y02P40/60—Production of ceramic materials or ceramic elements, e.g. substitution of clay or shale by alternative raw materials, e.g. ashes
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Abstract
Gas mud basal granule sub-electrode that the present invention relates to a kind of 3 D electrode reactor and preparation method thereof: be made up of gas mud, shale, pore former, activator, by weight percentage, dry thin gas mud particle is 50-60%, dry thin shale is 10-20%, pore former is 10-20%, activator is 10-20%.Granule electrode porous prepared by the present invention, has very large specific surface area, very strong absorption property, good conductivity and catalytic performance, is a kind of new and effective granule electrode.A kind of gas mud basal granule sub-electrode provided by the invention and preparation method thereof, makes full use of trade waste-gas mud, both can turn waste into wealth, and can reduce again the pollution of environment, solve the problems such as land seizure.
Description
Technical field
The invention belongs to technical field of waste water processing, particularly a kind of gas mud basal granule sub-electrode for the treatment of hardly degraded organic substance in municipal effluent and preparation method thereof.
Background technology
Three-diemsnional electrode is a kind of novel advanced oxidization method, its conversion zone is no longer confined to the simple geometry of electrode on the surface, but carry out on the surface at the three-dimensional space of whole bed, be particularly useful for the reaction system that in the low or system of DeR speed, limit current density is little.The working mechanism of three-diemsnional electrode is that multipole bed (not having barrier film) makes working electrode particle (high resistance) bring positive and negative charge respectively because of static induction mainly through the electric field between main electrode, each particle is made to become an independently electrode, electrochemical oxidation and reduction reaction can be carried out at each electrode particle surface simultaneously, shorten mass transfer distance.The treatment effect of the performance remarkably influenced 3 D electrode reactor of granule electrode, conventional several granule electrodes comprise gac, the metal of metal oxide and load or metal oxide.
Gas mud (ash) is the material that the dust of the raw material carried out along with blast furnace gas in iron manufacturing process and the particle that generated by intense reaction in high-temperature zone are obtained through wet type or dry gas cleaning, and its main component is ferric oxide and carbon.These materials are also exactly effective constituent prepared by granule electrode.
Along with developing rapidly of China's economy, constantly increase the demand of metallic substance, the demand sharply expanded causes the various problems of environment, resource and the energy, therefore carries out recycle to metal secondary resource, becomes the effective way solving development problem.These the utilized materials in the waste-gas mud produced in iron manufacturing process are utilized to carry out the granule electrode of synthesizing efficient, environmental protection, for the treatment of municipal effluent, gas mud can be made to be utilized effectively, thus to reach the object of " treatment of wastes with processes of wastes against one another ", obtain good economic benefit.
Summary of the invention
The object of the invention is with gas mud is matrix, provides a kind of gas mud basal granule sub-electrode and preparation method thereof.Granule electrode material provided by the present invention is as the working electrode of 3 D electrode reactor, and the organism that can effectively degrade in municipal effluent, and current efficiency is high, energy consumption is low.
A kind of gas mud basal granule sub-electrode, according to weight percent meter, dry thin gas mud particle accounts for 50-60%, dry carefully shale accounts for 10-20%, pore former accounts for 10-20%, activator accounts for 10-20%.
Described pore former can be the one in powdered carbon, saw dust, starch, polyvinyl alcohol (PVA), polyvinyl butyral acetal (PVB), granules of polystyrene.
Described activator can be Fe
3o
4, Fe
2o
3,mnO
2, one in ZnO.
Described gas mud is the material that the dust of the raw material carried out along with blast furnace gas in iron manufacturing process and the particle that generated by intense reaction in high-temperature zone are obtained through wet type or dry gas cleaning, its main component is ferric oxide and carbon, is a kind of trade waste.
The preparation method of above-mentioned gas mud basal granule sub-electrode, comprises the steps:
A, gas mud particle ball milling in ball mill, washing after taking out, immersion (washing, the object of soaking are desorption of impurities), dry at 120 DEG C, then cross 60 mesh sieves, get the thin gas mud particle of drying for subsequent use in baking oven;
B, shale are put in 120 DEG C of oven dry in baking oven, are pulverized by the shale of oven dry in mortar, then cross 60 mesh sieves, get dry thin shale for subsequent use;
C, by the thin shale of drying, pore former and the activator in thin for the drying in steps A gas mud particle, step B according to certain weight percent, mix and stir, being squeezed into raw material ball;
D, by the raw material ball in step C in an oven 120 DEG C dry 24 hours;
E, by step D dry after raw material ball, be placed in High Temperature Furnaces Heating Apparatus and rise to 300 DEG C from room temperature with 120 DEG C/h, heating 2h, then 550 DEG C are risen to 60 DEG C/h, activation 10-30min, rise to 1050 DEG C of roasting 10-30min with 300 DEG C/h again, naturally cool to room temperature, obtain gas mud basal granule sub-electrode material.
According to weight percent meter, dry thin gas mud particle accounts for 50-60%, dry carefully shale accounts for 10-20%, pore former accounts for 10-20%, activator accounts for 10-20%.
Described pore former can be the one in powdered carbon, saw dust, starch, polyvinyl alcohol (PVA), polyvinyl butyral acetal (PVB), granules of polystyrene.
Described activator can be Fe
3o
4, Fe
2o
3,mnO
2, one in ZnO.
The gas mud basal granule sub-electrode prepared by above-mentioned preparation method, getting solid waste gas mud is raw material.Containing multiple element material in gas mud, wherein mainly ferric oxide and carbon, these materials are also exactly effective constituent prepared by granule electrode.Gas mud basal granule sub-electrode particle surface is rough, has good absorption, removal effect to the pollution substance in waste water, and the waste gas mud produced in Bayer process aluminium metallurgy process, and its stacking not only needs fund and large-area storage yard, and contaminate environment.Utilize gas mud to make the particle-catalytic electrode of three-diemsnional electrode, can turn waste into wealth, reduce the problem such as pollution, appropriation of land of environment.
Gas mud basal granule sub-electrode provided by the invention and preparation method thereof, meets the environmental protection policy of current national energy-saving and emission-reduction.The granule electrode porous of preparation, and aperture is large, having very large specific surface area, very strong absorption property, good electroconductibility and catalytic performance is a kind of new and effective granule electrode.
Below in conjunction with embodiment, the invention will be further described.
Embodiment
Embodiment one:
A, gas mud particle ball milling in ball mill, washing after taking out, immersion (washing, the object of soaking are desorption of impurities), dry at 120 DEG C, then cross 60 mesh sieves, get the thin gas mud particle of drying for subsequent use in baking oven;
B, shale are put in 120 DEG C of oven dry in baking oven, are pulverized by the shale of oven dry in mortar, then cross 60 mesh sieves, get dry thin shale for subsequent use;
C, by the thin shale of drying, powdered carbon and the Fe in thin for the drying in steps A gas mud particle, step B
3o
4according to the weight percent of 50%:20%:20%:10%, mix and stir, being squeezed into raw material ball;
D, by the raw material ball in step C in an oven 120 DEG C dry 24 hours;
E, by step D dry after raw material ball, be placed in High Temperature Furnaces Heating Apparatus and rise to 300 DEG C from room temperature with 120 DEG C/h, heating 2h, then rise to 550 DEG C with 60 DEG C/h, activation 20min, then rise to 1050 DEG C of roasting 30min with 300 DEG C/h, naturally cool to room temperature, obtain gas mud basal granule sub-electrode material.
Get the gas mud basal granule sub-electrode 5.0g prepared in above-described embodiment, be filled in reactor, obtained 3 D electrode reactor, is 6.0V at voltage, and when electric current is 0.2A, energising degraded 30ml dyeing waste water 45min, CODcr clearance reaches 95%.
Embodiment two:
A, gas mud particle ball milling in ball mill, washing after taking out, immersion (washing, the object of soaking are desorption of impurities), dry at 120 DEG C, then cross 60 mesh sieves, get the thin gas mud particle of drying for subsequent use in baking oven;
B, shale are put in 120 DEG C of oven dry in baking oven, are pulverized by the shale of oven dry in mortar, then cross 60 mesh sieves, get dry thin shale for subsequent use;
C, by the thin shale of drying, saw dust and the Fe in thin for the drying in steps A gas mud particle, step B
2o
3according to the weight percent of 55%:15%:15%:15%, mix and stir, being squeezed into raw material ball;
D, by the raw material ball in step C in an oven 120 DEG C dry 24 hours;
E, by step D dry after raw material ball, be placed in High Temperature Furnaces Heating Apparatus and rise to 300 DEG C from room temperature with 120 DEG C/h, heating 2h, then rise to 550 DEG C with 60 DEG C/h, activation 20min, then rise to 1050 DEG C of roasting 30min with 300 DEG C/h, naturally cool to room temperature, obtain gas mud basal granule sub-electrode material.
Get the gas mud basal granule sub-electrode 5.0g prepared in above-described embodiment, be filled in reactor, obtained 3 D electrode reactor, is 6.0V at voltage, and when electric current is 0.2A, energising degraded 30ml dyeing waste water 45min, CODcr clearance reaches 94%.
Embodiment three:
A, gas mud particle ball milling in ball mill, washing after taking out, immersion (washing, the object of soaking are desorption of impurities), dry at 120 DEG C, then cross 60 mesh sieves, get the thin gas mud particle of drying for subsequent use in baking oven;
B, shale are put in 120 DEG C of oven dry in baking oven, are pulverized by the shale of oven dry in mortar, then cross 60 mesh sieves, get dry thin shale for subsequent use;
C, by the thin shale of drying, starch and the MnO in thin for the drying in steps A gas mud particle, step B
2according to the weight percent of 60%:15%:15%:10%, mix and stir, being squeezed into raw material ball;
D, by the raw material ball in step C in an oven 120 DEG C dry 24 hours;
E, by step D dry after raw material ball, be placed in High Temperature Furnaces Heating Apparatus and rise to 300 DEG C from room temperature with 120 DEG C/h, heating 2h, then rise to 550 DEG C with 60 DEG C/h, activation 20min, then rise to 1050 DEG C of roasting 30min with 300 DEG C/h, naturally cool to room temperature, obtain gas mud basal granule sub-electrode material.
Get the gas mud basal granule sub-electrode 5.0g prepared in above-described embodiment, be filled in reactor, obtained 3 D electrode reactor, is 6.0V at voltage, and when electric current is 0.2A, energising degraded 30ml dyeing waste water 45min, CODcr clearance reaches 94%.
Embodiment four:
A, gas mud particle ball milling in ball mill, washing after taking out, immersion (washing, the object of soaking are desorption of impurities), dry at 120 DEG C, then cross 60 mesh sieves, get the thin gas mud particle of drying for subsequent use in baking oven;
B, shale are put in 120 DEG C of oven dry in baking oven, are pulverized by the shale of oven dry in mortar, then cross 60 mesh sieves, get dry thin shale for subsequent use;
C, by the thin shale of drying, starch and the MnO in thin for the drying in steps A gas mud particle, step B
2according to the weight percent of 60%:10%:10%:20%, mix and stir, being squeezed into raw material ball;
D, by the raw material ball in step C in an oven 120 DEG C dry 24 hours;
E, by step D dry after raw material ball, be placed in High Temperature Furnaces Heating Apparatus and rise to 300 DEG C from room temperature with 120 DEG C/h, heating 2h, then rise to 550 DEG C with 60 DEG C/h, activation 20min, then rise to 1050 DEG C of roasting 30min with 300 DEG C/h, naturally cool to room temperature, obtain gas mud basal granule sub-electrode material.
Get the gas mud basal granule sub-electrode 5.0g prepared in above-described embodiment, be filled in reactor, obtained 3 D electrode reactor, is 6.0V at voltage, and when electric current is 0.2A, energising degraded 30ml dyeing waste water 45min, CODcr clearance reaches 96%.
Embodiment five:
A, gas mud particle ball milling in ball mill, washing after taking out, immersion (washing, the object of soaking are desorption of impurities), dry at 120 DEG C, then cross 60 mesh sieves, get the thin gas mud particle of drying for subsequent use in baking oven;
B, shale are put in 120 DEG C of oven dry in baking oven, are pulverized by the shale of oven dry in mortar, then cross 60 mesh sieves, get dry thin shale for subsequent use;
C, the thin shale of drying, polyvinyl alcohol (PVA) and ZnO by thin for the drying in steps A gas mud particle, step B, according to the weight percent of 55%:15%:20%:10%, mix and stir, being squeezed into raw material ball;
D, by the raw material ball in step C in an oven 120 DEG C dry 24 hours;
E, by step D dry after raw material ball, be placed in High Temperature Furnaces Heating Apparatus and rise to 300 DEG C from room temperature with 120 DEG C/h, heating 2h, then rise to 550 DEG C with 60 DEG C/h, activation 20min, then rise to 1050 DEG C of roasting 30min with 300 DEG C/h, naturally cool to room temperature, obtain gas mud basal granule sub-electrode material.
Get the gas mud basal granule sub-electrode 5.0g prepared in above-described embodiment, be filled in reactor, obtained 3 D electrode reactor, is 6.0V at voltage, and when electric current is 0.2A, energising degraded 30ml dyeing waste water 45min, CODcr clearance reaches 96%.
Embodiment six:
A, gas mud particle ball milling in ball mill, washing after taking out, immersion (washing, the object of soaking are desorption of impurities), dry at 120 DEG C, then cross 60 mesh sieves, get the thin gas mud particle of drying for subsequent use in baking oven;
B, shale are put in 120 DEG C of oven dry in baking oven, are pulverized by the shale of oven dry in mortar, then cross 60 mesh sieves, get dry thin shale for subsequent use;
C, the thin shale of drying, polyvinyl butyral acetal (PVB) and ZnO by thin for the drying in steps A gas mud particle, step B, according to the weight percent of 55%:15%:20%:10%, mix and stir, being squeezed into raw material ball;
D, by the raw material ball in step C in an oven 120 DEG C dry 24 hours;
E, by step D dry after raw material ball, be placed in High Temperature Furnaces Heating Apparatus and rise to 300 DEG C from room temperature with 120 DEG C/h, heating 2h, then rise to 550 DEG C with 60 DEG C/h, activation 20min, then rise to 1050 DEG C of roasting 30min with 300 DEG C/h, naturally cool to room temperature, obtain gas mud basal granule sub-electrode material.
Get the gas mud basal granule sub-electrode 5.0g prepared in above-described embodiment, be filled in reactor, obtained 3 D electrode reactor, is 6.0V at voltage, and when electric current is 0.2A, energising degraded 30ml dyeing waste water 45min, CODcr clearance reaches 97%.
Embodiment seven:
A, gas mud particle ball milling in ball mill, washing after taking out, immersion (washing, the object of soaking are desorption of impurities), dry at 120 DEG C, then cross 60 mesh sieves, get the thin gas mud particle of drying for subsequent use in baking oven;
B, shale are put in 120 DEG C of oven dry in baking oven, are pulverized by the shale of oven dry in mortar, then cross 60 mesh sieves, get dry thin shale for subsequent use;
C, by the thin shale of drying, polystyrene and the ZnO in thin for the drying in steps A gas mud particle, step B according to the weight percent of 55%:10%:15%:20%, mix and stir, being squeezed into raw material ball;
D, by the raw material ball in step C in an oven 120 DEG C dry 24 hours;
E, by step D dry after raw material ball, be placed in High Temperature Furnaces Heating Apparatus and rise to 300 DEG C from room temperature with 120 DEG C/h, heating 2h, then rise to 550 DEG C with 60 DEG C/h, activation 20min, then rise to 1050 DEG C of roasting 30min with 300 DEG C/h, naturally cool to room temperature, obtain gas mud basal granule sub-electrode material.
Get the gas mud basal granule sub-electrode 5.0g prepared in above-described embodiment, be filled in reactor, obtained 3 D electrode reactor, is 6.0V at voltage, and when electric current is 0.2A, energising degraded 30ml dyeing waste water 45min, CODcr clearance reaches 94%.
Claims (6)
1. a gas mud basal granule sub-electrode, is characterized in that: according to weight percent meter, comprises dry thin gas mud particle 50-60%, dry thin shale 10-20%, pore former 10-20%, activator 10-20%.
2. gas mud basal granule sub-electrode as claimed in claim 1, is characterized in that: pore former is the one in powdered carbon, saw dust, starch, polyvinyl alcohol (PVA), polyvinyl butyral acetal (PVB), granules of polystyrene.
3. gas mud basal granule sub-electrode as claimed in claim 1, is characterized in that: activator is Fe
3o
4, Fe
2o
3, MnO
2, one in ZnO.
4. a preparation method for gas mud basal granule sub-electrode, is characterized in that, comprises the following steps:
A, gas mud particle ball milling in ball mill, washing after taking out, immersion, dry at 120 DEG C in baking oven, then crosses 60 mesh sieves, gets dry thin gas mud particle;
B, shale are put in 120 DEG C of oven dry in baking oven, are pulverized by the shale of oven dry in mortar, then cross 60 mesh sieves, get dry thin shale;
C, by the thin shale of drying, pore former and the activator in thin for the drying in steps A gas mud particle, step B according to certain weight percent, comprise dry thin gas mud particle 50-60%, dry thin shale 10-20%, pore former 10-20%, activator 10-20%, mix and stir, being squeezed into raw material ball;
D, by the raw material ball in step C in an oven 120 DEG C dry 24 hours;
E, by step D dry after raw material ball, be placed in High Temperature Furnaces Heating Apparatus and rise to 300 DEG C from room temperature with 120 DEG C/h, heating 2h, then 550 DEG C are risen to 60 DEG C/h, activation 10-30min, rise to 1050 DEG C of roasting 10-30min with 300 DEG C/h again, naturally cool to room temperature, obtain gas mud basal granule sub-electrode material.
5. the preparation method of gas mud basal granule sub-electrode as claimed in claim 4, is characterized in that: described pore former is the one in powdered carbon, saw dust, starch, polyvinyl alcohol (PVA), polyvinyl butyral acetal (PVB), granules of polystyrene.
6. the preparation method of gas mud basal granule sub-electrode as claimed in claim 4, is characterized in that: described activator is Fe
3o
4, Fe
2o
3, MnO
2, one in ZnO.
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CN101191150A (en) * | 2007-05-29 | 2008-06-04 | 六盘水四维三友工贸有限公司 | Comprehensive utilization method for blast furnace gas mud and combustion furnace for processing |
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CN104276842A (en) * | 2013-07-03 | 2015-01-14 | 济南大学 | Ironmaking sludge based particle electrode and preparation method thereof |
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JP5535505B2 (en) * | 2009-03-19 | 2014-07-02 | 住友化学株式会社 | Method for producing porous ceramic molded body and porous ceramic molded body |
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CN1470657A (en) * | 2002-07-25 | 2004-01-28 | 宝钢集团上海梅山有限公司 | Steel making and iron making superlow zine dust recovery and treatment process |
CN101191150A (en) * | 2007-05-29 | 2008-06-04 | 六盘水四维三友工贸有限公司 | Comprehensive utilization method for blast furnace gas mud and combustion furnace for processing |
CN102392125A (en) * | 2011-10-25 | 2012-03-28 | 内蒙古科技大学 | Technology for recovering iron ore concentrate and coke powder from blast furnace gas dust or gas sludge |
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