CN105499251A - Glass solidification stabilization method for treating aluminum electrolysis waste slot lining based on F-Si chemical bond - Google Patents
Glass solidification stabilization method for treating aluminum electrolysis waste slot lining based on F-Si chemical bond Download PDFInfo
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- CN105499251A CN105499251A CN201510920833.4A CN201510920833A CN105499251A CN 105499251 A CN105499251 A CN 105499251A CN 201510920833 A CN201510920833 A CN 201510920833A CN 105499251 A CN105499251 A CN 105499251A
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- glass
- waste lining
- stabilization method
- chemical bond
- waste
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
- B09B—DISPOSAL OF SOLID WASTE
- B09B3/00—Destroying solid waste or transforming solid waste into something useful or harmless
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
- B09B—DISPOSAL OF SOLID WASTE
- B09B5/00—Operations not covered by a single other subclass or by a single other group in this subclass
Abstract
The invention discloses a glass solidification stabilization method for treating an aluminum electrolysis waste slot lining based on an F-Si chemical bond. The glass solidification stabilization method comprises the following steps: crushing the waste slot lining into particles with a particle size smaller than 15mm; putting the crushed waste slot lining into a metal curing tank to carry out medium-temperature roasting, adding glass substances, weight of which is 0.8-2.0 times that of the waste slot lining, as a curing agent to continuously roast after controlling a temperature to 750-850 DEG C and preserving the heat for 2-3.5 hours to carry out the medium-temperature roasting, increasing the temperature to 1050-1200 DEG C and preserving the heat for 2-4 hours; and enabling a molten glass-state mixture to flow into a receiving container, and carrying out annealing/quenching to obtain a glass form containing a waste slot lining fluoride. The finally formed glass-state residues have relatively strong chemical stability and mechanical resistance, are relatively small in size, are easy to store and transfer, can be used as a building material or can be used as common solid waste to carry out landfill treatment or can be used as a coating material for being used for the industries of buildings, roads or heat engines.
Description
Technical field
The present invention relates to a kind of aluminium electroloysis waste lining treatment technology, particularly relate to a kind of glass solidification stabilization method based on F-Si chemical bond process aluminum electrolytic waste lining, comprise all cell linings discarded in the aluminum electrolysis process of useless negative electrode carbon, graphite liner etc.
Background technology
Produce primary aluminum per ton, 30kg ~ 50kg waste lining will be produced.Waste lining is because the harm such as the fluoride containing great amount of soluble, poisonous cyanide element and be put into National Hazard refuse register, if mishandling and direct air storage not only atmosphere pollution, and enters river pollution earth surface water source along with rainwater; Landfill disposal simultaneously also can contaminated soil, and above-mentioned fluoride is very easy penetrates into underground, polluted underground water along with rainwater, and the vegeto-animal growth of serious harm, more has a strong impact on the healthy of the mankind.Therefore, the harmless treatment of waste lining and disposal seem very necessary and urgent.Because of wet processing technique exist sodium fluoride and limewash sluggish, react halfway problem and operation field because of the precipitation of the gases such as HCN and there is potential safety hazard, so the main method of process waste lining is burning method at present, cyanide can realize decomposing, but content of fluoride is higher, be difficult to disposable thorough realization solidification transform, incineration residue still has certain environmental risk and hidden danger.
Summary of the invention
The object of this invention is to provide a kind of glass solidification stabilization method based on F-Si chemical bond process aluminum electrolytic waste lining.
The object of the invention is to be achieved through the following technical solutions:
Glass solidification stabilization method based on F-Si chemical bond process aluminum electrolytic waste lining of the present invention, comprises step:
A, waste lining is carried out break process, be broken into the particle that particle diameter is less than 15mm;
B, the waste lining after fragmentation inserted and is equipped with in the metal-cured tank of heat induction device, middle temperature calcining heating is carried out by heater, and produced dust is enclosed in solidification tank, control temperature 750 ~ 850 DEG C, be incubated 2 ~ 3.5 hours, innoxious with the pyrolysis of the burning production capacity and cyanide that realize waste lining carbonaceous composition;
After C, middle temperature are calcined, in metal-cured tank, allocate the category of glass material of waste lining weight 0.8 ~ 2.0 times into as curing agent;
D, continue calcining, be warming up to 1050 ~ 1200 DEG C, be incubated 2 ~ 4 hours, reach molten condition with the mixture making the category of glass material that adds and waste lining tentatively calcine residue;
E, under controlled conditions, the glassy state mixture of melting flows into receiving vessel from metal-cured tank, just obtains the glass solidified body containing waste lining fluoride after annealing/quenching.
As seen from the above technical solution provided by the invention, the glass solidification stabilization method based on F-Si chemical bond process aluminum electrolytic waste lining that the embodiment of the present invention provides, burn carbonaceous material at general incineration technology (temperature is lower than 900 DEG C) and produce the energy, destroy by fire on the basis of decomposition cyanide, using scrap glass goods as reactant, vitrification is adopted thoroughly to be fixed in vitreous structure by soluble fluoride in aluminium electroloysis waste lining, reduce the activity of fluoride, the glassy state residue of final formation has stronger stability, and small volume, be easy to store and transfer, can be used as building materials use or as Ordinary solid waste landfill disposal.
Accompanying drawing explanation
The schematic flow sheet of the glass solidification stabilization method based on F-Si chemical bond process aluminum electrolytic waste lining that Fig. 1 provides for the embodiment of the present invention.
Detailed description of the invention
To be described in further detail the embodiment of the present invention below.
Glass solidification stabilization method based on F-Si chemical bond process aluminum electrolytic waste lining of the present invention, its preferably detailed description of the invention be:
Comprise step:
A, waste lining is carried out break process, be broken into the particle that particle diameter is less than 15mm;
B, the waste lining after fragmentation inserted and is equipped with in the metal-cured tank of heat induction device, the calcining of middle temperature is carried out by heater, and produced dust is enclosed in solidification tank, control temperature 750 ~ 850 DEG C, be incubated 2 ~ 3.5 hours, innoxious with the pyrolysis of the burning production capacity and cyanide that realize waste lining carbonaceous composition;
After C, middle temperature are calcined, in metal-cured tank, allocate the category of glass material of waste lining weight 0.8 ~ 2.0 times into as curing agent;
D, continue calcining, be warming up to 1050 ~ 1200 DEG C, be incubated 2 ~ 4 hours, reach molten condition with the mixture making the category of glass material that adds and waste lining tentatively calcine residue;
E, under controlled conditions, the glassy state mixture of melting flows into receiving vessel from metal-cured tank, just obtains the glass solidified body containing waste lining fluoride after annealing/quenching.
In described step B, be enclosed in metal-cured tank in middle temperature calcination process by produced dust, after burning, the content of organics of bottom ash is less than 1%.
Be enclosed in by dust in metal-cured tank, one is achieve the purification to combustion product gases, and two is that the dust be enclosed in incinerator can strengthen solidification to soluble fluoride, stabilisation.
In described step B, the selection of middle temperature calcination stage temperature, one is that two is the fluorine steam pressures that will keep below 5mmHg, to realize the minimum volatile quantity of fluoride according to the Thorough combustion of the decomposition and carbonaceous composition that realize waste lining cyanide to form ash.
In described step C, the category of glass material allocated in metal-cured tank comprise following any one or more:
Scrap glass slag, cullet, sand, gangue, flyash, kaolin, shale.
In described step C, the mol ratio of Si:Na element is made to be greater than 1.5.
Glass solidification stabilization method based on F-Si chemical bond process aluminum electrolytic waste lining of the present invention, burn carbonaceous material at general incineration technology (temperature is lower than 900 DEG C) and produce the energy, destroy by fire on the basis of decomposition cyanide, using scrap glass goods as reactant, vitrification is adopted thoroughly to be fixed in vitreous structure by soluble fluoride in aluminium electroloysis waste lining, reduce the activity of fluoride, the glassy state residue of final formation has stronger chemical stability and mechanical resistance, and small volume, be easy to store and transfer, can be used as building materials use or carry out landfill disposal as Ordinary solid waste, or be used for building as coating material, road or heat engine industry.
It is motionless that soluble fluoride to be stabilized in glass lattice internal fixtion by F-Si chemical bond by the present invention, is physically stable and chemically stable acting in conjunction, and by controlling heat treatment process, glass solidified body is converted into glass lattice, and common is: CaOSiO
2, CaOMgO2SiO
2, CaOAl
2o
32SiO
2, Na
2oAl
2o
32SiO
2, Fe
2o
3, Fe
3o
4.
Specific embodiment:
As shown in Figure 1, its processing procedure is followed successively by: waste lining is carried out break process by (1), is broken into the particle that particle diameter is less than 15mm; (2) waste lining after fragmentation is inserted be equipped with in the metal-cured tank of heat induction device, heating and calcining is carried out by heater, and produced dust is enclosed in solidification tank, control temperature 750 ~ 850 DEG C, be incubated 2 ~ 3.5 hours, innoxious with the pyrolysis of the burning production capacity and cyanide that realize waste lining carbonaceous composition; (3) in temperature calcined after, to solidification tank in allocate the category of glass material of waste lining weight 0.8 ~ 2.0 times into as curing agent; (4) continue calcining, be warming up to 1050 ~ 1200 DEG C, be incubated 2 ~ 4 hours, reach molten condition with the mixture making the category of glass material that adds and waste lining tentatively calcine residue; (5) under controlled conditions, the glassy state mixture of melting flows into receiving vessel from metal-cured tank, just obtains the glass solidified body containing waste lining fluoride after annealing/quenching.The product of solidification is the monoblock dense solid of structural integrity, size can transport easily, without the need to any additional reservoir, can carry out landfill by general refuse, or is used for building, road or heat engine industry as coating material.
Embodiment 1:
First waste lining is broken into the particle that particle diameter is less than 10mm, takes 1500g and insert and be equipped with in the metal-cured tank of heat induction device, carry out closed heating and calcining by heater, control temperature 830 DEG C, be incubated 3 hours.After middle temperature is calcined, in solidification tank, allocate discarded cullet 2500g into as curing agent, continue calcining and be warming up to 1150 DEG C, be incubated 3.5 hours, the mixture in solidification tank is molten condition.Then, under controlled conditions, the glassy state mixture of melting flows into the effigurate receiving vessel of tool from metal-cured tank, just obtains the glass solidified body containing waste lining fluoride after quenching program cools fast.
According to hazardous waste judging standard, Leaching standard (GB5085.3-2007), harmfulness detection is carried out to final glass solidified body, result shows: in leachate, inorganic fluoride (not comprising calcirm-fluoride, in F-) is 0.72mg/L; Cyanide, for not detect, shows that glass solidified body is no longer hazardous waste; Even if according to the landfill decree (Directive1999/31/EConthelandfillofwaste) of European Union, this Leaching level is also lower than inert waste judging standard, and therefore the inventive method thoroughly achieves the innoxious of waste lining.
Embodiment 2:
First waste lining is broken into the particle that particle diameter is less than 5mm, takes 1000g and insert and be equipped with in the metal-cured tank of heat induction device, carry out closed heating and calcining by heater, control temperature 800 DEG C, be incubated 2.5 hours.After middle temperature is calcined, in solidification tank, allocate discarded cullet 1500g into as curing agent, continue calcining and be warming up to 1100 DEG C, be incubated 3 hours, the mixture in solidification tank is molten condition.Then, under controlled conditions, the glassy state mixture of melting flows into the effigurate receiving vessel of tool from metal-cured tank, just obtains the glass solidified body containing waste lining fluoride after quenching program cools fast.
According to hazardous waste judging standard, Leaching standard (GB5085.3-2007), harmfulness detection is carried out to final glass solidified body, result shows: in leachate, inorganic fluoride (not comprising calcirm-fluoride, in F-) is 0.97mg/L; Cyanide, for not detect, shows that glass solidified body is no longer hazardous waste; Even if according to the landfill decree (Directive1999/31/EConthelandfillofwaste) of European Union, this Leaching level is also lower than inert waste judging standard, and therefore the inventive method thoroughly achieves the innoxious of waste lining.
The above; be only the present invention's preferably detailed description of the invention, but protection scope of the present invention is not limited thereto, is anyly familiar with those skilled in the art in the technical scope that the present invention discloses; the change that can expect easily or replacement, all should be encompassed within protection scope of the present invention.Therefore, protection scope of the present invention should be as the criterion with the protection domain of claims.
Claims (6)
1., based on a glass solidification stabilization method for F-Si chemical bond process aluminum electrolytic waste lining, it is characterized in that, comprise step:
A, waste lining is carried out break process, be broken into the particle that particle diameter is less than 15mm;
B, the waste lining after fragmentation inserted and is equipped with in the metal-cured tank of heat induction device, the calcining of middle temperature is carried out by heater, and produced dust is enclosed in solidification tank, control temperature 750 ~ 850 DEG C, be incubated 2 ~ 3.5 hours, innoxious with the pyrolysis of the burning production capacity and cyanide that realize waste lining carbonaceous composition;
After C, middle temperature are calcined, in metal-cured tank, allocate the category of glass material of waste lining weight 0.8 ~ 2.0 times into as curing agent;
D, continue calcining, be warming up to 1050 ~ 1200 DEG C, be incubated 2 ~ 4 hours, reach molten condition with the mixture making the category of glass material that adds and waste lining tentatively calcine residue;
E, under controlled conditions, the glassy state mixture of melting flows into receiving vessel from metal-cured tank, just obtains the glass solidified body containing waste lining fluoride after annealing/quenching.
2. the glass solidification stabilization method based on F-Si chemical bond process aluminum electrolytic waste lining according to claim 1, it is characterized in that, in described step B, be enclosed in metal-cured tank in middle temperature calcination process by produced dust, after burning, the content of organics of bottom ash is less than 1%.
3. the glass solidification stabilization method based on F-Si chemical bond process aluminum electrolytic waste lining according to claim 2, it is characterized in that, dust is enclosed in metal-cured tank, one is achieve the purification to combustion product gases, and two is that the dust be enclosed in incinerator can strengthen solidification to soluble fluoride, stabilisation.
4. the glass solidification stabilization method based on F-Si chemical bond process aluminum electrolytic waste lining according to claim 1, it is characterized in that, in described step B, the selection of middle temperature calcination stage temperature, one is to form ash according to the Thorough combustion of the decomposition and carbonaceous composition that realize waste lining cyanide, two is the fluorine steam pressures that will keep below 5mmHg, to realize the minimum volatile quantity of fluoride.
5. the glass solidification stabilization method based on F-Si chemical bond process aluminum electrolytic waste lining according to any one of Claims 1-4, is characterized in that, in described step C, the category of glass material allocated in metal-cured tank comprise following any one or more:
Scrap glass slag, cullet, sand, gangue, flyash, kaolin, shale.
6. the glass solidification stabilization method based on F-Si chemical bond process aluminum electrolytic waste lining according to claim 5, is characterized in that, in described step C, makes the mol ratio of Si:Na element be greater than 1.5.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201510920833.4A CN105499251A (en) | 2015-12-11 | 2015-12-11 | Glass solidification stabilization method for treating aluminum electrolysis waste slot lining based on F-Si chemical bond |
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| CN201510920833.4A CN105499251A (en) | 2015-12-11 | 2015-12-11 | Glass solidification stabilization method for treating aluminum electrolysis waste slot lining based on F-Si chemical bond |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108435751A (en) * | 2018-03-11 | 2018-08-24 | 沈阳银海再生资源科技有限公司 | A kind of aluminium electroloysis waste lining is innoxious and resource utilization method and device |
| CN110590153A (en) * | 2019-10-17 | 2019-12-20 | 北京矿冶科技集团有限公司 | Low-temperature vitrification harmless treatment method for overhaul slag, solid flux co-melted with overhaul slag, preparation method of solid flux, glass granules and application of glass granules |
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| US4956158A (en) * | 1988-03-29 | 1990-09-11 | Aluminum Company Of America | Stabilization of fluorides of spent potlining by chemical dispersion |
| CN1358581A (en) * | 2001-11-20 | 2002-07-17 | 舒大平 | Harmless treatment and comprehensive utilization method for aluminium electrolytic carbon slag and waste cathode material |
| CN1583301A (en) * | 2004-05-24 | 2005-02-23 | 中国铝业股份有限公司 | Harmless treating method for waste tank lining of aluminium electrolytic bath |
| CN1785537A (en) * | 2005-11-28 | 2006-06-14 | 中国铝业股份有限公司 | Treatment method of aluminium electrolytic bath waste cathode carbon blook innocuousnes |
| CN101119943A (en) * | 2005-02-16 | 2008-02-06 | 诺沃福特国际有限公司 | Process and apparatus for converting spent potliners into a glass frit, and resulting products |
| CN101357367A (en) * | 2008-09-19 | 2009-02-04 | 昆明理工大学 | Method for processing waste cell-lining of aluminum cell using coal slack |
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2015
- 2015-12-11 CN CN201510920833.4A patent/CN105499251A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4956158A (en) * | 1988-03-29 | 1990-09-11 | Aluminum Company Of America | Stabilization of fluorides of spent potlining by chemical dispersion |
| CN1358581A (en) * | 2001-11-20 | 2002-07-17 | 舒大平 | Harmless treatment and comprehensive utilization method for aluminium electrolytic carbon slag and waste cathode material |
| CN1583301A (en) * | 2004-05-24 | 2005-02-23 | 中国铝业股份有限公司 | Harmless treating method for waste tank lining of aluminium electrolytic bath |
| CN101119943A (en) * | 2005-02-16 | 2008-02-06 | 诺沃福特国际有限公司 | Process and apparatus for converting spent potliners into a glass frit, and resulting products |
| CN1785537A (en) * | 2005-11-28 | 2006-06-14 | 中国铝业股份有限公司 | Treatment method of aluminium electrolytic bath waste cathode carbon blook innocuousnes |
| CN101357367A (en) * | 2008-09-19 | 2009-02-04 | 昆明理工大学 | Method for processing waste cell-lining of aluminum cell using coal slack |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108435751A (en) * | 2018-03-11 | 2018-08-24 | 沈阳银海再生资源科技有限公司 | A kind of aluminium electroloysis waste lining is innoxious and resource utilization method and device |
| CN110590153A (en) * | 2019-10-17 | 2019-12-20 | 北京矿冶科技集团有限公司 | Low-temperature vitrification harmless treatment method for overhaul slag, solid flux co-melted with overhaul slag, preparation method of solid flux, glass granules and application of glass granules |
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