CN101357367B - Method for processing waste cell-lining of aluminum cell using coal slack - Google Patents

Method for processing waste cell-lining of aluminum cell using coal slack Download PDF

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Publication number
CN101357367B
CN101357367B CN200810058935XA CN200810058935A CN101357367B CN 101357367 B CN101357367 B CN 101357367B CN 200810058935X A CN200810058935X A CN 200810058935XA CN 200810058935 A CN200810058935 A CN 200810058935A CN 101357367 B CN101357367 B CN 101357367B
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China
Prior art keywords
waste
percent
gangue
waste lining
lining
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CN200810058935XA
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Chinese (zh)
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CN101357367A (en
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宁平
杨月红
欧根能
赵健蓉
方祖国
张慧娜
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昆明理工大学
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Abstract

The present invention provides a method for using coal gangue to dispose an aluminum cell waste slot liner. The method comprises the steps as follows: after being crushed and milled, the coal gangue with the adding quantity being 10 percent to 30 percent of the quantity of the waste slot liner and quick lime with the adding quantity being 5 percent to 35 percent of the quantity of the waste slot liner are mixed with the waste slot liner uniformly; the material is calcined for 40-70 minutes at the temperature of 900-1,200 DEG C; the calcined material is milled until the granularity is less than0.074mm; residual soluble F<-> is leached by limewater with the concentration being 0.5 percent to 5 percent, the leaching time is 30-60 minutes; then the material is filtered; filtrate is used for other purposes; filter residue is recycled as usable material. The method achieves the comprehensive using purpose of treating a waste with another waste and changing waste into valuable. The method has the advantages of reliable technology, low price and wide source and low price of raw material, is easy for industrial treatment and also completely and effectively uses the self thermal value of waste electrode and the thermal value of the coal gangue during the disposing process, thereby ensuring the disposing cost to be reduced and the disposal effect to be good. The filtrate is disposed, recycled and reused, and the filter residue is directly used as cement raw material or filling material for road construction.

Description

Utilize the method for gangue process aluminum electrolytic groove waste lining

Technical field

The present invention relates to a kind of method of process aluminum electrolytic groove waste lining, especially a kind of method of utilizing gangue, quick lime process aluminum electrolytic groove waste lining belongs to the electrolysis tech field.

Background technology

Aluminium cell in use for some time; be generally 4 years; must carry out large repairs; change protective layer---the slot liner in the groove; because the material of slot liner mainly is refractory brick, insulating brick and carbon piece etc.; so the slot liner material that changes has formed the overhaul slag of electrolytic cell, the slot liner amount that aluminium per ton produces is approximately 0.04 ton.Need to add fluoride salt in the Aluminium Electrolysis process, aluminium per ton consumes fluoride salt 33kg approximately, and wherein a part of chloride enters atmosphere, and another part residues in the slot liner, causes the concentration of fluoride in the overhaul slag higher.Content of fluoride accounts for 3.49%~11.48% of waste residue total amount.By the regulation of State Bureau of Environmental Protection, the inorganic fluoride refuse belongs to hazardous waste, in case the leaching of process rainwater must be separated out wherein harmful components, after permeating the ground, will cause the pollution of body of groundwater and surface water body, serious harm human health and animals and plants existence.Therefore to prevent and reduce electrolytic cell overhaul slag pollution on the environment, must prevent earlier that the following of high-concentration fluorine-contained leaching liquor from oozing.Therefore how to remove fluorine-containing material and just seem that particular importance, the pollution of waste lining have become one of significant problem that influences the healthy coordination of aluminium industry sustainable development.

Gangue is meant the solid waste that produces in coal mining, the dressing of coal by washing process, belongs to available resource, has dual nature.From coal mining, the annual 100000000 t coals of producing of China are about discharging spoil 1,400 ten thousand t; Process from coal washing, every washing 100,000,000 t coking coals discharging spoil amount 2,000 ten thousand t whenever wash 100,000,000 t thermal coals, discharging spoil amount 15,000,000 t.2005, domestic all kinds of Coal Production coal 1,045 hundred million t, coal washing 38,500,000,000 t, discharging spoil amount 19-20 hundred million t.Thereby, seat surplus the existing hillock 1500 in national state-owned colliery, accumulating amount 3,000,000,000 t above (accounting for more than 40% of Chinese industrial solid waste total emission volumn).

A large amount of stackings of gangue, not only cover the soil, influence ecological environment, spoil leaching water will pollute surrounding soil and underground water, and contain certain combustible in the gangue, issue in suitable condition and to be conigenous combustion, pernicious gas pollutant atmospheres such as discharging sulfur dioxide, nitrogen oxide, oxycarbide and flue dust influence the healthy of mining area resident.The accident of being poisoned to death because of the spoil spontaneous combustion personnel that cause once took place as mining area, Benxi, Liaoning.

About the harmless treatment and the method for comprehensive utilization of aluminium electrolytic tank, what former studies was more is that Wet technique is handled waste lining.Adopt Wet technique to handle waste lining, recyclable part carbonaceous material and fluoride salt, but the technical barrier that Wet technique exists it to overcome: the clearance of 1. poisoning thing is lower, easily causes secondary pollution; 2. the corrosion of treatment facility is difficult to solve; 3. only useless negative electrode is produced effect, little to the waste refractory materials effect.Therefore the wet-treating technology can not realize the innoxious fully of waste lining.

In the patent of publication number CN1895803A, reported a kind of method of process aluminum electrolytic groove waste lining, it is to add a certain amount of lime stone and flyash in waste lining, it is levigate to mix the back, carries out calcination process in rotary kiln, handles the back material and carries out secondary response with limewash.In the industrial implementation process, this method is limit by the rotary kiln running performance, has the material deficiency of caking easily.

Having reported a kind of in the patent of publication number CN101147913A is the method for additive treating aluminium electrolytic tank with the magnesium reduction slag, it is characterized in that its processing procedure is: (1) will comprise useless negative electrode, waste refractory materials the waste lining fragmentation, levigate to granularity less than 0.15mm; (2) with magnesium reduction slag, lime stone broken, levigate respectively to granularity less than 1mm; (3) waste lining, lime stone and magnesium reduction slag are prepared burden, mixed, wherein the lime stone amount of allocating into is 20%~45% of a waste lining weight, and the magnesium reduction slag amount of allocating into is 5%~45% of a waste lining weight; (4) blended stock is added in rotary kiln or the similar devices, under 900~1200 ℃ of temperature, carry out calcination process, 45~75 minutes roasting reaction time; (5) make after the roasting good dispersion, can be used as cement raw material or the solid material of the fill material of building the road.Eliminated the pollution of waste lining after the processing, and made waste lining, magnesium reduction slag obtain effective utilization.In the industrial implementation process, this method is big to lime and magnesium reduction slag demand, therefore to requiring also just than higher in rotary kiln or the similar devices.

In the patent of publication number CN1583301A, reported a kind of method for innocent treatment of aluminium electrolytic tank, relate to cell lining discarded in a kind of electrolysis production metallic aluminium process, particularly comprise the method for innocent treatment of all waste tank linings of waste cathode carbon block, waste refractory materials.With the mineral that contain calcium oxide is reactant, is additive with silica containing material, is extra fuel with bituminous coal, the employing rotary kiln is heat-treated, and the tail gas alumina adsorption is handled the back material and carried out secondary response with limewash drip washing, limewash is recycling, makes the innoxious method of waste lining.Can make after the processing that soluble fluoride and cyanide content descend more than 95% in the waste lining, soluble fluoride content is lower than 50mg/L in the solid slag, and cyanide content is lower than 1.0mg/L, and solid slag and flue gas satisfy the national environmental protection emission request.Eliminated the pollution of waste lining, carbon-free non-toxic solid slag can be used as the raw material of cement industry, refractory industry or is used to pave the way, and fluorinated alumina returns aluminium cell and uses.In the industrial implementation process, this method is higher to relative cost, exists reaction speed slow, the deficiency that production efficiency is low.

Summary of the invention

For overcoming prior art above shortcomings in process aluminum electrolytic groove waste lining, the invention provides a kind of method of utilizing gangue, quick lime process aluminum electrolytic groove waste lining, its treatment of wastes with processes of wastes against one another, turn waste into wealth, make waste lining innoxious fully, and processing cost low, be easy to industrial implementation and production efficiency height.

The objective of the invention is to be achieved through the following technical solutions: a kind of method with gangue, quick lime process aluminum electrolytic groove waste lining is characterized in that its processing procedure is:

A, with the waste lining fragmentation, levigate to granularity less than 0.2mm;

B, with gangue levigate to granularity less than 0.5mm;

C, be the gangue of waste lining quality 10~30%, and addition is the quick lime of waste lining quality 5~35%, mixes with waste lining with addition;

D, be under 900~1200 ℃ of conditions in temperature with the blended stock of C step, roasting 40~70min, calcining matter;

E, with the calcining matter of D step levigate to granularity less than 0.074mm, be that 0.5~5% limewash did not have calcining matter with concentration, to leach remaining solvable F -, extraction time is 30~60min, filters afterwards, collects filtrate and filter residue respectively.

Existing roaster or rotary kiln, rotary furnace are adopted in the roasting of described D step, go out good dispersion with roasting, can be used as cement raw material or the solid material of the fill material of building the road.

The limewash leaching amount of described E step is crossed the particulate calcining matter with the limewash submergence and is advisable.

Gangue caloric value of the present invention is generally 800~1500 card/grams, and its inorganic constituents mainly is oxide and some rare metal of silicon, aluminium, calcium, magnesium, iron.Its chemical composition is: SiO 2Be 52~65; Al 2O 3Be 16~36; Fe 2O 3Be 2.28~14.63; CaO is 0.42~8.32; MgO is 0.44~2.41.Quick lime contains CaO〉85%.

Roasting process key reaction of the present invention is:

2NaCN+(2X+5)/2O 2=Na 2O+2CO 2+2NO x

2NaF+CaO=CaF 2+Na 2O,

2NaF+4CaO+4SiO 2+Al 2O 3=Ca 4Si 2O 7F 2+2NaAlSiO 4

2CaO+SiO 2=CaSiO 4

The present invention has following advantage and effect: adopt such scheme, be additive promptly with gangue, quick lime, in the process of process aluminum electrolytic groove waste lining, effectively having utilized solid waste---the gangue of discharging in driving, exploitation and coal washing process, specifically is the SiO that has utilized gangue contained 2, Al 2O 3, useful component such as combustible, the comprehensive utilization purpose that reached the treatment of wastes with processes of wastes against one another, turns waste into wealth.This method and technology is reliable, is easy to industrial treatment, and wide, the low price of used various raw material sources has also fully effectively utilized useless negative electrode self and calorific value gangue in the processing procedure, makes that processing cost reduces, treatment effect is good.Handling gained filtrate is NaOH solution, can be used as other commercial Application after reclaiming, and gained filter residue main component is CaF 2, CaSiO 4, Ca 4Si 2O 7F 2, nepheline and β-aluminium oxide, can directly use as the cement raw material or the fill material of building the road.

The specific embodiment

Embodiment 1

Aluminium scrap electrolytic cell slot liner, gangue is broken, levigate in advance, take by weighing waste lining 1000 grams of granularity less than 0.2mm, granularity is less than gangue 100 grams of 0.5mm, quick lime 350 grams, three kinds of mixing of materials are even, blended stock is sent in the roaster of prior art and carried out roasting, under 900 ℃ of sintering temperatures, roasting reaction time 70min, material abrasive dust after the roasting is that the fine powder calcining matter is crossed in 5% limewash submergence with concentration, leach 30min, after the method for prior art was filtered, filtrate NaOH can supply industrial production usefulness, and the filter residue main component is CaF 2, CaSiO 4, Ca 4Si 2O 7F 2, nepheline and β-aluminium oxide, as the solid material of the cement raw material or the fill material of building the road.

Embodiment 2

Aluminium scrap electrolytic cell slot liner, gangue is broken, levigate in advance, take by weighing waste lining 1000 grams of granularity less than 0.2mm, granularity is less than gangue 150 grams of 0.5mm, quick lime 250 grams, three kinds of mixing of materials are even, blended stock sent into carry out roasting in the existing calciner, 1000 ℃ of sintering temperatures, roasting reaction time 60min, material abrasive dust after the roasting is that the fine powder calcining matter is crossed in 3% limewash submergence with concentration, leach 40min, after existing method was filtered, filtrate NaOH can supply industrial production usefulness, and filter residue is as the solid material of the cement raw material or the fill material of building the road.

Embodiment 3

Aluminium scrap electrolytic cell slot liner, gangue is broken, levigate in advance, take by weighing waste lining 1000 grams of granularity less than 0.2mm, granularity is less than gangue 200 grams of 0.5mm, quick lime 150 grams, three kinds of mixing of materials are even, blended stock is sent in the calciner of prior art and carried out roasting, 1100 ℃ of sintering temperatures, roasting reaction time 50min, material abrasive dust after the roasting is that the fine powder calcining matter is crossed in 1.5% limewash submergence with concentration, leach 50min, after filtration, filtrate NaOH can supply industrial production usefulness, and filter residue is as the solid material of the cement raw material or the fill material of building the road.

Embodiment 4

With aluminium scrap electrolytic cell slot liner, gangue is broken in advance, levigate, take by weighing waste lining 1000 grams of granularity less than 0.2mm, granularity is less than gangue 300 grams of 0.5mm, quick lime 50 grams, three kinds of mixing of materials are even, the roasting apparatus of blended stock being sent into prior art carries out roasting, 1200 ℃ of sintering temperatures, roasting reaction time 40min, material abrasive dust after the roasting is that the fine powder calcining matter is crossed in 0.5% limewash submergence with concentration, leach 60min, after the filter method filtration with prior art, filtrate NaOH can supply industrial production usefulness, and filter residue is as the solid material of the cement raw material or the fill material of building the road.

Claims (2)

1. method of utilizing gangue process aluminum electrolytic groove waste lining is characterized in that its processing procedure is:
A, with the waste lining fragmentation, levigate to granularity less than 0.2mm;
B, with gangue levigate to granularity less than 0.5mm;
C, be the gangue of waste lining quality 10~30%, and addition is the quick lime of waste lining quality 5~35%, mixes with waste lining with addition;
D, be under 900~1200 ℃ of conditions in temperature with the blended stock of C step, roasting 40~70min, calcining matter;
E, with the calcining matter of D step levigate to granularity less than 0.074mm, be that 0.5~5% limewash did not have calcining matter with concentration, to leach remaining solvable F -, extraction time is 30~60min, filters afterwards, collects filtrate and filter residue respectively.
2. the method for utilizing gangue process aluminum electrolytic groove waste lining according to claim 1, existing roaster or rotary kiln, rotary furnace are adopted in the roasting that it is characterized in that described D step, go out good dispersion with roasting, can be used as cement raw material or the solid material of the fill material of building the road.
CN200810058935XA 2008-09-19 2008-09-19 Method for processing waste cell-lining of aluminum cell using coal slack CN101357367B (en)

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Families Citing this family (9)

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Publication number Priority date Publication date Assignee Title
CN102330117A (en) * 2010-07-13 2012-01-25 厦门热工环保系统工程有限公司 Safe aluminium cell exhaust gas waste heat recovery method
CN102011145B (en) * 2010-12-03 2012-08-29 伊川龙海科技实业有限公司 Method for recycling electrolytes and producing aluminum-silicon alloy as byproduct by using aluminum electrolysis waste mixing material
CN102010932B (en) * 2010-12-03 2012-08-29 伊川龙海科技实业有限公司 Method for producing deoxidizer by utilizing waste silicon carbide of aluminium electrolysis
CN103755312B (en) * 2014-01-25 2015-06-24 云南蓝天铝业环保科技有限公司 Coal gangue brick prepared from aluminum-electrolytic cell waste thermal-insulation materials and preparation method thereof
CN103831286B (en) * 2014-03-12 2015-11-11 郑州经纬科技实业有限公司 The heat resolve system and method for aluminium electroloysis waste lining
CN105457972A (en) * 2015-12-10 2016-04-06 北京京碧蓝环保科技有限公司 Aluminum electrolysis waste slot lining hazard-free treatment method for carrying out wet strengthening for defluorination after heat treatment
CN105499251A (en) * 2015-12-11 2016-04-20 北京京碧蓝环保科技有限公司 Glass solidification stabilization method for treating aluminum electrolysis waste slot lining based on F-Si chemical bond
CN105327933B (en) * 2015-12-14 2017-10-24 北京京碧蓝环保科技有限公司 Aluminium electrolytic tank processing method based on chemical precipitation and redox reaction
CN106086938B (en) * 2016-06-30 2019-01-04 中南大学 A kind of method that electrolyte in aluminium electroloysis waste lining is recycled in the leaching of ultrasonic wave auxiliary pressurized alkali

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Assignee: Yunnan Yingjiang Xingyun Co., Ltd.

Assignor: Kunming University of Science and Technology

Contract record no.: 2011530000065

Denomination of invention: Method for processing waste cell-lining of aluminum cell using coal slack

Granted publication date: 20100616

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Record date: 20110811

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Termination date: 20130919