CN1253369C - Process for recovering fluoride salt from aluminium electrolyzing carbon slag - Google Patents
Process for recovering fluoride salt from aluminium electrolyzing carbon slag Download PDFInfo
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- CN1253369C CN1253369C CN 200410069389 CN200410069389A CN1253369C CN 1253369 C CN1253369 C CN 1253369C CN 200410069389 CN200410069389 CN 200410069389 CN 200410069389 A CN200410069389 A CN 200410069389A CN 1253369 C CN1253369 C CN 1253369C
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- fluoride salt
- carbon slag
- reclaims
- alumina
- aluminium electrolyzing
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 65
- 150000004673 fluoride salts Chemical class 0.000 title claims abstract description 59
- 238000000034 method Methods 0.000 title claims abstract description 40
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 title claims abstract description 30
- 229910052782 aluminium Inorganic materials 0.000 title claims abstract description 30
- 229910052799 carbon Inorganic materials 0.000 title claims description 31
- 239000002893 slag Substances 0.000 title claims description 28
- 239000004411 aluminium Substances 0.000 title claims description 24
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 29
- 239000000446 fuel Substances 0.000 claims abstract description 19
- 239000007788 liquid Substances 0.000 claims abstract description 8
- 239000003575 carbonaceous material Substances 0.000 claims abstract description 7
- 238000005516 engineering process Methods 0.000 claims abstract description 4
- 238000011084 recovery Methods 0.000 claims description 17
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 13
- 239000007789 gas Substances 0.000 claims description 12
- 238000001179 sorption measurement Methods 0.000 claims description 12
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 10
- 239000002245 particle Substances 0.000 claims description 9
- 239000003795 chemical substances by application Substances 0.000 claims description 8
- 239000006185 dispersion Substances 0.000 claims description 8
- 239000003034 coal gas Substances 0.000 claims description 5
- 238000002485 combustion reaction Methods 0.000 claims description 4
- 239000000295 fuel oil Substances 0.000 claims description 4
- 235000009508 confectionery Nutrition 0.000 claims description 3
- 239000003345 natural gas Substances 0.000 claims description 3
- 238000005868 electrolysis reaction Methods 0.000 abstract description 7
- 239000000463 material Substances 0.000 abstract description 3
- 239000002270 dispersing agent Substances 0.000 abstract 2
- 230000002411 adverse Effects 0.000 abstract 1
- 238000001354 calcination Methods 0.000 abstract 1
- 238000013329 compounding Methods 0.000 abstract 1
- 230000000694 effects Effects 0.000 abstract 1
- 239000003792 electrolyte Substances 0.000 abstract 1
- 239000012535 impurity Substances 0.000 abstract 1
- PUZPDOWCWNUUKD-UHFFFAOYSA-M sodium fluoride Chemical compound [F-].[Na+] PUZPDOWCWNUUKD-UHFFFAOYSA-M 0.000 description 16
- WUKWITHWXAAZEY-UHFFFAOYSA-L calcium difluoride Chemical compound [F-].[F-].[Ca+2] WUKWITHWXAAZEY-UHFFFAOYSA-L 0.000 description 12
- 229910001634 calcium fluoride Inorganic materials 0.000 description 12
- 230000001698 pyrogenic effect Effects 0.000 description 10
- 239000002994 raw material Substances 0.000 description 9
- -1 sodium aluminum fluoride Chemical compound 0.000 description 9
- 239000011775 sodium fluoride Substances 0.000 description 8
- 235000013024 sodium fluoride Nutrition 0.000 description 8
- 238000004458 analytical method Methods 0.000 description 6
- 239000007921 spray Substances 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 4
- 239000002253 acid Substances 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000000428 dust Substances 0.000 description 2
- 238000005188 flotation Methods 0.000 description 2
- 239000002594 sorbent Substances 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000003637 basic solution Substances 0.000 description 1
- 150000001669 calcium Chemical class 0.000 description 1
- 239000008396 flotation agent Substances 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 235000010755 mineral Nutrition 0.000 description 1
- 231100000989 no adverse effect Toxicity 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 235000015598 salt intake Nutrition 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000004513 sizing Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Abstract
The present invention provides a method for recovering fluoride salts in aluminum electrolysis anode carbon residues, which relates to a method for treating anode carbon residues generated in aluminum electrolysis, particularly to a method for recovering fluoride salts in anode carbon residues. The present invention is characterized in that in the technology, alumina is compounded in anode carbon residues and is used as dispersing agents, the compounding quantity of alumina used as dispersing agents and accounts for 10% to 60% of the weight ratio of total material quantity, liquid or gas fuel with the fuel ash content smaller than 1% is used, calcining is carried out at the temperature of 650 DEG C to 930 DEG C until carbon materials in carbon residues are completely combusted, tail gas is adsorbed by alumina, and fluoride salts are reserved and recovered. Products contain about 15% to 70% of alumina and 30% to 85% of fluoride salts after treatment, the content of impurities is low, and treated products can be directly and wholly returned to an electrolytic tank and do not have adverse effect on the quality of electrolytes and aluminum liquid.
Description
Technical field
A kind of method that reclaims fluoride salt in the aluminium electrolyzing carbon slag relates to the treatment process of the anodic carbon residue that produces in a kind of aluminium electrolysis process, particularly reclaims the method for fluoride salt in the anodic carbon residue.
Background technology
In the Aluminum Electrolysis Production process, can produce the anodic carbon residue of a large amount of fluorinated salt.1 ton of about output 3-10 kilogram of primary aluminum of common every production anodic carbon residue contains 70% the fluoride salt (being mainly Sodium Fluoride and sodium aluminum fluoride) of having an appointment in the anodic carbon residue of output, this fluoride salt mainly comes from ionogen, is extremely valuable electrolysis raw material.At present owing to can not be effectively fluoride salt be wherein reclaimed and returns and make ionogen and use, caused the fluoride salt consumption big, increased the Aluminum Electrolysis Production cost.
Handled in the past anodic carbon residue reclaim fluoride salt method acid hydrolyzation or flotation process are arranged.The acid hydrolyzation technical essential is: with mineral acid fluoride salt in the carbon slag is converted into the HF volatilization earlier, then absorbs HF with basic solution, the fluoride salt rate of recovery about 90%.The flotation process technical essential is: earlier that carbon sizing is thin, add flotation agent, and make carbon dust float over solution surface, pull carbon dust out, then from solution, extract fluoride salt, the fluoride salt rate of recovery about 85%.But there is the cost height in aforesaid method, pollutes difficult points such as big, that waste liquid is difficult, and the fluoride salt rate of recovery is low, is unfavorable for technical scale enforcement.
Summary of the invention
Purpose of the present invention is exactly to be the problem that exists at above-mentioned prior art, provide a kind of cost low, pollute little, fluoride salt rate of recovery height, help the method for fluoride salt in the recovery aluminium electrolyzing carbon slag of industrial-scale production.
The objective of the invention is to be achieved through the following technical solutions.
A kind of method that reclaims fluoride salt in the aluminium electrolyzing carbon slag, it is characterized in that its technology is to allocate aluminum oxide into as dispersion agent in the anodic carbon residue, the weight ratio that accounts for total inventory as the aluminum oxide amount of allocating into of dispersion agent is 10%-60%, use the liquid or the geseous fuel of fuel ash<1%, under 650 ℃ of-930 ℃ of temperature, be fired to the carbonaceous material perfect combustion in the carbon slag, the tail gas alumina adsorption keeps recovery with fluoride salt.
A kind of method that reclaims fluoride salt in the aluminium electrolyzing carbon slag is characterized in that: anodic carbon residue adds with the particle form less than 5mm.
A kind of method that reclaims fluoride salt in the aluminium electrolyzing carbon slag is characterized in that: the aluminum oxide of adding is the technical grade aluminum oxide.
A kind of method that reclaims fluoride salt in the aluminium electrolyzing carbon slag is characterized in that: the fuel that uses is heavy oil or coal gas.
A kind of method that reclaims fluoride salt in the aluminium electrolyzing carbon slag is characterized in that: the fuel that uses is methane or Sweet natural gas.
A kind of method that reclaims fluoride salt in the aluminium electrolyzing carbon slag is characterized in that: used treatment facility is Industrial Stoves, comprises that rotary kiln and other similar devices are as revolution bed, fluidizing furnace, fluidized bed.
A kind of method that reclaims fluoride salt in the aluminium electrolyzing carbon slag is characterized in that: tail gas reclaims the evaporable fluorochemical with alumina adsorption.
A kind of method that reclaims fluoride salt in the aluminium electrolyzing carbon slag of the present invention, aluminum oxide is made dispersion agent in treating processes, avoided the material bonding, keeps material that good flowability is arranged, and increases the contact area of carbonaceous material and oxygen, and carbonaceous material is fully burnt.
Fluoride salt in the aluminium electrolyzing carbon slag of the present invention adopts the pyrogenic process method to reclaim, the selection of treatment temp is the carbonaceous material perfect combustion to guarantee in the carbon slag about 30%, guarantee again in the carbon slag that about 70% fluoride salt does not melt, tangible chemical reaction do not take place or volatilization is advisable, temperature ranges is 650 ℃-930 ℃.In the anodic carbon residue most fluorochemicals non-volatile in the pyrogenic attack process, chemical transformation does not take place, the evaporable fluorochemical is less, less than 2% of total fluorochemical in the anodic carbon residue.Handling back product main component is aluminum oxide, sodium aluminum fluoride, Sodium Fluoride, low amount of fluorinated calcium, can all return electrolyzer and use directly as the electrolysis raw material.Pollution-free, fluoride salt rate of recovery height, processing cost is low, is easy to technical scale and implements.
Embodiment
A kind of method that reclaims fluoride salt in the aluminium electrolyzing carbon slag, its removal process is followed successively by: (1) is broken into particle less than 5mm with anodic carbon residue, and the amount of allocating into accounts for the 40%-90% of total inventory; (2) be dispersion agent and sorbent material with the commercial alumina, the weight ratio that the aluminum oxide amount of allocating into of making dispersion agent accounts for total inventory is 10%-60%, evenly sneaks in the anodic carbon residue; (3) use clean liquid or geseous fuel, fuel ash<1%, in Industrial Stoves, carry out pyrogenic attack, 650 ℃-930 ℃ of treatment temps, the tail gas alumina adsorption, make in the carbon slag about 30% carbonaceous material perfect combustion, about 70% fluoride salt keeps, and reclaims the method for fluoride salt in the anodic carbon residue.
Of the present invention is main raw material with the anodic carbon residue, with the aluminum oxide is dispersion agent and sorbent material, use clean liquid or geseous fuel, in Industrial Stoves, carry out pyrogenic attack, tail gas alumina adsorption, the method for fluoride salt in the recovery anodic carbon residue, handle in the product of back and contain the aluminum oxide of 15%-70% and the fluoride salt of 30%-85%, foreign matter content is few, can directly all return electrolyzer and use, and ionogen and aluminium liquid quality are had no adverse effect.Method energy efficient recovery fluoride salt of the present invention, the rate of recovery is easy to industrial implementation greater than 98%.
Below in conjunction with example method of the present invention is described further.
Embodiment 1
To allocate weight into be 60% to anodic carbon residue in the control pyrogenic attack raw material, adds with the particle form less than 5mm; It is 40% that commercial alumina is allocated weight into, evenly sneaks in the anodic carbon residue; With heavy oil is that fuel sprays into the rotary kiln burning, and treatment temp is controlled at 800 ℃, the tail gas alumina adsorption.
By analysis, total fluoride salt (comprising Sodium Fluoride, sodium aluminum fluoride and Calcium Fluoride (Fluorspan)) content is 51.41% in the product, and Calcium Fluoride (Fluorspan) is 1.93%, and alumina content is 48.58%, and product purity satisfies the electrolyzer service requirements, and total fluoride salt rate of recovery is 99.52%.
Embodiment 2
Anodic carbon residue content is 70% in the control pyrogenic attack raw material, adds with the particle form less than 5mm; The commercial alumina amount of allocating into is 30%, evenly sneaks in the anodic carbon residue; With coal gas is that fuel sprays into the rotary kiln burning, and treatment temp is controlled at 850 ℃, the tail gas alumina adsorption.
By analysis, total fluoride salt (comprising Sodium Fluoride, sodium aluminum fluoride and Calcium Fluoride (Fluorspan)) content is 62.27% in the product, and wherein Calcium Fluoride (Fluorspan) is 1.66%; Alumina content is 37.72%, and product purity satisfies the electrolyzer service requirements.Total fluoride salt rate of recovery is 99.39%.
Embodiment 3
Anodic carbon residue content is 50% in the control pyrogenic attack raw material, adds with the particle form less than 5mm; The commercial alumina amount of allocating into is 50%, evenly sneaks in the anodic carbon residue; With heavy oil is that fuel sprays into the rotary kiln burning, and treatment temp is controlled at 750 ℃, the tail gas alumina adsorption.
By analysis, total fluoride salt (comprising Sodium Fluoride, sodium aluminum fluoride and Calcium Fluoride (Fluorspan)) content is 41.25% in the product, and wherein Calcium Fluoride (Fluorspan) is 2.06%; Alumina content is 58.74%, and product purity satisfies the electrolyzer service requirements.Total fluoride salt rate of recovery is 99.71%.
Embodiment 4
Anodic carbon residue content is 80% in the control pyrogenic attack raw material, adds with the particle form less than 5mm; The commercial alumina amount of allocating into is 20%, evenly sneaks in the anodic carbon residue; With coal gas is that fuel sprays into the rotary kiln burning, and treatment temp is controlled at 750 ℃, the tail gas alumina adsorption.
By analysis, total fluoride salt (comprising Sodium Fluoride, sodium aluminum fluoride and Calcium Fluoride (Fluorspan)) content is 73.95% in the product, and wherein Calcium Fluoride (Fluorspan) is 1.77%; Alumina content is 26.04%, and product purity satisfies the electrolyzer service requirements.Total fluoride salt rate of recovery is 99.91%.
Embodiment 5
Anodic carbon residue content is 40% in the control pyrogenic attack raw material, adds with the particle form less than 5mm; The commercial alumina amount of allocating into is 60%, evenly sneaks in the anodic carbon residue; With the Sweet natural gas is that fuel sprays into the rotary kiln burning, and treatment temp is controlled at 900 ℃, the tail gas alumina adsorption.
By analysis, total fluoride salt (comprising Sodium Fluoride, sodium aluminum fluoride and Calcium Fluoride (Fluorspan)) content is 31.71% in the product, and wherein Calcium Fluoride (Fluorspan) is 1.87%; Alumina content is 68.27%, and product purity satisfies the electrolyzer service requirements.Total fluoride salt rate of recovery is 98.21%.
Embodiment 6
Anodic carbon residue content is 85% in the control pyrogenic attack raw material, adds with the particle form less than 5mm; The commercial alumina amount of allocating into is 15%, evenly sneaks in the anodic carbon residue; With coal gas is that fuel sprays into the rotary kiln burning, and treatment temp is controlled at 700 ℃, the tail gas alumina adsorption.
By analysis, total fluoride salt (comprising Sodium Fluoride, sodium aluminum fluoride and Calcium Fluoride (Fluorspan)) content is 80.17% in the product, and wherein Calcium Fluoride (Fluorspan) is 1.79%; Alumina content is 19.82%, and product purity satisfies the electrolyzer service requirements.Total fluoride salt rate of recovery is 99.67%.
Claims (8)
1. method that reclaims fluoride salt in the aluminium electrolyzing carbon slag, it is characterized in that its technology is to allocate aluminum oxide into as dispersion agent in the anodic carbon residue, the weight ratio that accounts for total inventory as the aluminum oxide amount of allocating into of dispersion agent is 10%-60%, use the liquid or the geseous fuel of fuel ash<1%, under 650 ℃ of-930 ℃ of temperature, be fired to the carbonaceous material perfect combustion in the carbon slag, the tail gas alumina adsorption keeps recovery with fluoride salt.
2. a kind of method that reclaims fluoride salt in the aluminium electrolyzing carbon slag according to claim 1 is characterized in that: anodic carbon residue adds with the particle form less than 5mm.
3. a kind of method that reclaims fluoride salt in the aluminium electrolyzing carbon slag according to claim 1 is characterized in that: the aluminum oxide of adding is the technical grade aluminum oxide.
4. a kind of method that reclaims fluoride salt in the aluminium electrolyzing carbon slag according to claim 1 is characterized in that: the fuel that uses is heavy oil or coal gas.
5. a kind of method that reclaims fluoride salt in the aluminium electrolyzing carbon slag according to claim 1 is characterized in that: the fuel that uses is methane or Sweet natural gas.
6. a kind of method that reclaims fluoride salt in the aluminium electrolyzing carbon slag according to claim 1 is characterized in that: used treatment facility is Industrial Stoves.
7. a kind of method that reclaims fluoride salt in the aluminium electrolyzing carbon slag according to claim 1 is characterized in that: tail gas reclaims the evaporable fluorochemical with alumina adsorption.
8. a kind of method that reclaims fluoride salt in the aluminium electrolyzing carbon slag according to claim 6 is characterized in that: described Industrial Stoves are revolution bed, fluidizing furnace or fluidized bed.
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CN 200410069389 CN1253369C (en) | 2004-07-22 | 2004-07-22 | Process for recovering fluoride salt from aluminium electrolyzing carbon slag |
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CN 200410069389 CN1253369C (en) | 2004-07-22 | 2004-07-22 | Process for recovering fluoride salt from aluminium electrolyzing carbon slag |
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CN1253369C true CN1253369C (en) | 2006-04-26 |
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Families Citing this family (10)
Publication number | Priority date | Publication date | Assignee | Title |
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CN101063215B (en) * | 2007-05-31 | 2010-11-10 | 中国铝业股份有限公司 | Method for extracting electrolyte in aluminum electrolytic anodic carbon residue |
CN101318680B (en) * | 2007-06-07 | 2010-09-15 | 多氟多化工股份有限公司 | Process for preparing kryocide |
CN101318678B (en) * | 2007-06-07 | 2013-02-20 | 多氟多化工股份有限公司 | Process for preparing kryocide |
CN100577885C (en) * | 2007-12-17 | 2010-01-06 | 中国铝业股份有限公司 | Method for reclaiming electrolyte in carbon dross of aluminium electrolysis |
CN102011148B (en) * | 2010-12-02 | 2012-07-04 | 云南云铝涌鑫铝业有限公司 | Method for innocent treatment of aluminum electrolysis anode carbon residue and recovery of electrolyte |
CN103302079B (en) * | 2013-06-20 | 2015-06-10 | 郑州经纬科技实业有限公司 | Comprehensive treatment and utilization method of aluminum smelting fluorine-carbon hazardous solid wastes |
CN103343363B (en) * | 2013-06-28 | 2016-05-11 | 湖南中大冶金设计有限公司 | The electrolytical production method of a kind of electrolgtic aluminium |
CN108085088A (en) * | 2017-12-27 | 2018-05-29 | 郑州紫竹林健康管理有限公司 | A kind of electrolytic aluminium waste Slag treatment compound additive, preparation method and applications |
CN108557814B (en) * | 2018-05-11 | 2020-01-17 | 中南大学 | Method for purifying and separating carbon and fluoride in waste carbon material of aluminum electrolysis cell and prolonging service life of equipment |
CN109650343A (en) * | 2018-11-21 | 2019-04-19 | 国家电投集团宁夏能源铝业科技工程有限公司 | A kind of high temperature purification method of fluoride salt in anodic carbon residue |
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