CN106637299A - Method for recovering fluoride from fluorine-containing smoke - Google Patents
Method for recovering fluoride from fluorine-containing smoke Download PDFInfo
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- CN106637299A CN106637299A CN201610916033.XA CN201610916033A CN106637299A CN 106637299 A CN106637299 A CN 106637299A CN 201610916033 A CN201610916033 A CN 201610916033A CN 106637299 A CN106637299 A CN 106637299A
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- Prior art keywords
- fluoride
- containing fluorine
- gas containing
- temperature
- fluorine
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25C—PROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
- C25C3/00—Electrolytic production, recovery or refining of metals by electrolysis of melts
- C25C3/06—Electrolytic production, recovery or refining of metals by electrolysis of melts of aluminium
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F23—COMBUSTION APPARATUS; COMBUSTION PROCESSES
- F23G—CREMATION FURNACES; CONSUMING WASTE PRODUCTS BY COMBUSTION
- F23G7/00—Incinerators or other apparatus for consuming industrial waste, e.g. chemicals
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- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Materials Engineering (AREA)
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- Organic Chemistry (AREA)
- Environmental & Geological Engineering (AREA)
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- General Engineering & Computer Science (AREA)
- Treating Waste Gases (AREA)
Abstract
The invention provides a method for recovering fluoride from fluorine-containing smoke. The method is characterized in that waste carbon cathodes are treated by fire burning to obtain high-temperature fluorine-containing smoke; the high-temperature fluorine-containing smoke is charged into a rapid cooler, and the temperature of the high-temperature fluorine-containing smoke can be decreased from 300-500 DEG C to be less than 50 DEG C at the rate of 5-9 DEG C per second, thus fluoride in the high-temperature smoke is deposited under the rapid temperature decreasing condition and can be directly converted from gaseous fluoride into solid fluoride; the fluorine-containing smoke which is cooled to be less than 50 DEG C is conveyed to an electrolytic aluminum supplying purifying system and is absorbed and purified through fresh aluminum oxide; the smoke purified by electrolytic aluminum is discharged through a chimney; and fluorine-carrying aluminum oxide in which the fluoride is absorbed is returned to an electrolytic bath to be used as a raw material. The method is simple in treatment process, low in treatment cost, and low in environmental pollution.
Description
Technical field
The invention belongs to aluminium electroloysis solid waste resource recovery utilizes technical field, and in particular to a kind of smoking gas containing fluorine fluorination
The recovery method of thing.
Background technology
It is many to the method for aluminum electrolysis waste carbon anode/cathode process both at home and abroad, pyrogenic process and the big class of wet method two are generally divided into, it is all
It is the referred to as wet method carried out with water/vapor as main reactant or in aqueous in processing procedure, other are referred to as pyrogenic process.Jing
Crossing years of researches and practical experience proves, during the wet-treating of aluminum electrolysis waste carbon anode/cathode, can be with HF, HCN
Precipitation, cause equipment heavy corrosion, operating environment of pollution, endanger human health.In addition, aluminum electrolysis waste carbon anode/cathode is wet
Method processing technological flow is long, and process is complicated, and investment is big.And pyrogenic attack technology has simple flow process, small investment, processes nuisance
The characteristics of matter is thorough, it is possible to realize the innoxious and recycling of aluminum electrolysis waste carbon anode/cathode, therefore pyrogenic process well
Treatment technology will be the dominant direction of the harmless treatment of domestic and international aluminum electrolysis waste carbon anode/cathode and comprehensive utilization.
The pyrogenic attack technology of aluminum electrolysis waste carbon anode/cathode is typically all to utilize combustion method, by the aluminum electrolysis waste that burns
Carbon anode/cathode carbon, by poisonous and hazardous aluminum electrolysis waste carbon anode/cathode carbon dioxide is changed into, and using pyrolytic cyanide,
Vapor-phase fluoride is separated out by vulcanization reaction and aluminum fluoride is generated with oxidation reactive aluminum.According to national standard《Dangerous waste incineration
Environmental capacity standard (GB18484-2001)》The HF discharge standards of burning amount 300kg/h are ＜ 9mg/m at regulation3, burning amount
The HF discharge standards of 300～2500kg/h are ＜ 7mg/m3, the HF discharge standards of burning amount ＞ 2500kg/h are ＜ 5mg/m3.So
And the smoking gas containing fluorine major part that aluminum electrolysis waste carbon anode/cathode carbon is produced in prior art does not reach the requirement of national standard, part
Although treatment technology can reach national emission request, it is complicated, easy that presence processes not thorough, processing cost height, apparatus and process
The problems such as causing secondary pollution, causes pyrogenic attack technology that commercial application is also not implemented at home.Therefore, it is necessary to existing
Smoking gas containing fluorine treatment technology in the pyrogenic attack technology of aluminum electrolysis waste carbon anode/cathode is improved, so as to reduce being processed into
This, simplifies processing equipment and technological process, realizes the industrial application of aluminum electrolysis waste carbon anode/cathode pyrogenic attack technology.
The content of the invention
To solve above-mentioned the deficiencies in the prior art, the present invention provides a kind of recovery method of smoking gas containing fluorine fluoride, with letter
Change handling process, reduce processing cost, reduce environmental pollution.
The technical scheme that the present invention takes is as follows：
A kind of recovery method of smoking gas containing fluorine fluoride, method and step is as follows：
A. waste and old carbon anode/cathode is carried out into pyrogenic process burning process, high temperature smoking gas containing fluorine is obtained after process, flue-gas temperature is 300
～500 DEG C；
B. the high temperature smoking gas containing fluorine obtained in step A is passed into into rapidly cooler, high temperature smoking gas containing fluorine is by 300～500
Less than 50 DEG C DEG C are down to, rate of temperature fall is controlled at 5～9 DEG C/sec, make the fluoride in high-temperature flue gas under conditions of rapid cooling
Sublimate, directly solid-state fluoride is changed into by vapor-phase fluoride；
C. the smoking gas containing fluorine that less than 50 DEG C are cooled in step B is delivered to into electrolytic aluminium feed cleaning system, using fresh oxygen
Change aluminium absorption cleaning gas, electrolytic aluminium purifying smoke returns electrolytic cell by smoke stack emission, the fluorinated alumina for adsorbing fluoride
When raw material is used.
Rapidly cooler of the present invention is water cooling plant, and water cooling plant one end is provided with water inlet, and the other end is provided with
Delivery port.
The present invention compared with prior art, with following beneficial effect：
(1) a kind of recovery method process is simple of smoking gas containing fluorine fluoride involved in the present invention is easy to operate, and can be in height
Physical characteristic in warm smoking gas containing fluorine directly using material prepares highly purified fluoride, and the fluoride is the original of aluminium cell
Material, the high-purity aluminum fluoride that can directly replace aluminum electrolysis is used, and significantly reduces smoking gas containing fluorine processing cost and aluminium electroloysis
Production cost；
(2) electrolytic aluminium feed cleaning system completes to contain CO in the flue gas after adsorbing2Gas and a small amount of fluoride gas, and
F contents well below《Dangerous waste incineration Environmental capacity standard (GB18484-2001)》With《Aluminum i ndustry pollutant emission standard
(GB25465-2010)》Discharge standard, can directly empty.
(3) present invention achieves the fume treatment of pyrogenic attack aluminum electrolysis waste carbon anode/cathode it is innoxious, and realize
Recycling, has prevented the uncontrollable discharge of waste and old cathode pernicious gas in processing procedure.
Specific embodiment
Embodiment 1
A. waste and old carbon anode/cathode pyrogenic process burning is processed, high temperature smoking gas containing fluorine is obtained after process, flue-gas temperature is 300 DEG C；
B. the high temperature smoking gas containing fluorine obtained in step A is passed into into rapidly cooler, high temperature smoking gas containing fluorine is down to by 300 DEG C
Less than 45 DEG C, rate of temperature fall is controlled at 5 DEG C/sec；Fluoride in high-temperature flue gas is sublimated under conditions of rapid cooling, directly by
Vapor-phase fluoride changes into solid-state fluoride；The rapidly cooler is water cooling plant, and water cooling plant one end is provided with water inlet,
The other end is provided with delivery port, and when high-temperature flue gas are after water cooling plant, the low melting point fluoride rapid condensation in flue gas is formed
Solid fluoride powder, the fluoride is electrolytic cell conventional additives, can directly return electrolytic cell and use；
C. the smoking gas containing fluorine for being cooled to less than 45 DEG C in stepb delivers to electrolytic aluminium feed cleaning system, using fresh oxygen
Change aluminium absorption cleaning gas, electrolytic aluminum smoke purification utilization smoke stack emission, the fluorinated alumina for adsorbing fluoride returns electrolytic cell
When raw material is used.The electrolytic aluminium feed cleaning system is the obturator being interconnected, and fluoro-gas passes through stair oxidation aluminium
Absorption plant bottom, fluoro-gas blows fresh aluminum oxide during floating so that aluminum oxide forms suspended state, suspends
State aluminum oxide is fully contacted with fluoro-gas, expands the specific surface of aluminum oxide, and fluoro-gas fully adsorbs in alumina surface
Upper fluorinated alumina, so as to reach the purpose for removing fluoride in flue gas.
Embodiment 2
A. waste and old carbon anode/cathode pyrogenic process burning is processed, high temperature smoking gas containing fluorine is obtained after process, flue-gas temperature is 400 DEG C；
B. the high temperature smoking gas containing fluorine obtained in step A is passed into into rapidly cooler, high temperature smoking gas containing fluorine is down to by 400 DEG C
Less than 50 DEG C, rate of temperature fall is controlled at 7 DEG C/sec；Fluoride in high-temperature flue gas is sublimated under conditions of rapid cooling, directly by
Vapor-phase fluoride changes into solid-state fluoride；
C. the smoking gas containing fluorine for being cooled to less than 50 DEG C in stepb delivers to electrolytic aluminium feed cleaning system, using fresh oxygen
Change aluminium absorption cleaning gas, electrolytic aluminum smoke purification utilization smoke stack emission, the fluorinated alumina for adsorbing fluoride returns electrolytic cell
When raw material is used.
Embodiment 3
A. waste and old carbon anode/cathode pyrogenic process burning is processed, high temperature smoking gas containing fluorine is obtained after process, flue-gas temperature is 500 DEG C.
B. the high temperature smoking gas containing fluorine obtained in step A is passed into into rapidly cooler, high temperature smoking gas containing fluorine is down to by 500 DEG C
Less than 40 DEG C, rate of temperature fall control at 9 DEG C/sec, the fluoride in high-temperature flue gas is sublimated under conditions of rapid cooling, directly by
Vapor-phase fluoride changes into solid-state fluoride；
C. the smoking gas containing fluorine for being cooled to less than 40 DEG C in stepb delivers to electrolytic aluminium feed cleaning system, using fresh oxygen
Change aluminium absorption cleaning gas, electrolytic aluminum smoke purification utilization smoke stack emission, the fluorinated alumina for adsorbing fluoride returns electrolytic cell
When raw material is used.
Rapidly cooler of the present invention, electrolytic aluminium feed cleaning system can adopt prior art device.
Claims (2)
1. a kind of recovery method of smoking gas containing fluorine fluoride, it is characterised in that method and step is as follows：
A. waste and old carbon anode/cathode being carried out into pyrogenic process burning process, obtains high temperature smoking gas containing fluorine after process, flue-gas temperature is 300～
500℃；
B. the high temperature smoking gas containing fluorine obtained in step A is passed into into rapidly cooler, high temperature smoking gas containing fluorine is by 300～500 DEG C of drops
To less than 50 DEG C, rate of temperature fall is controlled at 5～9 DEG C/sec, the fluoride in high-temperature flue gas is coagulated under conditions of rapid cooling
China, directly changes into solid-state fluoride by vapor-phase fluoride；
C. the smoking gas containing fluorine that less than 50 DEG C are cooled in step B is delivered to into electrolytic aluminium feed cleaning system, using fresh aluminum oxide
Absorption cleaning gas, electrolytic aluminium purifying smoke returns electrolytic cell when original by smoke stack emission, the fluorinated alumina for adsorbing fluoride
Material is used.
2. the recovery method of a kind of smoking gas containing fluorine fluoride according to claim 1, it is characterised in that described rapidly to cool down
Device is water cooling plant, and water cooling plant one end is provided with water inlet, and the other end is provided with delivery port.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610916033.XA CN106637299A (en) | 2016-10-20 | 2016-10-20 | Method for recovering fluoride from fluorine-containing smoke |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610916033.XA CN106637299A (en) | 2016-10-20 | 2016-10-20 | Method for recovering fluoride from fluorine-containing smoke |
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| Publication Number | Publication Date |
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| CN106637299A true CN106637299A (en) | 2017-05-10 |
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| CN201610916033.XA Pending CN106637299A (en) | 2016-10-20 | 2016-10-20 | Method for recovering fluoride from fluorine-containing smoke |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107502922A (en) * | 2017-10-23 | 2017-12-22 | 常宁市华兴冶化实业有限责任公司 | A kind of system and method for electrolytic aluminium waste gas disposal |
| CN107998814A (en) * | 2017-11-24 | 2018-05-08 | 中南大学 | The processing system and its application process of a kind of smoking gas containing fluorine |
| CN111646454A (en) * | 2020-05-22 | 2020-09-11 | 中铝郑州有色金属研究院有限公司 | System and method for separating carbon and electrolyte in aluminum electrolysis carbon slag |
| CN113802007A (en) * | 2021-09-03 | 2021-12-17 | 中国恩菲工程技术有限公司 | Method and system for treating waste cathode of aluminum electrolysis cell |
-
2016
- 2016-10-20 CN CN201610916033.XA patent/CN106637299A/en active Pending
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107502922A (en) * | 2017-10-23 | 2017-12-22 | 常宁市华兴冶化实业有限责任公司 | A kind of system and method for electrolytic aluminium waste gas disposal |
| CN107998814A (en) * | 2017-11-24 | 2018-05-08 | 中南大学 | The processing system and its application process of a kind of smoking gas containing fluorine |
| CN107998814B (en) * | 2017-11-24 | 2020-06-16 | 中南大学 | Fluorine-containing flue gas treatment system and application method thereof |
| CN111646454A (en) * | 2020-05-22 | 2020-09-11 | 中铝郑州有色金属研究院有限公司 | System and method for separating carbon and electrolyte in aluminum electrolysis carbon slag |
| CN113802007A (en) * | 2021-09-03 | 2021-12-17 | 中国恩菲工程技术有限公司 | Method and system for treating waste cathode of aluminum electrolysis cell |
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Application publication date: 20170510 |