CN109628695A - A kind of technique using the production LF submerged arc refining agent of electrolytic aluminium slag from delining - Google Patents
A kind of technique using the production LF submerged arc refining agent of electrolytic aluminium slag from delining Download PDFInfo
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- CN109628695A CN109628695A CN201910083743.2A CN201910083743A CN109628695A CN 109628695 A CN109628695 A CN 109628695A CN 201910083743 A CN201910083743 A CN 201910083743A CN 109628695 A CN109628695 A CN 109628695A
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- submerged arc
- refining agent
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- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21C—PROCESSING OF PIG-IRON, e.g. REFINING, MANUFACTURE OF WROUGHT-IRON OR STEEL; TREATMENT IN MOLTEN STATE OF FERROUS ALLOYS
- C21C7/00—Treating molten ferrous alloys, e.g. steel, not covered by groups C21C1/00 - C21C5/00
- C21C7/04—Removing impurities by adding a treating agent
- C21C7/06—Deoxidising, e.g. killing
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- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21C—PROCESSING OF PIG-IRON, e.g. REFINING, MANUFACTURE OF WROUGHT-IRON OR STEEL; TREATMENT IN MOLTEN STATE OF FERROUS ALLOYS
- C21C7/00—Treating molten ferrous alloys, e.g. steel, not covered by groups C21C1/00 - C21C5/00
- C21C7/0025—Adding carbon material
-
- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21C—PROCESSING OF PIG-IRON, e.g. REFINING, MANUFACTURE OF WROUGHT-IRON OR STEEL; TREATMENT IN MOLTEN STATE OF FERROUS ALLOYS
- C21C7/00—Treating molten ferrous alloys, e.g. steel, not covered by groups C21C1/00 - C21C5/00
- C21C7/04—Removing impurities by adding a treating agent
- C21C7/076—Use of slags or fluxes as treating agents
-
- 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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- 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
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Treatment Of Steel In Its Molten State (AREA)
Abstract
The invention discloses a kind of technique using the production LF submerged arc refining agent of electrolytic aluminium slag from delining, by the slag from delining of electrolytic aluminium aluminium manufacturer carbon block and electrolyte sorted, be crushed, carbon block granularity 1mm is hereinafter, electrolyte is crushed to 5 ± 0.53mm；The magnesium oxide powder that content of magnesia is greater than 80% is purchased, roping is stand-by to pressure ball production line；The additional amount of carbon block powder and electrolyte powder is determined according to phosphorus content, it is ensured that the carbon content control among submerged arc agent is below 35%.According to the content of fluorine ion, determine that the additive amount of magnesia is the 10% of fluorinion concentration.Various raw material are uniformly mixed；The sphere submerged arc refining agent of 30~50mm of diameter, each predominant quantity degree in refining agent are as follows: C 15-35%, F is made in dry type pressure ball‑~35%, MgO 5-9%, Na+Al2O3It is not required Deng remaining ingredient, in LF refining furnace smelting process, the additional amount of this refining agent is 2~5kg/ tons of steel, and specific usage amount is determined according to the case where refined molten steel.
Description
Technical field
The present invention relates to a kind of techniques using the production LF submerged arc refining agent of electrolytic aluminium slag from delining.
Background technique
Aluminium cell carries out large repairs in 4 years~7 Nian Houxu that work, and the waste removed is known as slag from delining, mainly
Waste cathode carbon block, waste refractory materials, useless thermal insulation material etc., while a certain amount of anode carbon granule is also generated in electrolytic process.By
In each electrolytic aluminium factory current capacity, interior village's structure, inner lining material type, Electrolytic conditions, operating duty, groove life difference
Larger, the concrete composition of waste also has bigger difference, but main component is essentially identical.According to existing research it is found that overhaul
Mineral tissue among slag is main are as follows: NaF 12.7, Na3AlF6 65.7、Al2O3 5.6、NaAl11O17 4.6、CaF2 2.9、LiF
2.7。
Consulting literatures (1) Li Hong disclosed that entitled " aluminium cell is big in 2003 on " non-ferrous metal " magazine of volume 55
Repair the prevention and cure of pollution and comprehensive utilization of slag " paper, have that " electrolytic cell overhaul slag should reinforce cinder field during stockpiling among paper
Management, prevents secondary pollution, and find can generally applicable comprehensive Utilization Ways, turned harm into good with final realization, change give up into
It is precious." content statement；(2) Li Chaonan discloses entitled " aluminium electricity on " industry security and dust-proof " magazine of the 9th phase in 2000
Solve groove overhaul slag harmless treatment " paper, centre have " sanitary landfills is the final process method of solid waste, health
Landfill requires stockyard bottom to take Anti-seeping technology, and innoxious landfill is made in solid waste layering, top layer overlying soil after compacting,
The method for realizing also woods (cultivated).Sanitary landfills requires to accomplish to store up safely, without collapsing, does not stay hidden danger, and accomplish harmless
Change, not contaminated land and underground water." content statement；(3) Gao Kangning, Chao Boyang, Shen Wenbin, Yan Xionghua were at 2017 years the 8th
Entitled " electrolytic aluminium factory slag from delining contamination analysis and Preventing Countermeasures " paper is disclosed on " resource-effective and environmentally friendly " magazine of phase, in
Between have that " the processing disposal technology of slag from delining mainly has: rotary kiln baking processing, cement kiln synergic processing, Bauxite Sintering, flotation
Processing, limewash immersion treatment etc..Bauxite Sintering can only generally handle carbonaceous waste material in slag from delining, cannot carry out to slag from delining
Thoroughly processing, flotation processing, limewash immersion treatment can generate the toxic harmful exhaust gas such as a large amount of hydrogenation cyanogen, environment influence compared with
Greatly." content statement.
According to above document introduction it is found that there is presently no the technique skills using LF refining furnace processing electrolytic aluminium slag from delining
Art.
Summary of the invention
The purpose of the present invention is to provide a kind of techniques using the production LF submerged arc refining agent of electrolytic aluminium slag from delining, can disappear
Except adverse effect of the slag from delining intermediate species in LF smelting process, slag from delining production is become to the submerged arc agent during LF refining
It uses, realizes the resource utilization of slag from delining.
The object of the present invention is achieved like this, a kind of technique using the production LF submerged arc refining agent of electrolytic aluminium slag from delining,
1, by the slag from delining of electrolytic aluminium aluminium manufacturer carbon block and electrolyte sort；2, by carbon block and electrolyte sorting after, respectively plus
Enter ball mill and carry out break process, wherein the maximum particle size of carbon block, is worked into 1mm hereinafter, electrolyte is crushed to 5 ± 0.53mm；
3, the content of fluorine in phosphorus content and the electrolyte powder in the above broken carbon block powder is chemically examined, then roping is raw to pressure ball
Producing line is stand-by；4, buying content of magnesia is greater than 80% magnesium oxide powder, and roping is stand-by to pressure ball production line；5, according to carbon containing
Measure the additional amount for determining carbon block powder and electrolyte powder, it is ensured that the carbon content control among submerged arc agent is below 35%；6, root
According to the content of fluorine ion, determine that the additive amount of magnesia, additive amount are determined according to the height of content of fluoride ion, wherein magnesia
Additive amount be the 10% of fluorinion concentration；7, after calculating above, various raw material are uniformly mixed；8, it will be uniformly mixed
Various raw materials the sphere of 30~50mm of diameter is suppressed into using the method for dry type pressure ball, submerged arc refining agent, unit is made
Each predominant quantity degree in this refining agent of quality are as follows: C 15-35%, F-~35%, MgO 5-9%, Na+
Al2O3It is not required Deng remaining ingredient, this refining agent of roping is stand-by to LF refining furnace；9, in LF refining furnace smelting process, according to biography
This refining agent is added in the case where electric arc is exposed, submerged arc situation is bad in the smelting process of system, can also be in LF refining furnace power transmission
Smelting starts, this refining agent is added, and carries out slugging, submerged arc, deoxidation operation；10, the additional amount of this refining agent is 2~5kg/ tons
Steel, specific usage amount are determined according to the case where refined molten steel.
Technical principle of the invention: inventor after study by having found, in LF smelting process, the foamed of refining slag is grasped
Make, has and stablize electric arc, improve heating efficiency, protection furnace lining, reduce electrode material and fire proof material of furnace lining consumption, prevent steel
Water inhales nitrogen, increases slag interface product, improves the effect of the dynamic conditions of deoxidation and desulfurization.The basis of clinker foaming is promoted to exist
Have that good melt fluidity energy, the viscosity of clinker be suitable, have bubble formation in clinker, also to have the shape of bubble formation in clinker
Nuclear particle, inventor is under the premise of above functions requires, it was found that technology contents below:
1) in LF refining furnace technical process, at a temperature of steel-making, fluoride and sodium salt therein can occur below anti-
It answers:
Na3AlF6+CaO+SiO2→xNa2O·yCaO·zSiO2+nCaO·mAl2O3+(3CaO·SiO2)3•CaF2
According to phasor rudimentary knowledge it is found that more than product be low melting point compound, the fusing of clinker can be conducive to
And blistering.
2) LF refining furnace is added by practice discovery, slag from delining in inventor, and the MgO-C based refractory of ladle is corroded
Phenomenon is obvious, and chemical reaction below mainly has occurred:
Na3AlF6→Na2O+ Al2O3+F-
F-+MgO→MgF2+O2-
3) wherein MgF2Fusing point be 1536 DEG C, be easy to take off from refractory material molten, be that refractory material is caused to corrode serious original
Cause.
4) carbon block among slag from delining, can play the role of deoxidation after the addition, and the CO bubble that deoxidation generates becomes again
The gas source of clinker foaming, the equation of reaction are as follows:
(FeO)+C→[Fe]+CO↑
(F-)+(MgO) +[C]→MgF2+CO↑
5) in LF refining furnace technical process, in order to quickly form molten slag, fluorite (CaF2) it is the most common slugging material.
6) under the conditions of the temperature of steelmaking operations (temperature is greater than 1550 DEG C), cyanide thoroughly decomposes, and generates gas H2With
N2, realize the innocuously transformation of cyanide；
7) fluoride among slag from delining forms various mineral tissues, is converted into steel slag, steel slag is as a kind of building materials and material of building the road
After use, hydration reaction occurs for material, and fluorine is fixed among cementitious material, realizes the innocuously transformation of fluoride；
According to above discovery, inventor uses innovative point below, produces novel LF refining furnace submerged arc agent:
1) according to mechano-chemical reation principle, the carbon block among slag from delining is used into ball mill, 1mm is worked into, makes it have
Good chemical reactivity；
2) electrolyte (non-carbon block) among slag from delining is crushed to 5 ± 0.53mm using ball mill, as the aggregate of pelletizing,
Its reactivity is excited simultaneously；
3) use MgO as additive, so that submerged arc agent is added after LF refining furnace, after fluoride therein decomposes, part fluorine
Ion is reacted with the magnesia of addition first, generates the clinker of low melting point, is avoided fluoride and is reacted with refractory material, is caused resistance to
The erosion problem of fiery material.
4) it using carbon block powder as the gas source of deoxidier and foaming agent, is added among submerged arc agent, with traditional submerged arc agent
Charcoal hydrochlorate is compared, and has the advantages that economize on electricity, slugging speed and expansion rate are fast, whole submerged-arc smelting effect is better than traditional LF
Refining furnace submerged arc agent.
Specific embodiment
Embodiment: by taking 120 tons of LF production line applications as an example,
(1) by the slag from delining of electrolytic aluminium aluminium manufacturer carbon block and electrolyte sort；
(2) it by after carbon block and electrolyte sorting, is separately added into ball mill and carries out break process, wherein the maximum particle size of carbon block, adds
Work is to 1mm hereinafter, electrolyte is crushed to 5 ± 0.53mm；
(3) content of fluorine in phosphorus content and the electrolyte powder in the above broken carbon block powder is chemically examined, then roping is arrived
Pressure ball production line is stand-by；
(4) buying content of magnesia is greater than 80% magnesium oxide powder, and roping is stand-by to pressure ball production line；
(5) additional amount of carbon block powder and electrolyte powder is determined according to phosphorus content, it is ensured that the carbon content control among submerged arc agent
Below 35%.Citing: carbon block pulvurent carbonaceous 85%, wherein carbon block powder is 25% ÷ 85% with addition of ratio, i.e., with addition of carbon block powder
The ratio at end is 29%；
(6) according to the content of fluorine ion, determine that the additive amount of magnesia, additive amount are determined according to the height of content of fluoride ion,
Wherein the additive amount of magnesia is the 10% of fluorinion concentration.Citing: chemical examination fluorine ion 25%, magnesia additive amount is 25% ×
10%, i.e. the ratio of addition magnesia is 2.5%；
(7) after calculating above, various raw material are uniformly mixed；
(8) uniformly mixed various raw materials are suppressed into the sphere of 30~50mm of diameter using the method for dry type pressure ball, made
At submerged arc refining agent, each predominant quantity degree in this refining agent of unit mass are as follows: C 15-35%, F-~
35%、MgO 5—9%、Na+Al2O3It is not required Deng remaining ingredient, this refining agent of roping is stand-by to LF refining furnace；
(9) in LF refining furnace smelting process, according to traditional smelting process, add in the case where electric arc is exposed, submerged arc situation is bad
Enter this refining agent, can also smelt and start in LF refining furnace power transmission, this refining agent is added, carry out slugging, submerged arc, deoxidation operation；
(10) additional amount of this refining agent is 2~5kg/ tons of steel, and specific usage amount is determined according to the case where refined molten steel.
Claims (1)
1. a kind of technique using the production LF submerged arc refining agent of electrolytic aluminium slag from delining, it is characterised in that: 1, by electrolytic aluminium aluminium manufacturer
Carbon block and electrolyte in slag from delining are sorted；2, it by after carbon block and electrolyte sorting, is separately added into ball mill and is crushed
Processing, wherein the maximum particle size of carbon block, is worked into 1mm hereinafter, electrolyte is crushed to 5 ± 0.53mm；3, after more than chemical examination broken
Carbon block powder in phosphorus content and electrolyte powder in fluorine content, then roping is stand-by to pressure ball production line；4, it purchases
Content of magnesia is greater than 80% magnesium oxide powder, and roping is stand-by to pressure ball production line；5, according to phosphorus content determine carbon block powder and
The additional amount of electrolyte powder, it is ensured that the carbon content control among submerged arc agent is below 35%；6, according to the content of fluorine ion, really
Determine the additive amount of magnesia, additive amount determines that wherein the additive amount of magnesia is fluorine ion according to the height of content of fluoride ion
The 10% of concentration；7, after calculating above, various raw material are uniformly mixed；8, by uniformly mixed various raw materials, using dry
The method of formula pressure ball is suppressed into the sphere of 30~50mm of diameter, is made submerged arc refining agent, each in this refining agent of unit mass
Predominant quantity degree are as follows: C 15-35%, F-~35%, MgO 5-9%, Na+Al2O3Do not make Deng remaining ingredient
It is required that this refining agent of roping is stand-by to LF refining furnace；9, in LF refining furnace smelting process, according to traditional smelting process, in electricity
This refining agent is added in the case that arc is exposed, submerged arc situation is bad, can also smelt and start in LF refining furnace power transmission, this essence is added
Agent is refined, slugging, submerged arc, deoxidation operation are carried out；10, the additional amount of this refining agent be 2~5kg/ tons of steel, specific usage amount according to
The case where refined molten steel, determines.
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110820017A (en) * | 2019-12-10 | 2020-02-21 | 中南大学 | Preparation method of aluminum-manganese alloy |
| CN111235354A (en) * | 2020-04-03 | 2020-06-05 | 北京璞域环保科技有限公司 | Production process of LF multifunctional deoxidation submerged arc slag |
| CN111575430A (en) * | 2020-05-19 | 2020-08-25 | 西安热工研究院有限公司 | Method for treating waste cathode carbon block waste of electrolytic aluminum by using steelmaking converter |
| CN112195311A (en) * | 2020-09-24 | 2021-01-08 | 邹平积华环保科技有限公司 | Process for producing steelmaking deoxidization fluxing slag refining complexing agent by using waste electrolyte |
| CN112452499A (en) * | 2020-09-28 | 2021-03-09 | 甘肃酒钢集团宏兴钢铁股份有限公司 | Method for harmless treatment and multistage utilization of aluminum industry waste cathode carbon blocks |
| CN114774992A (en) * | 2022-05-18 | 2022-07-22 | 中国铝业股份有限公司 | Aluminum electrolysis production method |
| CN115044796A (en) * | 2022-06-29 | 2022-09-13 | 铜山县丰华工贸有限公司 | Chlorine-free high-efficiency refining agent and preparation method thereof |
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110820017A (en) * | 2019-12-10 | 2020-02-21 | 中南大学 | Preparation method of aluminum-manganese alloy |
| CN110820017B (en) * | 2019-12-10 | 2020-11-20 | 中南大学 | Preparation method of aluminum-manganese alloy |
| CN111235354A (en) * | 2020-04-03 | 2020-06-05 | 北京璞域环保科技有限公司 | Production process of LF multifunctional deoxidation submerged arc slag |
| CN111575430A (en) * | 2020-05-19 | 2020-08-25 | 西安热工研究院有限公司 | Method for treating waste cathode carbon block waste of electrolytic aluminum by using steelmaking converter |
| CN112195311A (en) * | 2020-09-24 | 2021-01-08 | 邹平积华环保科技有限公司 | Process for producing steelmaking deoxidization fluxing slag refining complexing agent by using waste electrolyte |
| CN112452499A (en) * | 2020-09-28 | 2021-03-09 | 甘肃酒钢集团宏兴钢铁股份有限公司 | Method for harmless treatment and multistage utilization of aluminum industry waste cathode carbon blocks |
| CN114774992A (en) * | 2022-05-18 | 2022-07-22 | 中国铝业股份有限公司 | Aluminum electrolysis production method |
| CN114774992B (en) * | 2022-05-18 | 2023-08-08 | 中国铝业股份有限公司 | Aluminum electrolysis production method |
| CN115044796A (en) * | 2022-06-29 | 2022-09-13 | 铜山县丰华工贸有限公司 | Chlorine-free high-efficiency refining agent and preparation method thereof |
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