CN109735678A - A method of converter slagging agent is produced using electrolytic aluminium slag from delining - Google Patents
A method of converter slagging agent is produced using electrolytic aluminium slag from delining Download PDFInfo
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- CN109735678A CN109735678A CN201910129210.3A CN201910129210A CN109735678A CN 109735678 A CN109735678 A CN 109735678A CN 201910129210 A CN201910129210 A CN 201910129210A CN 109735678 A CN109735678 A CN 109735678A
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- slagging agent
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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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Abstract
The invention discloses a kind of methods using electrolytic aluminium slag from delining production converter slagging agent: 1) electrolytic aluminium slag from delining being classified, after wherein carbon block is chosen, remaining electrolyte, using ball mill, being worked into granularity is 1~5mm；2) vermiculite raw material is bought, the weight percent content of each ingredient in vermiculite: SiO230‑45、Fe2O35‑35、Al2O3< 20, MgO 15-26, CaO < 1, using jaw crusher, being crushed to granularity is 3~5mm, as the aggregate application of pelletizing；3) it by above material, is uniformly mixed according to the ratio that mass percent is 80:17, the heavy oil for adding 3% makees binder；4) the above material is pressed into the sphere slagging agent of 30~50mm using dry powder ball press, each composition by weight percent content range of the sphere slagging agent is as follows: Fe2O32-10,F<35,MgO<5,Na<20；5) by above slagging agent sphere, roping is stand-by to converter lines；6) according to the application method normal use of slagging agent；7) usage amount of the above slagging agent is in 0.8~3kg/ tons of steel.
Description
Technical field
The present invention relates to a kind of methods using electrolytic aluminium slag from delining production converter slagging agent.Electrolytic aluminium slag from delining is due to richness
It is a kind of danger wastes containing a variety of fluorides and cyanide, the present invention relates to electrolytic aluminium solid wastes recyclings to utilize technology and steel
The technical field of iron smelting converter process for making two different industries of technology.By the electrolyte among slag from delining, with addition of auxiliary material
Material produces the slagging agent in converter steelmaking process, and it is the new skill that different metallurgy industry technologies intersect innovation that substitution fluorite, which uses,
Art, and it is capable of the innovative technology of full dose resource utilization 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 percentage composition among slag electrolyte is as follows: electrolyte ingredient: 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 to slag from delining into
Row thoroughly processing, flotation processing, limewash immersion treatment can generate the toxic harmful exhaust gas such as a large amount of hydrogenation cyanogen, and environment influences
It is larger." content statement.
According to above document introduction it is found that there is presently no the techniques using electrolytic aluminium slag from delining production converter slagging agent
Technology.
Summary of the invention
The purpose of the present invention is to provide a kind of methods using electrolytic aluminium slag from delining production converter slagging agent, using electrolysis
The discarded slag from delining of aluminium, produces coverter pig slagging agent, substitutes fluorite slugging, can play the role of slugging simultaneously, additionally it is possible to
Maintain the effect of slugging.
The object of the present invention is achieved like this, and a kind of method using electrolytic aluminium slag from delining production converter slagging agent is real
Construction skill is as follows: 1) electrolytic aluminium slag from delining being classified, after wherein carbon block is chosen, return to aluminium manufacturer's regeneration, remaining electricity
Xie Zhi, according to mechano-chemical reation principle, using ball mill, being worked into granularity is 1~5mm, makes it have good chemistry
Reactivity；2) vermiculite raw material is bought, the weight percent content of each ingredient in vermiculite: SiO2 30-45、Fe2O3 5-35、
Al2O3< 20, MgO 15-26, CaO < 1, using jaw crusher, being crushed to granularity is 3~5mm, is answered as the aggregate of pelletizing
With；3) it by above material, is uniformly mixed according to the ratio that mass percent is 80:17, the heavy oil for adding 3% makees binder；4)
The above material is pressed into the sphere slagging agent of 30~50mm, each Ingredients Weight hundred of the sphere slagging agent using dry powder ball press
Divide as follows than content range: Fe2O32-10,F<35,MgO <5,Na <20；5) by above slagging agent sphere, roping to converter
Production line is stand-by；6) it opens and blows in converter that is, during converter smelting process according to the application method normal use of slagging agent
The above slagging agent is added in 1~3min afterwards, mid-term can also bessemerized, when slag getting dry is added；7) above slagging agent
Usage amount is in 0.8~3kg/ tons of steel.
Inventor has studied the principle that lime melts in convertor steelmaking process, according to " melting of lime CaO, mainly turns
The iron oxide immersion surface CaO generated during furnace oxygen blast, the calcium ferrite for forming low melting point is de- molten from lime surface, continues and refines
The SiO generated during steel2Equal substance reactions, generate with 2CaOSiO2Based on various compounds, fluorite is using fluorine ion
Cutting silicate ion achievees the purpose that slugging " this common knowledge, according to the fusing point of the various compounds of clinker, using electrolytic aluminium
Discarded slag from delining cooperates with vermiculite, produces coverter pig slagging agent, substitutes fluorite slugging, same that can play the role of slugging
When, additionally it is possible to the effect for maintaining slugging shows the strength of technological innovation.
The technology of the present invention principle:
Inventor after study by having found, in converter steelmaking process, the basic principle of fluorite slugging is:
1) main ingredient of fluorite is CaF2, other also contain a small amount of SiO2、Al203、Fe2O3Equal compounds, the fusing point of fluorite
Lower (930 DEG C or so).After being added in furnace, i.e. explosion is melted at fragment and rapidly at high temperature.
2) eutectic that fusing point is 1362 DEG C can be formed with CaO, directly facilitates the fusing of lime.It can also be generated with MgO
Low-melting compound (1350 DEG C) improves the mobility of caustic slag, is adapted to pneumatic steelmaking so that lime be made to melt rapidly
The requirement of fast slagging.
3) it can significantly reduce 2CaOSiO2Fusing point, generate low-melting compound 3CaOCaF2·2SiO2, make clinker
There is lower fusion temperature under high alkalinity.
Oxygen stream stock shock zone flame temperature is up to 2000~2600 DEG C of high temperature in converter, not only each composition in metal
It is also easy to produce volatile matter, each composition of the clinker of metal surface is also different degrees of to be volatilized, when fluorite slag making is added, main ingredient
Following reaction has occurred under the collective effect of furnace high-temperature and clinker in CaF2:
(CaF2)+{H2O}=(CaO)+2{HF}
2(CaF2)+{SiO2}=2(CaO)+{SiF4}
(CaF2)+(MgO)=(CaO)+{MgF2}
So from the viewpoint of clinker ionic theory, it is believed that be since F- ion has cut off the reason of the chain structure of silicate.Institute
With it can rapid slugging, and do not reduce the basicity of clinker.But though fluorite slugging effect is fast, the duration is shorter, greatly
Amount will increase splash using fluorite；Accelerate lining wear, F therein will cause environmental pollution, and industry is in control fluorite at present
Dosage.
In the ingredient discovery of research electrolytic aluminium slag from delining, slag from delining haves the characteristics that following inventor simultaneously:
1) slag from delining is in electrolytic process, and under high temperature action, surface texture is fine and close, and after dismounting, lumpiness is larger, and lumpiness is in 30mm
Above, converter is added and does slugging test, technique requirement is not achieved in reaction effect, it was demonstrated that untreated slag from delining is as metallurgy
Flux uses, and haves the characteristics that chemical reactivity is poor.
2) in the presence of having iron oxide composition reaction below occurs for the fluoride among slag from delining:
6FeO+2Na3AlF6+Q→3Na2O+ Al2O3+6Fe+12F-
3) inventor learns to learn after study simultaneously, Na2O is easy to react with acidic oxide, Al2O3It is easy to react with CaO,
F-Ion generates HF after meeting water, if control composition, reduces the H of raw material2O can reduce the generation of HF, improve fluorine ion
Utilization rate.
4) the mineral tissue 8CaONa containing sodium oxide molybdena2O·Al2O3、3CaO·2Na2O·5Al2O3、2Na2O·
CaO·3SiO2、Na2O·3CaO·6SiO2、Na2O·2CaO·3SiO2Fusing point be below 1540 DEG C, the characteristics of reaction is
After sodium oxide molybdena is in conjunction with acidic materials, then slagging occurs with CaO and reacts.
5) erosion of the fluorite for furnace lining is used, the mainly magnesia among fluorine ion and refractory material has occurred instead
It answers, reaction equation is as follows:
2F-+MgO→MgF2 (1536℃) +O2-
6) iron oxide among vermiculite plays the role of clinker fluxing.
7) vermiculite is a kind of porous material, and grease can have good adhesive attraction, for producing pelletizing, can be played
Reinforce the effect of pellet strength.
Inventor proposes innovative point below according to above discovery:
1) mechano-chemical reation principle is used, break process is carried out for slag from delining, it is broken using mechanical energy while broken
The crystal structure of bad overhaul slag electrolyte, reduces the bond energy of crystal, improves reactivity at high temperature；
2) using the fluorine ion feature among slag from delining, in the material between, be added and be rich in SiO2Material vermiculite, for changing change
The chemical reaction course of slag, and using vermiculite it is heated after cubical expansivity it is higher, can quick fragmentation the characteristics of, increase reaction
Reaction speed is improved at interface.The ingredient of vermiculite is as follows: degree: SiO2 30-45、Fe2O3 5-35、Al2O3 <20、MgO
15-26、CaO <1。
3) it is reacted first with the sodium salt among electrolyte after being decomposed using vermiculite, generates low melting point, further
It is reacted with calcium oxide, improves the speed of slugging, the equation of this process reaction is as follows:
Na3AlF6+CaO+SiO2→xNa2O·yCaO·zSiO2+nCaO·mAl2O3+( 3CaO·SiO2)3•CaF2
4) after converter is added, since the magnesia among vermiculite can be at a distance from the contact of the fluoride among slag from delining most
Closely, the magnesia among vermiculite can take the lead in reacting with fluoride, generate the MgF of low melting point2, reduce or fluoride avoided to invade
The magnesia among furnace lining is lost, the maintenance of furnace lining is facilitated.
5) it by above material pelletizing, uses, starts bessemerizing, or bessemerize as the slagging agent of converter
When phase slag getting dry, substitution fluorite plays the role of slugging, wherein low-melting compound 8CaONa2O·Al2O3、3CaO·
2Na2O·5Al2O3、2Na2O·CaO·3SiO2、Na2O·3CaO·6SiO2、Na2O·2CaO·3SiO2Presence, Neng Gouwei
Hold slugging effect.
6) binder of pellet forming process uses heavy oil or grease, avoids material aqueous, reduces the life of HF during slugging
At, reduce the pollution of environment, improve fluorine ion slugging effect.
Using the method for the present invention: 1) 1 ton of electrolytic aluminium of every generation generates the slag from delining of 30kg or so, domestic at present annual
Electrolytic aluminium yield generates 1,350,000 tons/year of slag from delining at 35,000,000 tons~45,000,000 tons, slag from delining recycling benefit domestic at present
Technique is seldom, most of process using landfill；The steel production capacity of China is 8.5 hundred million tons/year, the ratio column of converter steel
80%, calculated according to ton steel using the slagging agent of 2kg, Chinese converter producing can digest 130 using slag from delining slagging agent
Ten thousand tons or more of slag from delining, therefore the present invention is the process for being expected to realize slag from delining full dose resource utilization.2) of the invention
Technique is the best technique model of slag from delining resource utilization, on Henan Xixia Mine and other places, has 10 years or more applicating histories, but
It is simple process, principle is unclear, so being not carried out the application of industry size.The present invention facilitate push steel industry and
The intersection of nonferrous metallurgy industry is innovated, and realizes the fusion development of two different industries.3) present invention can substitute fluorite, therefore can
The exploitation for fluorite is reduced, the protection of environment and the sustainable use of mineral resources are facilitated.
Specific embodiment
According to above discovery, a kind of method implementing process using electrolytic aluminium slag from delining production converter slagging agent is as follows:
1) electrolytic aluminium slag from delining is classified, after wherein carbon block is chosen, returns to aluminium manufacturer's regeneration, remaining electrolyte is pressed
According to mechano-chemical reation principle, using ball mill, being worked into granularity is 1~5mm, makes it have good chemical reaction and lives
Property；
2) vermiculite raw material is bought, the weight percent content of each ingredient in vermiculite: SiO2 30-45、Fe2O3 5-35、Al2O3 <
20, MgO 15-26, CaO < 1, using jaw crusher, being crushed to granularity is 3~5mm, as the aggregate application of pelletizing；
3) it by above material, is uniformly mixed according to the ratio that mass percent is 80:17, the heavy oil for adding 3% makees binder.
4) the above material is pressed into the sphere slagging agent of 30~50mm using dry powder ball press, the sphere slagging agent it is each
Composition by weight percent content range is as follows: Fe2O32-10,F<35,MgO <5,Na <20；
5) by above slagging agent sphere, roping is stand-by to converter lines；
6) according to the application method normal use of slagging agent, i.e., during converter smelting process, 1 after converter is opened and is blown~
The above slagging agent is added in 3min, mid-term can also bessemerized, when slag getting dry is added.
7) usage amount of the above slagging agent is in 0.8~3kg/ tons of steel.
Claims (1)
1. a kind of method using electrolytic aluminium slag from delining production converter slagging agent, it is characterised in that implementing process is as follows: 1) will be electric
Solution aluminium slag from delining is classified, and after wherein carbon block is chosen, returns to aluminium manufacturer's regeneration, remaining electrolyte, according to mechanical force
Reaction principle is learned, using ball mill, being worked into granularity is 1~5mm, makes it have good chemical reactivity；2) leech is bought
Stone raw material, the weight percent content of each ingredient in vermiculite: SiO2 30-45, Fe2O3 5-35、Al2O3 <20、MgO 15-26、
CaO < 1, using jaw crusher, being crushed to granularity is 3~5mm, as the aggregate application of pelletizing；3) by above material,
It is uniformly mixed according to the ratio that mass percent is 80:17, the heavy oil for adding 3% makees binder；4) by the above material using dry
Powder ball press is pressed into the sphere slagging agent of 30~50mm, and each composition by weight percent content range of the sphere slagging agent is such as
Under: Fe2O32-10,F<35,MgO <5,Na <20；5) by above slagging agent sphere, roping is stand-by to converter lines；6)
According to the application method normal use of slagging agent, i.e., during converter smelting process, add in 1~3min after converter is opened and blown
Enter the above slagging agent, mid-term can also bessemerized, when slag getting dry is added；7) usage amount of the above slagging agent 0.8~
3kg/ tons of steel.
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Cited By (7)
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| CN110616295A (en) * | 2019-10-29 | 2019-12-27 | 新疆中合大正冶金科技有限公司 | Harmless utilization process of waste carbon blocks of electrolytic aluminum |
| CN110878385A (en) * | 2020-01-07 | 2020-03-13 | 王强 | Method for producing molten steel precipitation deoxidizer by using electrolytic aluminum carbon slag |
| 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 |
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| 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 |
| CN115433800A (en) * | 2021-10-08 | 2022-12-06 | 武汉山诚环保科技有限公司 | External refining process and application thereof |
| CN115449600A (en) * | 2021-10-08 | 2022-12-09 | 武汉山诚环保科技有限公司 | Novel steelmaking mixed fluxing agent and preparation method and application thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110616295A (en) * | 2019-10-29 | 2019-12-27 | 新疆中合大正冶金科技有限公司 | Harmless utilization process of waste carbon blocks of electrolytic aluminum |
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| 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 |
| CN111926148A (en) * | 2020-08-24 | 2020-11-13 | 内蒙古海亚新材料有限公司 | Slag melting agent for steelmaking and preparation method thereof |
| 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 |
| CN115433800A (en) * | 2021-10-08 | 2022-12-06 | 武汉山诚环保科技有限公司 | External refining process and application thereof |
| CN115449600A (en) * | 2021-10-08 | 2022-12-09 | 武汉山诚环保科技有限公司 | Novel steelmaking mixed fluxing agent and preparation method and application thereof |
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Application publication date: 20190510 |