CN104673965B - A kind of online method of modifying of liquid steel slag - Google Patents
A kind of online method of modifying of liquid steel slag Download PDFInfo
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Abstract
The invention discloses a kind of online method of modifying of liquid steel slag, belong to technical field of ferrous metallurgy.The present invention mixes first while the smelting devices such as converter, electric furnace, LF stoves are slagged tap, by the steel slag modification agent of liquid steel slag and certain particle size according to certain mass ratio, then cools down.The steel slag modification agent of the present invention, is one or more carbonate materials, the carbonate material is carbonate compound or carbonate mineral.Utilize the slag modification technology of the present invention, steel slag modification agent efficiently can be resolved into oxide using the heat of slag, the energy resource consumption of multiple stage crushing technique when reducing slag processing simultaneously, and modified high alkalinity slag is easy to slag to reuse equivalent to a kind of synthetic slag.
Description
Technical field
The present invention relates to technical field of ferrous metallurgy, and liquid is carried out using steel slag modification agent more specifically to a kind of
The method that slag is modified online.
Background technology
Slag as steel-making waste residue, generally crude steel yield 15% or so.In recent years, with China's steel and iron industry
Fast development, the accumulating amount of slag increase year by year, not only occupy substantial amounts of soil, also result in serious environmental pollution.Steel
Slag generally can not be utilized directly, generally utilize mould using the two-step method slag of " stabilizing pretreatment-later use " at present
Formula.First, in cognition, existing slag Land use models remain in when solving its free cao and tricalcium silicate by " digestion "
On the problems such as imitating split-phase and being destroyed with structure；Secondly, on tupe, despite the presence of such as the vexed, disk of heat is bold and vigorous, roller, wind are broken
Etc. multiple means, but above-mentioned means are almost without exception is used as " digestion " medium using water.The mineral group of slag can be made even so
Into relative with structure stable, but it is using very limited, is mainly used in road construction, or be finely ground to slag micro powder with cement to make
With largely can not being used in iron and steel enterprise inner loop.And above-mentioned tupe is by the liquid steel slag of 1600 DEG C or so high temperature
250 DEG C or so are cooled to, well imagines that its water resources consumption amount is very large.In addition, sprinkled using the vexed, disk of heat, roller, wind are broken etc.
The equipment funds input of technique is also larger, and energy resource consumption is high.
Slag contains a large amount of heat energy, is a kind of valuable Secondary Resource.Realize slag in iron and steel enterprise's inner loop always
It is taken seriously and generally uses, active development and application slag inner loop technology, not only contributes to energy-saving and greenhouse gas
Body emission reduction, to improving the valuable constituents such as the Fe in the ratio that recycled in vessel slag, effectively recovery vessel slag, have important
Meaning, it is development of iron and steel enterprises recycling economy, realizes one of important topic of sustainable development.
It is on June 2nd, 2010 through retrieval, China Patent No. ZL200710202507.5, authorized announcement date, innovation and creation name
Referred to as：Multifunctional slagging material findings and preparation method thereof；The scorification material supplementary material of this application case includes following weight proportioning
Component：Converter slag 8.0-9.5 parts, additive 0.5-2.0 parts；Wherein, the additive contains the group of following weight percentage
Point：Na2CO35.00~10.00%, FeO 70.00~80.00%, BaCO310.00~20.00%.The scorification material supplementary material is
It can be used for slag making, be also used as slagging agent and Dephosphorising agent uses, realize recycling for converter slag.This application case master
To reduce the fusing point of slag by adding FeO in solid steel slag, improve the dephosphorization effect of slag, but this application case is without very
The good heat resources using slag, and adding FeO raises cost；In addition, the basicity of slag is not high, with converter desiliconization
Carry out, slag basicity constantly reduces, converter dephosphorization effect is produced a very large impact, if adding lime, cost can be caused to increase again
Add, therefore be not easy to popularization and application.
China Patent No. ZL 200910039604.6, authorized announcement date are on April 27th, 2011, and invention and created name is：
Using converter slag waste heat to slag carry out activation modification method, this application case by performance adjustment material electric arc furnace restored slag,
Cinder and auxiliary material by weight parts mixing granulation；Dried performance adjustment material is placed in slag before slag is come out of the stove
It is transported in bag or using conveying worm in slag bag；Using the impulsive force that molten steel slag is toppled over by performance adjustment material and steel
Slag is mixed；By the performance adjustment material of mixing and slag in cinder ladle heat vexed 8~24 hours；Slag after reconstruct is used
P_ formula disintegrating machines are crushed, and carry out magnetic separation separation；Final powder is milled to 400~500m of specific surface area2/ kg, obtains active steel
Slag micro mist.Performance adjustment material is launched into slag bag and mixed with molten steel slag by this application case, utilizes molten steel slag
Waste heat causes both to chemically react at high temperature, improves the aquation and gelation activity of converter slag.But this application case profit
It is cumbersome that the whole process of activation modification is carried out to slag with waste heat, modified cost is high, and practical value is not high.
The content of the invention
1. invention technical problems to be solved
It is an object of the invention to overcome existing for prior art：1) slag is as a kind of valuable resource, by a large amount of heaps
Product fails to be utilized effectively；2) existing slag processing means water resources consumption amount is big, and input cost is high and pollutes lacking for environment
Fall into, there is provided a kind of online method of modifying of liquid steel slag；The present invention does not follow the solid-state modification R＆D direction of current hot topic, directly
Hot modification is carried out to molten state slag, not only takes full advantage of the waste heat of molten state slag, and because the present invention uses carbonic acid
Salt material is modified to slag, meets Ferrous Metallurgy principle, effectively can be changed slag into oxide carbonate decomposition
Property, and modified high alkalinity slag can largely substitute converter slag-making agent, be reused slag.
2. technical scheme
To reach above-mentioned purpose, technical scheme provided by the invention is：
A kind of online method of modifying of liquid steel slag of the present invention, its step are：
Step 1: while the metallurgical plants such as converter, electric furnace, LF stoves are slagged tap, add slag according to different purposes and change
Matter agent, and liquid steel slag and steel slag modification agent are well mixed in cinder ladle, the steel slag modification agent is one or more carbonic acid
Salt material, the carbonate material are carbonate compound or carbonate mineral；
Step 2: the gained batch mixing of cooling step one, modification terminates.
Further, the carbonate compound described in step 1 is CaMg (CO3)2、CaCO3、MgCO3、FeCO3In one
Kind is a variety of；Described carbonate mineral is the one or more in dolomite, lime stone, magnesite, siderite.
Further, the granularity of the carbonate mineral is respectively less than 50mm.
Further, the preferably low-phosphorous vessel slag of liquid steel slag described in step 1 or refining slag, described low-phosphorous vessel slag
The mass percent of middle phosphorus is less than 2%, is the liquid steel slag in order to reduce slag phosphorus load using low-phosphorous vessel slag or refining slag
Temperature be not less than 1350 DEG C, herein setting primarily to ensure slag mobility.
Further, the mass percent that steel slag modification agent accounts for total batch mixing in step 1 is 5.0%~40.0%, is less than
5% can not give full play to modification agent effect, and higher than 40.0% heat for being easily caused slag can not decompose carbonate completely,
The waste of modification agent is caused, liquid steel slag and steel slag modification agent are added in cinder ladle simultaneously, the steel slag modification agent and liquid steel slag
The ratio between feed rate be equal to the mass ratio of steel slag modification agent and liquid steel slag, charging rate can make very much slag heat unrestrained slowly
Take, too fast be also easy to produce that feed splashes slag, causes production accident.
3. beneficial effect
Using technical scheme provided by the invention, compared with existing known technology, there is following remarkable result：
(1) the online method of modifying of a kind of liquid steel slag of the invention, one or more carbonate materials are mixed, as changing
Matter agent modified steel scoria, carbonate material can utilize steel slag waste heat efficient-decomposition to improve the basicity of slag into oxide, make slag
It is modified, meet the principle of Ferrous Metallurgy, modified high alkalinity slag can largely substitute converter slag-making agent, slag is obtained weight
It is multiple to utilize, there is the value recycled；
(2) the online method of modifying of a kind of liquid steel slag of the invention, its modification agent sufficient raw, purchase cost is low,
Reduce slag and be modified cost, it is easy to utilize；
(3) the online method of modifying of a kind of liquid steel slag of the invention, whole modifying process do not have the participation of any water, significantly
Water resource is saved.
Embodiment
To further appreciate that present disclosure, with reference to embodiment, the invention will be further described.
Embodiment 1
A kind of steel slag modification agent of the present embodiment, include the component of following mass percent：Dolomite 25%, lime stone
40%th, magnesite 15% and siderite 20%.Described carbonate mineral dolomite, lime stone, the grain of magnesite and siderite
Degree is respectively less than 50mm, and the present embodiment setting granularity is beneficial to be thermally decomposed inside block carbonate mineral less than 50mm.This reality
Basicity and content of magnesia that dolomite in example, lime stone, magnesite are used to adjust liquid steel slag are applied, siderite is then used to adjust
The fusing point of liquid steel slag, it specifically modifies principle and will be described below.The steel slag modification agent of the present embodiment, sufficient raw,
Purchase cost is low, reduces slag and is modified cost, easy to utilize.
The present embodiment is to the detailed process that liquid steel slag is modified using steel slag modification agent：
Choose granularity be less than 50mm dolomite, lime stone, siderite and magnesite, dolomite, lime stone, siderite and
The mass percent of magnesite is 25%：40%：15%：20%, and mixing is dried.Applicant indicate that the present embodiment selects
The carbonate mineral for taking granularity to be less than 50mm, it is that it repeatedly attempts to sum up to come in actual practice.Due to dolomite, lime
Stone, siderite and magnesite are to be mixed in solid form with liquid steel slag.The mineral block product of input is excessive, will certainly influence it
Inside is thermally decomposed, and the personnel of this principle field of metallurgy know about.Also it is exactly constantly to be tasted from this angle, applicant
Examination, makes every effort to find an ideal value, this point of 50mm is finally determined.The granularity of carbonate mineral is less than 50mm, inside it
It can obtain being thermally decomposed well, without further dispersion and fining, waste energy, and the granularity of carbonate mineral is more than
50mm, then occur inside carbonate mineral by thermally decompose it is insufficient or by thermal decomposition time it is long the problem of.
Using the LF furnace refining slags of certain steel mill, the phosphorus load of the refining slag is relatively low, is easy to follow-up most of replacement converter
Slag former.Slag tap (slag mobility is strong at this temperature, is advantageous to subsequently mix with modification agent), will be mixed after drying at 1600 DEG C
Steel slag modification agent and slag using the method that liquidates while pour into cinder ladle, the impulsive force energy that the present embodiment is toppled over using liquid steel slag
It is enough to be well mixed steel slag modification agent and slag, avoid because carbonate mineral density ratio liquid steel slag is low, carbonate occur
Mineral float over liquid steel slag top, the problem of can only being modified to one layer of surface liquid steel slag.Meanwhile the present embodiment control liquid
State slag and steel slag modification agent are added in cinder ladle simultaneously, and the ratio between feed rate of steel slag modification agent and liquid steel slag changes equal to slag
Matter agent and the mass ratio of liquid steel slag, keep the feed rate to make full use of liquid steel slag heat, feed also unlikely
Slag is splashed in too fast generation, causes production accident.It should be noted that the present embodiment control steel slag modification agent accounts for the quality hundred of total batch mixing
Divide than being 5.0%, the proportioning can ensure that steel slag modification agent gives full play to its effect, while will not produce waste.
Making iron residue cool, (when temperature is less than 500 DEG C, carbonate stops point substantially to 500 DEG C for modification agent and liquid steel slag batch mixing
Solution, it is not necessary to when cooling completely, save processing time), modification terminates.
The online method of modifying of liquid steel slag of the present embodiment, carbonate mineral are decomposed using the waste heat of slag, and its
The decomposition reaction rate of itself is very high, dolomite, lime stone, magnesite can efficient-decomposition produce CaO and MgO so that slag alkali
Degree is improved, and siderite, which decomposes generation FeO, can make the reduction of slag fusing point, and the composition for the slag being now modified is equivalent to one
Kind synthetic slag, can largely substitute converter slag-making agent, slag has obtained effective recycling.In addition, the present embodiment utilizes
Liquid steel slag waste heat promotes carbonate efficient-decomposition to save heat energy needed for carbonate decomposition simultaneously, carbonate decomposition into oxide
It can also make it that solidifying slag is easy to crack granulation under force, further saves the energy of later stage crushing process
Consumption, is double gain, dual-use material, has given full play to the effect of carbonate mineral, also saved steel to the full extent
The cost that slag modification and following cycle recycle.Also what deserves to be explained is, the whole modifying process of the present embodiment does not have any water
Participate in, not only greatly save water resource, while evaded because water is present, the risk of production development accident, also help environment
Protection, the practical value of whole scheme are very high.
Embodiment 2
A kind of online method of modifying of liquid steel slag of the present embodiment, is with embodiment 1, its difference substantially：This reality
Applying the steel slag modification agent of example includes the component of following mass percent：Dolomite 5%, lime stone 85%, magnesite 5% and sparring
Ore deposit 5%.After the low-phosphorous vessel slag (mass percent of phosphorus is less than 2%) and mixing that the present embodiment temperature in use is 1350 DEG C are dried
Steel slag modification agent pour into simultaneously in cinder ladle, and control the ratio between feed rate of steel slag modification agent and liquid steel slag to be equal to slag
The mass ratio of modification agent and liquid steel slag, the mass percent that steel slag modification agent accounts for total batch mixing is 15.0%, and batch mixing is cooled down
To 500 DEG C, modification terminates.
Embodiment 3
A kind of online method of modifying of liquid steel slag of the present embodiment, is with embodiment 1, its difference substantially：This reality
Applying the steel slag modification agent of example includes the component of following mass percent：Dolomite 15%, lime stone 15%, magnesite 40% and water chestnut
Iron ore 30%.The low-phosphorous vessel slag (mass percent of phosphorus is less than 2%) and mix dry that the present embodiment temperature in use is 1400 DEG C
Steel slag modification agent after dry is poured into cinder ladle simultaneously, and controls the ratio between feed rate of steel slag modification agent and liquid steel slag to be equal to
Steel slag modification agent and the mass ratio of liquid steel slag, the mass percent that steel slag modification agent accounts for total batch mixing is 40.0%, by batch mixing
500 DEG C are cooled to, modification terminates.
Embodiment 4
A kind of online method of modifying of liquid steel slag of the present embodiment, the gross mass 158g of steel slag modification agent is taken, choose granularity
Dolomite, lime stone, siderite and magnesite less than 50mm, its mass percent is respectively 10%, 0%, 75%, 15%,
And mixing is dried.The low-phosphorous converter finishing slag 3000g of certain steel mill is weighed, modification agent is accounted for 5% of total amount or so, first should
3000g slags, which are placed in graphite crucible, to be preheated, and is placed into the Muffle furnace that furnace temperature is 1600 DEG C and is melted, treats that slag melts completely
Afterwards, it is well mixed with the steel slag modification agent contained in another preheated crucible, batch mixing is finally air-cooled to room temperature.
Embodiment 5
A kind of online method of modifying of liquid steel slag of the present embodiment, the gross mass 80kg of steel slag modification agent is taken, choose granularity
Dolomite, lime stone, siderite and magnesite less than 50mm, its mass percent is respectively 90%, 5%, 5%, 0%, and
Mixing is dried.Certain factory LF furnace refining slag 450kg are weighed, modification agent is accounted for 15% of total amount or so, first by 450kg slag
It is placed in the intermediate frequency furnace that furnace temperature is 1600 DEG C and melts, after slag melts completely, it is changed with mixing dried slag
Matter agent is together added in preheating cinder ladle and is well mixed, and batch mixing finally is air-cooled into 500 DEG C.
Embodiment 6
A kind of online method of modifying of liquid steel slag of the present embodiment, the gross mass 220kg of steel slag modification agent is taken, choose granularity
Dolomite, lime stone, siderite and magnesite less than 50mm, its mass percent is 0%: 45%: 50%: 5%, and is carried out
Dry and mix.Certain factory LF furnace refining slag 450kg are weighed, modification agent is accounted for 30% of total amount or so, are first placed in 450kg slag
Furnace temperature is to melt in 1600 DEG C of intermediate frequency furnace, after slag melts completely, by it with mixing dried steel slag modification agent
Together add in preheating cinder ladle and be well mixed, batch mixing is finally air-cooled to 500 DEG C.
Embodiment 7
A kind of online method of modifying of liquid steel slag of the present embodiment, the gross mass 1300kg of steel slag modification agent is taken, choose grain
Dolomite, lime stone, siderite and magnesite of the degree less than 50mm, its mass percent are 0%: 90%: 0%: 10%, are gone forward side by side
Row, which is dried, to be mixed.Weigh the 40 tons of converters of certain steel mill to slag tap 4 tons, estimation modification agent accounts for 25% of total amount or so, converter at 1600 DEG C
Slag tap, dried steel slag modification agent and clinker will be mixed while added in cinder ladle, make clinker and steel using the impulsive force of clinker
Slag modifier is mixed, and batch mixing finally is air-cooled into 500 DEG C.
Related experiment is carried out to the modified slag of the gained of embodiment 4~7, experimental result is referring to table 1：
The modified slag experimental result of the gained of 1 embodiment of table 4~7
| Sequence number | Carbonate decomposition rate % | All iron content % | Basicity | Content of magnesia % |
| Embodiment 4 | 95.3 | 37.2 | 3.9 | 12.7 |
| Embodiment 5 | 91.2 | 19.2 | 4.7 | 16.2 |
| Embodiment 6 | 80.2 | 29.2 | 4.6 | 13.1 |
| Embodiment 7 | 84.2 | 20.4 | 5.2 | 14.3 |
Commerical test is carried out in 40t converters with synthetic slag after modification, its experimental result is as shown in table 2.
The 2-in-1 slagging field experiment result of table
From above-mentioned experimental result, the decomposition reaction rate of carbonate itself is very high, dolomite, lime stone, magnesite, water chestnut
Iron ore using steel slag waste heat can efficient-decomposition produce CaO, MgO and FeO, the slag being modified can largely substitute converter and make
Slag agent, slag have obtained effective recycling.
Embodiment 8
A kind of online method of modifying of liquid steel slag of the present embodiment, is with embodiment 4, its difference substantially：This reality
Applying the steel slag modification agent of example includes the component of following mass percent：CaMg(CO3)25%th, CaCO370%th, MgCO315% He
FeCO310%.
Embodiment 9
A kind of online method of modifying of liquid steel slag of the present embodiment, is with embodiment 4, its difference substantially：This reality
Applying the steel slag modification agent of example includes the component of following mass percent：CaMg(CO3)260% and FeCO340%.
Embodiment 10
A kind of online method of modifying of liquid steel slag of the present embodiment, is with embodiment 4, its difference substantially：This reality
Applying the steel slag modification agent of example includes the component of following mass percent：CaMg(CO3)230%th, CaCO325% and FeCO345%.
Embodiment 11
A kind of online method of modifying of liquid steel slag of the present embodiment, is with embodiment 4, its difference substantially：This reality
The steel slag modification agent for applying example uses CaMg (CO3)2。
The online method of modifying of a kind of liquid steel slag described in embodiment 1~11, the solid-state modification of current hot topic is not followed to grind
Originating party is to directly to the hot modification of molten state slag progress, modification agent sufficient raw, purchase cost is low, not only fully sharp
With the waste heat of molten state slag, and the effect of carbonate is given full play to, it is modified and follow-up to have saved slag to the full extent
The cost of cycling and reutilization, it is easy to utilize.
Claims (2)
1. a kind of online method of modifying of liquid steel slag, its step are：
Step 1: liquid steel slag and steel slag modification agent using the method that liquidates while are added into well mixed in cinder ladle, the steel slag modification
Agent is carbonate mineral；Described carbonate mineral is the mixture of dolomite, lime stone, magnesite and siderite, mixture
Component proportion to be following several：1) dolomite 25%, lime stone 40%, magnesite 15% and siderite 20%, wherein, slag
The mass percent that modification agent accounts for total batch mixing is 5.0%；2) dolomite 5%, lime stone 85%, magnesite 5% and siderite
5%, wherein, the mass percent that steel slag modification agent accounts for total batch mixing is 15.0%；3) dolomite 15%, lime stone 15%, magnesite
Ore deposit 40% and siderite 30%, wherein, the mass percent that steel slag modification agent accounts for total batch mixing is 40.0%；The carbonate mineral
Granularity be respectively less than 50mm, the ratio between feed rate of the steel slag modification agent and liquid steel slag is equal to steel slag modification agent and liquid steel
The mass ratio of slag；
Step 2: the gained batch mixing of cooling step one, modification terminates.
A kind of 2. online method of modifying of liquid steel slag according to claim 1, it is characterised in that：Liquid steel described in step 1
Slag is low-phosphorous vessel slag or refining slag, and the temperature of the liquid steel slag is not less than 1350 DEG C.
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| CN105002316B (en) * | 2015-08-11 | 2017-07-21 | 青岛特殊钢铁有限公司 | A kind of novel slag basin separated to phosphorus in vessel slag and its manufacture method and application method |
| CN106492981B (en) * | 2016-09-20 | 2018-06-12 | 北京科技大学 | A kind of method for improving slag iron component recovery |
| CN106435060B (en) * | 2016-09-30 | 2019-03-15 | 攀钢集团攀枝花钢铁研究院有限公司 | The method of modifying of titanium-containing slag in a kind of molten iron |
| CN111018573A (en) * | 2019-12-24 | 2020-04-17 | 江阴硕人节能环保科技有限公司 | Silicon fertilizer and production process thereof |
| CN112322257B (en) * | 2020-10-30 | 2021-12-10 | 中国科学院过程工程研究所 | Modified steel slag, preparation method thereof and heat storage material |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| US4062672A (en) * | 1974-10-21 | 1977-12-13 | Entreprise Gagneraud Pere Et Fils | Process for improving the fragmentation capability of metallurgical slags and cinders |
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| CN85105246A (en) * | 1985-07-09 | 1987-01-07 | 日本磁力选矿株式会社 | The steel-making slag utilize method |
| CN1026796C (en) * | 1992-10-31 | 1994-11-30 | 冶金工业部建筑研究总院 | Complex hot heating treatment for lump steel slag |
| CN102337372A (en) * | 2011-10-27 | 2012-02-01 | 北京科技大学 | Cooling solidification recycling method for high-temperature liquid-state slag in steelmaking furnace |
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Effective date of registration: 20160810 Address after: A village of 243000 in Anhui province Ma'anshan City mountain rain Gangcheng garden 34-404 Applicant after: The metallurgical development in science and technology company limited in East China, Maanshan City Applicant after: Anhui University of Technology Address before: A village of 243000 in Anhui province Ma'anshan City mountain rain Gangcheng garden 34-404 Applicant before: The metallurgical development in science and technology company limited in East China, Maanshan City |
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