CN104673965A - On-line molten steel slag modification method - Google Patents
On-line molten steel slag modification method Download PDFInfo
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- CN104673965A CN104673965A CN201510116835.8A CN201510116835A CN104673965A CN 104673965 A CN104673965 A CN 104673965A CN 201510116835 A CN201510116835 A CN 201510116835A CN 104673965 A CN104673965 A CN 104673965A
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Abstract
The invention discloses an on-line molten steel slag modification method, and belongs to the technical field of ferrous metallurgy. The on-line molten steel slag modification method comprises the following steps: firstly, while slag is simultaneously discharged from smelting devices such as a rotary furnace, an electric furnace and an LF furnace, uniformly mixing liquid steel slag and a steel slag modifier with certain granularity according to a certain mass ratio, and subsequently cooling. The steel slag modifier is one or more carbonate substances, and the carbonate substances are carbonate compounds or carbonate minerals. By adopting the steel slag modification technique disclosed by the invention, heat of the steel slag can be efficiently utilized to decompose the steel slag modifier into oxides, at the same time, the energy consumption of a multi-stage crushing process used in steel slag treatment can be reduced, and the modified high-alkalinity steel slag is equivalent to synthesized slag, so that the steel slag can be conveniently and repeatedly utilized.
Description
Technical field
The present invention relates to technical field of ferrous metallurgy, more particularly, relate to a kind of method utilizing steel slag modification agent to carry out the online modification of liquid steel slag.
Background technology
Slag, as the waste residue of steel-making, is generally about 15% of crude steel output.In recent years, along with the fast development of China's Iron And Steel Industry, the accumulating amount of slag increases year by year, not only occupies a large amount of soils, also result in serious environmental pollution.Slag generally can not directly utilize, and generally adopts the two-step approach slag Land use models of " stabilization pre-treatment-later use " at present.First, in cognition, existing slag Land use models still rests on and solves its free cao and the phase-splitting of tricalcium silicate timeliness by " digestion " and with in the problems such as structure deteriorate; Secondly, on tupe, although there is the multiple means such as vexed in heat, dish sprinkles, cylinder, wind are broken, above-mentioned means are almost without exception using water as " digestion " medium.Can make even so the mineral composition of slag and structure relatively stable, but its utilization is very limited, is mainly used in Road construction, or being finely ground to slag micro powder water distribution mud uses, cannot in a large number in iron and steel enterprise's internal recycling use.And above-mentioned tupe is that the liquid steel slag of about 1600 DEG C high temperature is cooled to about 250 DEG C, well imagine that its water resources consumption amount is very big.In addition, use the equipment funds of the techniques such as heat is vexed, dish sprinkles, cylinder, wind are broken to drop into also comparatively large, energy consumption is high.
Slag contains a large amount of heat energy, is a kind of Secondary Resource of preciousness.Realize slag always come into one's own in iron and steel enterprise's internal recycling and generally adopt, active development and application slag internal recycling technology, not only be conducive to energy-saving and cost-reducing and reduction of greenhouse gas discharge, to valuable constituents such as the Fe improved in converter slag internal recycle proportion of utilization, efficient recovery converter slag, have great importance, development of iron and steel enterprises recycling economy, one of important topic realizing Sustainable development.
Through retrieval, China Patent No. ZL200710202507.5, authorized announcement date is on June 2nd, 2010, and invention and created name is: multifunctional slagging material findings and preparation method thereof; The scorification material supplementary material of this application case comprises the component of following weight proportioning: bessemer furnace slag 8.0-9.5 part, additive 0.5-2.0 part; Wherein, described additive contains the component of following weight per-cent: Na
2cO
35.00 ~ 10.00%, FeO 70.00 ~ 80.00%, BaCO
310.00 ~ 20.00%.Namely this scorification material supplementary material may be used for slag making, can also use, achieve the recycle of bessemer furnace slag as dissolving agent and dephosphorizing agent.This application case, mainly through adding FeO in solid steel slag, reduces the fusing point of slag, improve the dephosphorization effect of slag, but this application case does not well utilize the heat resources of slag, and adds FeO cost is raised; In addition, the basicity of slag is not high, and along with the carrying out of converter desiliconization, slag basicity constantly reduces, and produces a very large impact converter dephosphorization effect, if add lime, cost can be caused again to increase, be therefore not easy to apply.
China Patent No. ZL 200910039604.6, authorized announcement date is on April 27th, 2011, invention and created name is: utilize the waste heat of bessemer furnace slag to carry out the method for activation modification to slag, and this application case is by performance adjustment material electric arc furnace restored slag, cinder and auxiliary material by weight parts mixing granulation; Before slag is come out of the stove, dried performance adjustment material be placed in slag bag or utilize worm conveyor to be transported in slag bag; Performance adjustment material and slag mix by the surging force utilizing molten steel slag to topple over; By mixing performance adjustment material and slag in cinder ladle heat vexed 8 ~ 24 hours; Adopt P_ formula crusher to carry out fragmentation to the slag after reconstruct, and carry out magnetic separation separation; Final powder is milled to specific surface area 400 ~ 500m
2/ kg, obtains active slag micro powder.Performance adjustment material is rendered in slag bag and is mixed with molten steel slag by this application case, utilizes the waste heat of molten steel slag to make both at high temperature chemical reaction occur, improves aquation and the gelation activity of bessemer furnace slag.But the whole process operation that this application case utilizes waste heat to carry out activation modification to slag is loaded down with trivial details, and modification cost is high, and practical value is not high.
Summary of the invention
1. invent the technical problem that will solve
The object of the invention is to overcome that prior art exists: 1) slag is as a kind of resource of preciousness, is failed to be utilized effectively by bulk deposition; 2) existing slag processing means water resources consumption amount is large, and the high and defect of contaminate environment of input cost, provides the online method of modifying of a kind of liquid steel slag; The present invention does not follow solid-state upgrading R&D direction popular at present, directly hot upgrading is carried out to molten state slag, not only take full advantage of the waste heat of molten state slag, and use carbonate material to carry out modification to slag due to the present invention, meet ferrous metallurgy principle, can effectively carbonate decomposition be become oxide compound to make slag obtain modification, and modified high alkalinity slag major part can substitute converter slag-making agent, and slag is reused.
2. technical scheme
For achieving the above object, technical scheme provided by the invention is:
The online method of modifying of a kind of liquid steel slag of the present invention, the steps include:
Step one, while the metallurgical plant such as converter, electric furnace, LF stove are slagged tap, steel slag modification agent is added according to different objects, and liquid steel slag and steel slag modification agent are mixed in cinder ladle, described steel slag modification agent is one or more carbonate materials, and described carbonate material is carbonate cpds or carbonate minerals;
Step 2, cooling step one gained batch mixing, modification terminates.
Further, the carbonate cpds described in step one is CaMg (CO
3)
2, CaCO
3, MgCO
3, FeCO
3in one or more; Described carbonate minerals is one or more in rhombspar, Wingdale, magnesite, spathic iron ore.
Further, the granularity of described carbonate minerals is all less than 50mm.
Further, the preferred low-phosphorous converter slag of liquid steel slag described in step one or refining slag, in described low-phosphorous converter slag, the mass percent of phosphorus is lower than 2%, low-phosphorous converter slag or refining slag is used to be to reduce slag phosphorus load, the temperature of this liquid steel slag is not less than 1350 DEG C, sets mainly in order to ensure the mobility of slag herein.
Further, in step one, steel slag modification agent accounts for the mass percent of total batch mixing is 5.0% ~ 40.0%, modification agent effect can not be given full play to lower than 5%, easily cause the heat of slag carbonate can not be decomposed completely higher than 40.0%, cause the waste of modification agent, liquid steel slag and steel slag modification agent add in cinder ladle simultaneously, described steel slag modification agent equals the mass ratio of steel slag modification agent and liquid steel slag with the ratio of the feed rate of liquid steel slag, feed rate can make slag heat be wasted too slowly, slag is spattered in reinforced too fast easy generation, causes industrial accident.
3. beneficial effect
Adopt technical scheme provided by the invention, compared with existing known technology, there is following unusual effect:
(1) the online method of modifying of a kind of liquid steel slag of the present invention, one or more carbonate materials are mixed, as modification agent modified steel scoria, carbonate material can utilize steel slag waste heat efficient-decomposition to become oxide compound, improves the basicity of slag, makes slag modification, meet the principle of ferrous metallurgy, modified high alkalinity slag major part can substitute converter slag-making agent, slag is reused, has the value of recycle;
(2) the online method of modifying of a kind of liquid steel slag of the present invention, its modification agent sufficient raw, purchase cost is low, reduces slag modification cost, easy to utilize;
(3) the online method of modifying of a kind of liquid steel slag of the present invention, whole modifying process, without any the participation of water, has saved water resources greatly.
Embodiment
For understanding content of the present invention further, below in conjunction with embodiment, the invention will be further described.
Embodiment 1
A kind of steel slag modification agent of the present embodiment, comprises the component of following mass percent: rhombspar 25%, Wingdale 40%, magnesite 15% and spathic iron ore 20%.The granularity of described carbonate minerals rhombspar, Wingdale, magnesite and spathic iron ore is all less than 50mm, and the present embodiment setting granularity is less than 50mm will be conducive to the inner decomposes of block carbonate minerals.In the present embodiment, rhombspar, Wingdale, magnesite are for regulating basicity and the content of magnesia of liquid steel slag, and spathic iron ore is then for regulating the fusing point of liquid steel slag, and its concrete upgrading principle will be described below.The steel slag modification agent of the present embodiment, sufficient raw, purchase cost is low, reduces slag modification cost, easy to utilize.
The detailed process that the present embodiment utilizes steel slag modification agent liquid towards slag to carry out modification is:
Choose granularity and be less than the rhombspar of 50mm, Wingdale, spathic iron ore and magnesite, the mass percent of rhombspar, Wingdale, spathic iron ore and magnesite is 25%:40%:15%:20%, and carries out drying mixing.Applicant points out, the present embodiment chooses the carbonate minerals that granularity is less than 50mm, is that it repeatedly attempts summing up out in actual practice.Because rhombspar, Wingdale, spathic iron ore and magnesite mix with liquid steel slag in solid form.The mineral block dropped into amasss excessive, and will certainly affect its inner decomposes, the personnel of this principle field of metallurgy understand.Also just from this angle, applicant constantly attempts, and makes every effort to find an ideal value, finally determines this point of 50mm.The granularity of carbonate minerals is less than 50mm, its inside can obtain decomposes well, without the need to further dispersion and fining again, and waste energy, and the granularity of carbonate minerals is greater than 50mm, then there will be the problem that the inner decomposes of carbonate minerals is insufficient or the decomposes time is long.
Use the LF furnace refining slag of certain steelworks, the phosphorus load of this refining slag is lower, is convenient to follow-up major part and substitutes converter slag-making agent.Slagging tap when 1600 DEG C, (at this temperature, slag mobility is strong, be conducive to follow-uply mixing with modification agent), adopt the method that liquidates to pour in cinder ladle dried for mixing steel slag modification agent and slag simultaneously, steel slag modification agent and slag can mix by the surging force that the present embodiment utilizes liquid steel slag to topple over, avoid because carbonate minerals density ratio liquid steel slag is low, occur that carbonate minerals floats over liquid steel slag top, the problem of upgrading can only be carried out by effects on surface one deck liquid steel slag.Simultaneously, the present embodiment controls liquid steel slag and steel slag modification agent adds in cinder ladle simultaneously, steel slag modification agent equals the mass ratio of steel slag modification agent and liquid steel slag with the ratio of the feed rate of liquid steel slag, keep this feed rate can either make full use of liquid steel slag heat, slag is spattered in reinforced also unlikely too fast generation, causes industrial accident.Also it should be noted that, the mass percent that the agent of the present embodiment control steel slag modification accounts for total batch mixing is 5.0%, and this proportioning can ensure that steel slag modification agent gives full play to its effect, simultaneously unlikely generation waste.
Make iron residue cool modification agent and liquid steel slag batch mixing to 500 DEG C (when temperature is lower than 500 DEG C, carbonate stops decomposing substantially, does not need by the time to cool completely, saves the treatment time), and modification terminates.
The online method of modifying of liquid steel slag of the present embodiment, carbonate minerals utilizes the waste heat of slag to decompose, and the decomposition reaction rate of himself is very high, rhombspar, Wingdale, magnesite efficient-decomposition can produce CaO and MgO, slag basicity is improved, and spathic iron ore decomposes generation FeO can make slag fusing point reduce, and the composition of the slag be now modified is equivalent to a kind of synthetic slag, major part can substitute converter slag-making agent, slag obtains effective recycling.In addition; the present embodiment utilizes liquid steel slag waste heat to impel carbonate efficient-decomposition to become oxide compound; save heat energy needed for carbonate decomposition simultaneously; carbonate decomposition can also make to solidify slag and be easy to the granulation of cracking under force; save again the energy consumption of later stage crushing process further; be double gain, dual-use material, given full play to the effect of carbonate minerals, also saved the cost of slag modification and following cycle recycling to the full extent.Also what deserves to be explained is, the whole modifying process of the present embodiment, without any the participation of water, has not only saved water resources greatly, and evaded because water exists, the risk of production development accident, also helps environment protection, and the practical value of whole scheme is very high simultaneously.
Embodiment 2
The online method of modifying of a kind of liquid steel slag of the present embodiment, substantially with embodiment 1, its difference is: the steel slag modification agent of the present embodiment comprises the component of following mass percent: rhombspar 5%, Wingdale 85%, magnesite 5% and spathic iron ore 5%.The present embodiment use temperature be 1350 DEG C low-phosphorous converter slag (mass percent of phosphorus is lower than 2%) and mixing dried steel slag modification agent pour in cinder ladle simultaneously, and control the mass ratio that steel slag modification agent and the ratio of the feed rate of liquid steel slag equal steel slag modification agent and liquid steel slag, the mass percent that steel slag modification agent accounts for total batch mixing is 15.0%, batch mixing is cooled to 500 DEG C, modification terminates.
Embodiment 3
The online method of modifying of a kind of liquid steel slag of the present embodiment, substantially with embodiment 1, its difference is: the steel slag modification agent of the present embodiment comprises the component of following mass percent: rhombspar 15%, Wingdale 15%, magnesite 40% and spathic iron ore 30%.The present embodiment use temperature be 1400 DEG C low-phosphorous converter slag (mass percent of phosphorus is lower than 2%) and mixing dried steel slag modification agent pour in cinder ladle simultaneously, and control the mass ratio that steel slag modification agent and the ratio of the feed rate of liquid steel slag equal steel slag modification agent and liquid steel slag, the mass percent that steel slag modification agent accounts for total batch mixing is 40.0%, batch mixing is cooled to 500 DEG C, modification terminates.
Embodiment 4
The online method of modifying of a kind of liquid steel slag of the present embodiment, get the total mass 158g of steel slag modification agent, choose granularity and be less than the rhombspar of 50mm, Wingdale, spathic iron ore and magnesite, its mass percent is respectively 10%, 0%, 75%, 15%, and carries out drying mixing.Take certain steelworks low-phosphorous converter finishing slag 3000g, modification agent is made to account for about 5% of total amount, first this 3000g slag is placed in plumbago crucible preheating, putting into furnace temperature is again that the retort furnace of 1600 DEG C melts, after slag melts completely, it is mixed with the steel slag modification agent of splendid attire in another preheated crucible, finally by batch mixing air cooling to room temperature.
Embodiment 5
The online method of modifying of a kind of liquid steel slag of the present embodiment, get the total mass 80kg of steel slag modification agent, choose granularity and be less than the rhombspar of 50mm, Wingdale, spathic iron ore and magnesite, its mass percent is respectively 90%, 5%, 5%, 0%, and carries out drying mixing.Take certain factory LF furnace refining slag 450kg, modification agent is made to account for about 15% of total amount, first the slag of 450kg being placed in furnace temperature is that the medium-frequency induction furnace of 1600 DEG C melts, after slag melts completely, it is together added in preheating cinder ladle with the dried steel slag modification agent of mixing and mixes, finally by batch mixing air cooling to 500 DEG C.
Embodiment 6
The online method of modifying of a kind of liquid steel slag of the present embodiment, get the total mass 220kg of steel slag modification agent, choose granularity and be less than the rhombspar of 50mm, Wingdale, spathic iron ore and magnesite, its mass percent is 0%: 45%: 50%: 5%, and carries out drying mixing.Take certain factory LF furnace refining slag 450kg, modification agent is made to account for about 30% of total amount, first the slag of 450kg being placed in furnace temperature is that the medium-frequency induction furnace of 1600 DEG C melts, after slag melts completely, it is together added in preheating cinder ladle with the dried steel slag modification agent of mixing and mixes, finally by batch mixing air cooling to 500 DEG C.
Embodiment 7
The online method of modifying of a kind of liquid steel slag of the present embodiment, get the total mass 1300kg of steel slag modification agent, choose granularity and be less than the rhombspar of 50mm, Wingdale, spathic iron ore and magnesite, its mass percent is 0%: 90%: 0%: 10%, and carries out drying mixing.Take the 40 tons of converters of certain steel mill and slag tap 4 tons, when estimating that modification agent accounts for about 25%, 1600 DEG C of total amount, converter is slagged tap, and dried for mixing steel slag modification agent and slag is added in cinder ladle simultaneously, utilize the surging force of slag that slag and steel slag modification agent are mixed, finally by batch mixing air cooling to 500 DEG C.
Carry out related experiment to the modified slag of embodiment 4 ~ 7 gained, experimental result is referring to table 1:
The modified slag experimental result of table 1 embodiment 4 ~ 7 gained
| 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 |
In 40t converter, carry out commerical test with synthetic slag after upgrading, its experimental result is as shown in table 2.
Show 2-in-1 slagging field experiment result
From above-mentioned experimental result, the decomposition reaction rate of carbonate self is very high, rhombspar, Wingdale, magnesite, spathic iron ore utilize steel slag waste heat efficient-decomposition can produce CaO, MgO and FeO, the slag be modified major part can substitute converter slag-making agent, and slag obtains effective recycling.
Embodiment 8
The online method of modifying of a kind of liquid steel slag of the present embodiment, substantially with embodiment 4, its difference is: the steel slag modification agent of the present embodiment comprises the component of following mass percent: CaMg (CO
3)
25%, CaCO
370%, MgCO
315% and FeCO
310%.
Embodiment 9
The online method of modifying of a kind of liquid steel slag of the present embodiment, substantially with embodiment 4, its difference is: the steel slag modification agent of the present embodiment comprises the component of following mass percent: CaMg (CO
3)
260% and FeCO
340%.
Embodiment 10
The online method of modifying of a kind of liquid steel slag of the present embodiment, substantially with embodiment 4, its difference is: the steel slag modification agent of the present embodiment comprises the component of following mass percent: CaMg (CO
3)
230%, CaCO
325% and FeCO
345%.
Embodiment 11
The online method of modifying of a kind of liquid steel slag of the present embodiment, substantially with embodiment 4, its difference is: the steel slag modification agent of the present embodiment adopts CaMg (CO
3)
2.
The online method of modifying of a kind of liquid steel slag described in embodiment 1 ~ 11, do not follow solid-state upgrading R&D direction popular at present, directly hot upgrading is carried out to molten state slag, modification agent sufficient raw, purchase cost is low, not only takes full advantage of the waste heat of molten state slag, and has given full play to the effect of carbonate, save the cost of slag modification and following cycle recycling to the full extent, easy to utilize.
Claims (6)
1. the online method of modifying of liquid steel slag, the steps include:
Step one, liquid steel slag and steel slag modification agent to be added in cinder ladle simultaneously and mix, this steel slag modification agent is one or more carbonate materials, and described carbonate material is carbonate cpds or carbonate minerals;
Step 2, cooling step one gained batch mixing, modification terminates.
2. the online method of modifying of a kind of liquid steel slag according to claim 1, is characterized in that: the carbonate cpds described in step one is CaMg (CO
3)
2, CaCO
3, MgCO
3, FeCO
3in one or more.
3. the online method of modifying of a kind of liquid steel slag according to claim 1, is characterized in that: the carbonate minerals described in step one is one or more in rhombspar, Wingdale, magnesite, spathic iron ore.
4. the online method of modifying of a kind of liquid steel slag according to Claims 2 or 3, is characterized in that: the granularity of described carbonate minerals is all less than 50mm.
5. the online method of modifying of a kind of liquid steel slag according to claim 4, it is characterized in that: liquid steel slag described in step one is low-phosphorous converter slag or refining slag, the temperature of this liquid steel slag is not less than 1350 DEG C.
6. the online method of modifying of a kind of liquid steel slag according to claim 5, it is characterized in that: in step one, steel slag modification agent accounts for the mass percent of total batch mixing is 5.0% ~ 40.0%, and described steel slag modification agent equals the mass ratio of steel slag modification agent and liquid steel slag with the ratio of the feed rate of liquid steel slag.
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| CN105002316A (en) * | 2015-08-11 | 2015-10-28 | 青岛钢铁控股集团有限责任公司 | Novel slag basin for separating phosphorus in converter slag, manufacturing method thereof and using method thereof |
| CN106435060A (en) * | 2016-09-30 | 2017-02-22 | 攀钢集团攀枝花钢铁研究院有限公司 | Modifying method of titanium-contained slag in molten iron |
| CN106492981A (en) * | 2016-09-20 | 2017-03-15 | 北京科技大学 | A kind of method for improving slag iron component recovery |
| 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 |
| CN112322257A (en) * | 2020-10-30 | 2021-02-05 | 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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| CN105002316A (en) * | 2015-08-11 | 2015-10-28 | 青岛钢铁控股集团有限责任公司 | Novel slag basin for separating phosphorus in converter slag, manufacturing method thereof and using method thereof |
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| CN106435060A (en) * | 2016-09-30 | 2017-02-22 | 攀钢集团攀枝花钢铁研究院有限公司 | Modifying method of titanium-contained slag in molten iron |
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| 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 |
| CN112322257A (en) * | 2020-10-30 | 2021-02-05 | 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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|---|---|
| CN104673965B (en) | 2017-12-15 |
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