CN112010573B - Preparation method and use method of quick-dissolving lime for converter slag - Google Patents

Preparation method and use method of quick-dissolving lime for converter slag Download PDF

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CN112010573B
CN112010573B CN202010896273.4A CN202010896273A CN112010573B CN 112010573 B CN112010573 B CN 112010573B CN 202010896273 A CN202010896273 A CN 202010896273A CN 112010573 B CN112010573 B CN 112010573B
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lime
slag
limestone
converter slag
converter
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夏云进
范鼎东
李�杰
孙桂林
陶素芬
曹彦博
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Anhui University of Technology AHUT
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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
    • C21C7/076—Use of slags or fluxes as treating agents
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2/00—Lime, magnesia or dolomite
    • C04B2/10—Preheating, burning calcining or cooling
    • 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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  • Organic Chemistry (AREA)
  • Ceramic Engineering (AREA)
  • Metallurgy (AREA)
  • Physics & Mathematics (AREA)
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Abstract

The invention discloses a preparation method and a use method of quick-dissolving lime for converter slag, and belongs to the technical field of converter steelmaking. The invention calcines the limestone with the calcining temperature of 950 ℃ to 1200 ℃ and the calcining time of 0.5h to 2.5h to obtain the required lime, the lime contains part of the limestone, namely the physical structure and the chemical composition of the end product are changed, the limestone in the slag transferring process of the lime is decomposed to generate gas, and the gas is diffused outwards from the interior of the lime, so that the lime is quickly decomposed, a cosolvent is not required to be added in the whole process, the dephosphorization reaction rate of steel making is accelerated, the content of free calcium oxide in the slag is reduced, and the comprehensive reutilization of the slag is promoted.

Description

Preparation method and use method of quick-dissolving lime for converter slag
Technical Field
The invention relates to the technical field of converter steelmaking, in particular to a preparation method of quick-dissolving lime for converter slag and a using method thereof.
Background
The lime is one of main slagging materials for converter steelmaking, and the quick and full dissolution of the lime plays an important role in improving the dephosphorization reaction rate of steelmaking. However, in the actual steel making process, due to the influence of various factors, part of lime in the steel making slag is not fully dissolved, so that the dephosphorization efficiency is influenced. With the continuous compression of surplus capacity by steel enterprises in China, more converters are produced by adopting a double-slag and residual slag process or a converter duplex process in China in the future, the key of the double-slag and residual slag process or the converter duplex process lies in the realization of efficient dephosphorization by utilizing low temperature, and the rapid and sufficient dissolution of lime at the low temperature is the key of the process, so that the realization of the rapid and sufficient dissolution of lime at the low temperature is the problem concerned by steel-making workers at present.
In addition, the steelmaking slag is used as one of main byproducts of converter steelmaking, the yield of the steelmaking slag is about 10-15% of the yield of crude steel, however, the comprehensive treatment rate of the steel slag in China is not more than 10% at present, and is far from the comprehensive treatment rate of more than 90% abroad, so that the problems of great resource waste and environmental pollution are caused, and the main reasons for the difficulty in comprehensively utilizing the steelmaking slag are that lime is not fully dissolved and the content of free calcium oxide in the slag is high.
The main reason for slow dissolution of lime in the steel-making slag is that a compact dicalcium silicate layer is formed at the periphery in the lime dissolution process, and the compact dicalcium silicate layer has high melting point and is relatively compact, so that diffusion and reaction of molten slag to the interior of lime are hindered. Benkinxia et al published in "steelmaking" journal a research paper on the research on the dissolution of active lime in steelmaking slag "and proposed that the lime dissolution rate is increased by reducing the slag basicity and increasing the FeO content in the slag. In addition, Hamano et al have studied CaF by adding a cosolvent2、CaCl2、B2O3、Al2O3And the lime melting point is reduced, and lime dissolution is promoted, but the use of the cosolvent not only increases the steel-making cost, but also causes the problem of environmental pollution due to part of the cosolvent.
Disclosure of Invention
1. Technical problem to be solved by the invention
The invention aims to overcome the problem that lime in converter slag is slowly dissolved at low temperature in the prior art, and provides a preparation method and a use method of quickly dissolved lime for converter slag; according to the invention, the limestone is calcined, and the calcining temperature and the calcining time are controlled, so that the generated lime contains part of the limestone, the physical structure and the chemical composition of the end product are changed, the limestone in the slag is decomposed to generate gas in the use process of the lime, and the gas is diffused outwards from the interior of the lime, so that the lime is quickly decomposed.
2. Technical scheme
In order to achieve the purpose, the technical scheme provided by the invention is as follows:
the invention relates to a preparation method of quick dissolving lime for converter slag, which is characterized in that limestone is calcined at the temperature of 950-1200 ℃ for 0.5-2.5 h.
As a further improvement of the invention, the CO produced by the decomposition of the calcined limestone2The mass percent is 3-15%, and the mass percent of CaO is more than or equal to 80%.
As a further improvement of the invention, the size of the limestone is 2cm-8cm, and the average grain size of the lime is less than or equal to 20 mu m.
The invention relates to a use method of quick-dissolving lime for converter slag, which is characterized in that the lime obtained by the preparation method of the quick-dissolving lime for converter slag is added into the converter slag together with iron oxide after calcination.
As a further improvement of the invention, the adding ratio of the lime and the iron oxide is controlled to be 1-3.
As a further improvement of the invention, the converter slag contains 15 to 45 mass percent of FeO and has the alkalinity of less than or equal to 4.5.
As a further improvement of the invention, the iron oxide is one or more of iron ore, sintered ore or iron oxide ore, and FeO and Fe2O3The mass percentage of the iron oxide is more than or equal to 80 percent.
3. Advantageous effects
Compared with the prior art, the technical scheme provided by the invention has the following remarkable effects:
(1) the invention relates to a preparation method of quick dissolving lime for converter slag, which is characterized in that in the process of calcining limestone, the required lime is obtained by controlling the calcining time and the calcining temperature, in the whole process, partial calcining of the limestone is controlled, namely the peripheral calcining of the limestone is complete, raw calcining exists in the limestone, the calcined limestone is added into the slag, and CaCO which is not completely calcined and is positioned in the center of the interior is added under the action of high temperature3Decomposition occurs to produce CO2Gas, CO2The gas can move outwards along the pores and break through the 2 CaO. SiO coated outside the lime2A film for allowing slag to enter the interior of lime, thereby promoting rapid dissolution of lime;
(2) the invention relates to a preparation method of quick dissolving lime for converter slag, which controls the calcination degree, namely the CO in the lime2The content of (A) ensures that the lime can wrap the 2CaO & SiO outside the lime in the using process of the lime2On the basis of membrane breaking, C generated by decomposition is reduced as much as possibleO2In order to reduce CO2Influence on the converter steelmaking process;
(3) according to the preparation method of the quick-dissolving lime for the converter slag, disclosed by the invention, in order to further ensure that the dissolving rate of subsequent lime is high when the lime is used, the size and the average grain size of the lime are limited, after the lime is added into the slag, as the grain size is uniform, the heat transfer is uniform, and the heat can be better transferred to the interior of the lime under the action of high-temperature slag, so that CaCO is facilitated3Decomposition of (2); meanwhile, the overall grain size of the lime is smaller, and the overall dissolution rate of the lime can be increased.
(4) According to the application method of the quick dissolving lime for the converter slag, the adding content of the lime and the iron oxide is controlled during the use process of the calcined lime, the adding proportion of the iron oxide and the lime is controlled, the iron oxide and the lime are mixed to generate a low-melting-point substance, the high-melting-point substance formed on the surface of the lime can be reduced, namely the formed 2CaO SiO is reduced to a certain extent2Thickness of the film, facilitating subsequent CaCO3Decomposition to CO22CaO SiO by gas2The film breaks, so that the dissolution of lime can be accelerated;
(5) according to the application method of the quick-dissolving lime for the converter slag, provided by the invention, the content and alkalinity of FeO in the slag are limited, so that on one hand, a low-melting-point substance is convenient to form, and quick dissolving of the lime is facilitated; on the other hand, the heat consumption of the converter caused by the over-high total content of FeO is avoided, and meanwhile, the splashing generated when the converter is blown is avoided.
Detailed Description
For a further understanding of the present invention, reference will now be made to the following examples.
Example 1
In the method for preparing quick dissolving lime for converter slag according to the embodiment, in order to obtain the lime, the experimental preparation conditions are performed on a 200kg induction furnace, and the process is as follows: firstly, screening limestone with the size of 6cm, calcining the limestone in a muffle furnace, heating the limestone at the heating rate of 6-10 ℃/min after the limestone is placed in the muffle furnace,after the temperature of the muffle furnace reaches 950 ℃, controlling the calcining temperature to 950 ℃ and controlling the calcining time to 2.5h, and it is worth to say that the protection is carried out in the atmosphere of argon in the whole calcining process, and the argon has the important function of protecting generated CO except the protection2Thereby enabling CO to be discharged in the calcining process2The partial pressure is always lower, which is beneficial to the decomposition of limestone. And after the calcining time meets the requirement, cooling the lime for later use, sealing the cooled lime for later use to obtain the required lime, sampling the prepared lime, and detecting, wherein specific parameters of the lime are shown in table 1.
TABLE 1 main parameters of lime
Figure GDA0002681750940000031
In the application method of the quick-dissolving lime for converter slag in the embodiment, firstly, 100kg of industrial pig iron and 10kg of converter decarburization slag are taken and heated to 1400 ℃ by a silicon-molybdenum rod to fully melt the slag, and the temperature is kept for 30 min. The converter slag relevant parameters are shown in the table 2.
After heat preservation, the lime prepared in the embodiment and the iron oxide are mixed and added into the slag, then oxygen is blown into the induction furnace through an oxygen lance, and the oxygen flow is controlled to be 120m3And (t.h), the lance position of the oxygen lance is 5cm above the liquid level, and the experimental process control parameters are shown in Table 2.
The iron oxide is one or more of iron ore, sintered ore or iron oxide ore during the adding process. Preferably, the iron oxide in this embodiment is iron ore, in which FeO and Fe2O3Accounting for 82 percent of the mass of the iron oxide.
For the sake of comparison, a pair of proportions was increased, under the same experimental conditions, lime completely calcined was added to the slag, the specific parameters of which are shown in table 1, and the process control parameters are shown in table 2.
TABLE 2 Experimental Process control parameters
Figure GDA0002681750940000041
And after the experiment is carried out for three minutes, taking slag samples every 1 minute to analyze the content of CaO in the slag, taking the time when the content of CaO in the slag is not changed any more as the final dissolution time of the lime, taking the average value of the time to calculate the average dissolution rate of the lime, and checking the content of free CaO in the slag at the moment.
The results of the tests for example 1 and comparative example are shown in Table 3.
Table 3 main results of the experiment
Figure GDA0002681750940000042
In combination with table 3, it can be seen that the dissolution rate and dephosphorization rate of lime are significantly improved and the content of free CaO in slag is significantly reduced compared with the comparative example in this example 1, wherein the dephosphorization rate is improved from 60.00% to 87.14%, which is improved by 27.14%, the dissolution rate of lime is improved by 1.8 times, and the content of free CaO in slag is reduced from 8% to 1%.
Example 2
The method for preparing quick dissolving lime for converter slag in this embodiment is basically the same as that in embodiment 1, and is different therefrom in that the process is as follows: firstly, screening limestone with the size of 4cm, calcining the limestone in a muffle furnace, controlling the calcining temperature to be 1000 ℃ and the calcining time to be 2 hours under the protection atmosphere of argon, and then cooling and sealing the limestone for later use to obtain the required lime.
The prepared lime is sampled and detected, and the specific parameters of the lime are shown in table 1.
In the application method of the quick-dissolving lime for converter slag in the embodiment, firstly, 100kg of industrial pig iron and 10kg of converter decarburization slag are taken and heated to 1400 ℃ by a silicon-molybdenum rod to fully melt the slag, and the temperature is kept for 30 min. The converter slag relevant parameters are shown in the table 2. After the temperature is kept for 30min, the lime prepared in the embodiment and the iron oxide are mixed and added into the slag, then oxygen is blown into the induction furnace through an oxygen lance, and the oxygen flow is controlled to be 120m3V (t.h), and oxygenThe position of the gun is 5cm above the liquid level, and the control parameters of the experimental process are shown in a table 2.
The iron oxide added in this example is iron scale, in which FeO and Fe2O3Accounting for 88 percent of the mass of the iron oxide.
The components of the slag after the lime addition were sampled and examined, and the results are shown in Table 3.
According to the table 3, the present example has the advantages of significantly improved lime dissolution rate and dephosphorization rate, significantly reduced free CaO content in slag, wherein the dephosphorization rate is increased from 60.00% to 80.77%, increased by 20.77%, lime dissolution rate is increased by 2.27 times, and the free CaO content in slag is decreased from 8% to 1.5%, compared with the comparative example.
Example 3
The method for preparing quick dissolving lime for converter slag in this embodiment is basically the same as that in embodiment 1, and is different therefrom in that the process is as follows: firstly, screening limestone with the size of 7cm, calcining the limestone in a muffle furnace, controlling the calcining temperature to be 1100 ℃ and the calcining time to be 1.8h under the protection atmosphere of argon, cooling the limestone and sealing the limestone for later use, thereby obtaining the required lime.
The prepared lime is sampled and detected, and the specific parameters of the lime are shown in table 1.
In the application method of the quick-dissolving lime for converter slag in the embodiment, firstly, 100kg of industrial pig iron and 10kg of converter decarburization slag are taken and heated to 1400 ℃ by a silicon-molybdenum rod to fully melt the slag, and the temperature is kept for 30 min. The converter slag relevant parameters are shown in the table 2. After the temperature is kept for 30min, the lime prepared in the embodiment and the iron oxide are mixed and added into the slag, then oxygen is blown into the induction furnace through an oxygen lance, and the oxygen flow is controlled to be 120m3And (t.h), the lance position of the oxygen lance is 5cm above the liquid level, and the experimental process control parameters are shown in Table 2.
The iron oxide added in this example was a sinter in which FeO and Fe were present203Accounting for 83 percent of the mass of the iron oxide.
The components of the slag after the lime addition were sampled and examined, and the results are shown in Table 3.
According to the table 3, the present example has the advantages of significantly improved lime dissolution rate and dephosphorization rate, significantly reduced free CaO content in slag, wherein dephosphorization rate is increased from 60.00% to 87.69%, increased by 27.69%, lime dissolution rate is increased by 1.5 times, and free CaO content in slag is decreased from 8% to 1.8%, compared with the comparative example.
Example 4
The method for preparing quick dissolving lime for converter slag in this embodiment is basically the same as that in embodiment 1, and is different therefrom in that the process is as follows: firstly, screening limestone with the size of 7cm, calcining the limestone in a muffle furnace, controlling the calcining temperature to be 1100 ℃ and the calcining time to be 1.8h under the protection atmosphere of argon, cooling the limestone and sealing the limestone for later use, thereby obtaining the required lime.
The prepared lime is sampled and detected, and the specific parameters of the lime are shown in table 1.
In the application method of the quick-dissolving lime for converter slag in the embodiment, firstly, 100kg of industrial pig iron and 10kg of converter decarburization slag are taken and heated to 1400 ℃ by a silicon-molybdenum rod to fully melt the slag, and the temperature is kept for 30 min. The converter slag relevant parameters are shown in the table 2. After the temperature is kept for 30min, the lime prepared in the embodiment and the iron oxide are mixed and added into the slag, then oxygen is blown into the induction furnace through an oxygen lance, and the oxygen flow is controlled to be 120m3And (t.h), the lance position of the oxygen lance is 5cm above the liquid level, and the experimental process control parameters are shown in Table 2.
The iron oxide added in this example was a sinter in which FeO and Fe were present2O3Accounting for 85 percent of the mass of the iron oxide.
The components of the slag after the lime addition were sampled and examined, and the results are shown in Table 3.
According to the table 3, the present example has the advantages of significantly improved lime dissolution rate and dephosphorization rate, significantly reduced free CaO content in slag, wherein dephosphorization rate is increased from 60.00% to 77.50%, increased by 17.50%, lime dissolution rate is increased by 1.5 times, and free CaO content in slag is decreased from 8% to 2.0%, compared with the comparative example.
In view of the above, it is desirable to provide,with reference to tables 1, 2 and 3, it can be seen that, in the data related to comparative examples 1 to 4, as the average grain size of the calcined lime is taken as the influence factor, the average dissolution rate of the lime gradually decreases during the use of the lime as the average grain size increases; in addition, with respect to CO2In terms of content, the average rate of dissolution of lime as a whole is a function of CO2The trend toward a decrease in the content was, however, as for the data relating to examples 1, 2 and 3, it can be seen that when CO is present2The average dissolution rate of lime is not the highest at the highest content, but is the highest in example 2 because the average grain size is the smallest in example 2, while the size of limestone is relatively small; similarly, with respect to the data relating to examples 3 and 4, it can be seen that the average dissolution rates of the limes are the same but the average grain sizes of the limes are different, theoretically, under the relevant conditions of example 3, the average dissolution rate of the limes is higher than that of the limes under the relevant conditions of example 4, but in addition to this influence, the size of the limestone, CO, and the average dissolution rate of the lime are higher2The contents are different, so that the average dissolution rate and the average grain size of the lime and the CO can be obtained2The content and the size of the limestone are closely related.
It is worth to be noted that, in the lime addition process of the prior art, the dissolution process is as follows: adding the completely calcined lime into the slag, dissolving the lime by the slag, and in the dissolving process, under the action of high temperature, CaO and SiO2The reaction generates a high melting point phase-2 CaO. SiO2，2CaO·SiO2Will wrap the surface of the lime which is being dissolved to form a layer of 2 CaO. SiO2The film can hinder the further dissolution of lime, resulting in the problems of slow lime dissolution rate and incomplete lime dissolution in the prior art, and in order to solve the problems, the CaF is basically adopted in the prior art2And the cosolvent is used for assisting dissolution, but the cosolvent easily causes certain pollution to the environment.
Without the need for adding additional co-solventAnd (3) dissolving aid, namely, changing the physical structure and chemical composition of lime to quickly dissolve the lime, wherein in the embodiment, after the calcined lime and the iron oxide are mixed and simultaneously added into slag, 2CaO & SiO is formed on the surface of the lime2In the process of film, lime and iron oxide generate low-melting-point substance-2 CaO. Fe under the action of high temperature2O3Can reduce the generation of 2 CaO. SiO2I.e. reducing the content of 2 CaO. SiO2The thickness of the film is favorable for the subsequent quick dissolution of lime; under the action of high temperature, the heat is conducted among crystal grains, the whole temperature of the lime particles is more uniform, and when the heat is transferred to the center of the lime, CaCO3Gradually decomposed to continuously generate CO2Gas, CO2The gas moves outwards along the pores, so that the 2CaO & SiO & lt- & gt is wrapped outside the lime2The film is broken, and the slag continues to enter the lime, so that the lime is fully and quickly dissolved.
The invention has been described in detail hereinabove with reference to specific exemplary embodiments thereof. It will, however, be understood that various modifications and changes may be made without departing from the scope of the invention as defined in the appended claims. The detailed description is to be construed as illustrative only and not restrictive, and any such modifications and variations are intended to be included within the scope of the invention as described herein. Furthermore, the background is intended to be illustrative of the state of the art as developed and the meaning of the present technology and is not intended to limit the scope of the invention or the application and field of application of the invention.

Claims (4)

1. A preparation method of quick dissolving lime for converter slag is characterized by comprising the following steps: calcining limestone at 950-1200 ℃ for 0.5-2.5 h; CO produced by decomposition of calcined limestone23-15% of CaO and more than or equal to 80% of CaO; the size of the lime is 2cm-8cm, and the average grain size of the lime is less than or equal to 20 mu m.
2. A method for using quick dissolving lime for converter slag, which is the lime obtained by the method for preparing quick dissolving lime for converter slag according to claim 1, and is characterized in that: and simultaneously adding the calcined lime and the iron oxide into the converter slag, wherein the adding ratio of the lime to the iron oxide is controlled to be 1-3.
3. The use method of the quick dissolving lime for converter slag according to claim 2, characterized in that: the converter slag contains 15-45% of FeO by mass and has alkalinity less than or equal to 4.5.
4. The use method of the quick dissolving lime for converter slag according to claim 3, characterized in that: the iron oxide is one or more of iron ore, sinter or iron oxide ore, and FeO and Fe2O3The mass percentage of the iron oxide is more than or equal to 80 percent.
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CN112723760A (en) * 2021-02-05 2021-04-30 武汉科技大学 Partially calcined limestone for rapid slagging of converter and preparation method thereof
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DE2704108A1 (en) * 1977-02-01 1978-08-10 Sumitomo Metal Ind Phosphorus removal from molten iron - by adding iron oxide, converter slag, lime, and possibly oxygen
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CN102649627A (en) * 2012-06-08 2012-08-29 河北联合大学 Method for preparing active lime by calcining limestone
CN103172283A (en) * 2013-03-28 2013-06-26 嘉峪关大友嘉镁钙业有限公司 Calcining method of low carbon high-activity lime
CN106048129A (en) * 2016-07-11 2016-10-26 湖南华菱涟源钢铁有限公司 Converter high-carbon low-phosphorous end-point control metallurgy method under condition of phosphorous molten iron in blast furnace
CN108191268A (en) * 2018-01-31 2018-06-22 广西华洋矿源材料有限公司 A kind of method for refining of active metallurgical lime
CN108439828A (en) * 2018-01-31 2018-08-24 广西华洋矿源材料有限公司 A kind of production method of low-carbon active lime

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE2704108A1 (en) * 1977-02-01 1978-08-10 Sumitomo Metal Ind Phosphorus removal from molten iron - by adding iron oxide, converter slag, lime, and possibly oxygen
CN101003421A (en) * 2006-12-22 2007-07-25 湖北宜化集团有限责任公司 Method for calcining limestone by using relaxed discharged gas of synthetic ammonia as fuel
CN102649627A (en) * 2012-06-08 2012-08-29 河北联合大学 Method for preparing active lime by calcining limestone
CN103172283A (en) * 2013-03-28 2013-06-26 嘉峪关大友嘉镁钙业有限公司 Calcining method of low carbon high-activity lime
CN106048129A (en) * 2016-07-11 2016-10-26 湖南华菱涟源钢铁有限公司 Converter high-carbon low-phosphorous end-point control metallurgy method under condition of phosphorous molten iron in blast furnace
CN108191268A (en) * 2018-01-31 2018-06-22 广西华洋矿源材料有限公司 A kind of method for refining of active metallurgical lime
CN108439828A (en) * 2018-01-31 2018-08-24 广西华洋矿源材料有限公司 A kind of production method of low-carbon active lime

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