Journal Pre-proof

Dissolution behavior of partially calcined limestone with residual CO2 in converter

slag

Yufeng Tian, Yu Liu, Guangqiang Li, Yongqian Li, Zhan Zhang, Chong Tan

PII: S2238-7854(22)00163-6
DOI: https://doi.org/10.1016/j.jmrt.2022.01.163
Reference: JMRTEC 4360

To appear in: Journal of Materials Research and Technology

Received Date: 25 September 2021

Revised Date: 30 November 2021
Accepted Date: 28 January 2022

Please cite this article as: Tian Y, Liu Y, Li G, Li Y, Zhang Z, Tan C, Dissolution behavior of partially
calcined limestone with residual CO2 in converter slag, Journal of Materials Research and Technology,
https://doi.org/10.1016/j.jmrt.2022.01.163.

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 1 Dissolution behavior of partially calcined limestone with residual CO2 in

2 converter slag

3 Yufeng Tian1, Yu Liu1*, Guangqiang Li1,2,3*, Yongqian Li4, Zhan Zhang2, Chong Tan3

4 1) The State Key Laboratory of Refractories and Metallurgy, Wuhan University of

5 Science and Technology, Wuhan 430081, China.

6 2) Key Laboratory for Ferrous Metallurgy and Resources Utilization of Ministry of

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7 Education, Wuhan University of Science and Technology, Wuhan 430081, China.

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8 3) Hubei Provincial Key Laboratory for New Processes of Ironmaking and

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9
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Steelmaking, Wuhan University of Science and Technology, Wuhan 430081,
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10 China.
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11 4) China Baowu Steel Group Corporation Limited, Shanghai 201900, China.

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*
12 Corresponding author: Guangqiang Li; Yu Liu
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13 E-mail: liguangqiang@wust.edu.cn; liuyu629@wust.edu.cn

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14

1
 1 Abstract

2 Accelerating the dissolution rate of lime in converter slag at the initial stage of

3 steelmaking is conducive to the rapid slagging. In this work, partially calcined

4 limestone with a core-shell structure was prepared, and the dissolution behaviors of

5 lime, partially calcined limestone bearing ~28 wt% CO2, and limestone in converter

6 slag were studied. The results showed that the formation of 2CaO·SiO2 layer slows

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7 down the dissolution of lime. Different from lime, the CO2 bubbles produced by the

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8 limestone decomposition could destroy the 2CaO·SiO2 layer and accelerate the

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9
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dissolutions of limestone and partially calcined limestone. Compared with limestone,
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10 the slag temperature drop near the surface is less, and no stagnation stage occurs
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11 during the dissolution of partially calcined limestone due to the existence of

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12 decomposed lime surface layer. The most rapid dissolution rate and the higher
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13 substitution ratio of lime imply that the partially calcined limestone slagging mode
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14 would be more promising than limestone and lime.

15 Keywords: partially calcined limestone; converter slag; dissolution; 2CaO·SiO2 phase;

16 CO2 bubbles

17

2
 1 1. Introduction

2 The rapid dissolution of lime in converter slag is important for the rapid slagging,

3 which contributes to the fast dephosphorization during steelmaking. Enormous

4 researches on the dissolution behavior of lime in converter slag were conducted,

5 including the reaction mechanism [5] and factors to affect the dissolution rate, such as

6 the slag composition [1,6], physical properties [7,8] and temperature [9], dynamic

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7 conditions [10], lime properties [11-13] and so on. Deng et al. [6,14,15] found that the

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8 high FeO content in the slag is beneficial to accelerate the dissolution of lime because

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9
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the FeO can penetrate into the lime and help the exfoliation of the 2CaO·SiO2 reaction
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10 layer. Johan et al. [7] revealed that the violent movement of the large-sized gas
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11 channels in the foamed slag with high viscosity broadly also promotes the peeling of
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12 the 2CaO·SiO2 layer on the lime surface. The industry test also confirmed that
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13 increasing on the total iron content of the slag by using pre-melted flux can improve
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14 the dephosphorization effect [7]. Kobe Steel successfully produced high-carbon steel

15 with a low phosphorus content by using pre-melted flux. However, the cost of

16 pre-melted flux slagging is higher than the economic benefits, so the practical

17 application value of this method is limited [12]. Meanwhile, for a certain converter

18 process, it is impossible to adjust the composition of slag. It is more practical to speed

19 up the dissolution of lime by adjusting the lime properties.

20 It is generally considered that reducing the size of lime [16] and improving the

21 pore structure of lime surface to increase the specific surface area of lime [17] are

3
 1 effective ways to improve the dissolution rate of lime. It has been confirmed that the

2 dephosphorization effect of converter is improved by using small size lime slagging,

3 but the impact on the reduction of lime particle size is still less than expected [12].

4 Once the reaction layer is formed, the effect of specific surface area of lime on the

5 dissolution rate is weakened. In recent years, the slagging mode of using limestone

6 instead of lime has been proposed [19-22]. During the dissolution of limestone in

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7 converter slag, the CO2 generated by the decomposition of limestone can destroy the

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8 calcium silicate reaction layer, and dissolution of decomposed lime is greatly

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9
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accelerated [23]. Chen et al. [24] found that the dissolution process of limestone
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10 includes three stages: (a) stagnation stage, (b) coexistence stage of decomposition and
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11 dissolution, and (c) Sole dissolution stage. The stagnation stage is mainly caused by
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12 the decomposition of limestone, and the limestone hardly dissolves at this stage.
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13 Furthermore, limestone decomposition belongs to the endothermic reaction. It could

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14 affect the heat balance of the converter steelmaking and increase furnace burdens.

15 Maruoka et al. studied the dissolution behavior of lime with 0-25 wt% CO2, and

16 concluded that CaCO3 core is the key factor for rapid dissolution of lime [25,26].

17 In summary, lime can immediately begin to dissolve when added to the converter

18 slag, afterwards the formation of calcium silicate layer hinders the dissolution of lime.

19 The decomposition of limestone can destroy the dense calcium silicate layer and

20 accelerate the dissolution of limestone. But the limestone needs to decompose to form

21 calcium oxide before dissolution occurs. The limestone hardly dissolves at this stage,

4
 1 namely, the so-called stagnation stage. Moreover, the decomposition of limestone also

2 affects the heat balance of the converter, and the wide application is limited. This

3 inspired the author to consider how to combine the advantages of lime slagging and

4 limestone slagging. In this study, the partially calcined limestone with core-shell

5 structure was designed. It could be expected that the lime layer on the surface of

6 partially calcined limestone can be dissolved immediately when added into converter

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7 slag, and subsequently the decomposition of limestone core can destroy the calcium

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8 silicate layer and accelerate the dissolution. Furthermore, the decomposition of

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9
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partially calcined limestone can be expected to need less heat than that of limestone
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10 slagging.
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11 To confirm this idea, the dissolution behavior of partially calcined limestone with
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12 CO2 content of 28 wt% in converter slag was explored in present study, and compared
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13 with lime and limestone. Furthermore, the effect of the slagging mode of partially
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14 calcined limestone on the heat balance of converter was also analyzed.

15 2. Experimental

16 2.1 Sample preparation

17 The limestone (~98.86 wt% CaCO3) as raw materials was taken from a company

18 that provides metallurgical lime. To determine the CO2 content in limestone and

19 design calcination temperature, the differential scanning calorimeter (DSC) and

20 thermogravimetric analysis (TG) were carried out [27-29]. Raw limestone lumps were

21 processed into the cubic samples with the dimension of 10 mm × 10 mm × 10 mm by

5
 1 the cutter. The partially calcined limestone samples were prepared by calcining

2 limestone samples at 800 °C in an electrical resistance furnace, as shown in step 1 of

3 Figure 1. The CO2 content in partially calcined limestone can be calculated by the

4 following equation (1):

100(m 2  0.56 m1 )
x % (1)
m2

5 where m1 is the mass of the limestone sample (g), and m2 is the mass of partially

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6 calcined limestone. The CO2 content of partially calcined limestone sample is

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7 approximately 28 wt%. Lime sample was obtained by calcining limestone sample at
-p
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8 1000 °C for 2 h.
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9 CaO powder used for the synthesized slag was obtained by calcining the reagent

10 grade CaCO3 powder at 1000 °C for 10 h. The SiO2 powder was heated at 300 °C for
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11 5h to ensure sufficient drying. The wustite (FeOx) powder was prepared by

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12 decarburizing the reagent grade powder of FeC2O4 at 850 °C for 1 h under argon
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13 atmosphere [24]. After mixed in the proportion (as shown in Table 1), the synthesized

14 slag was premelted at 1400 °C in an iron crucible under argon atmosphere. The

15 composition of the synthesized slag was selected according to a slag formation route

16 with high iron oxide.

17 Table 1. Chemical composition of synthetic converter slag (wt%)

CaO SiO2 FeOx

20 40 40

18

6
 1

2 Figure 1. Schematic diagram of the preparation and dissolution of partially calcined

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3 limestone (1) calcination; (2) coexistence stage of decomposition and dissolution;

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4 (3) sole dissolution stage
-p
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5
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6 2.2 Dissolution of three lime samples in converter slag

7 The experimental apparatus is shown in Figure 2. The heating element of this

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8 tubular furnace is MoSi2. It is well known that the temperature of molten iron entering
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9 the converter is about 1300 °C, and the dephosphorization reaction of the converter
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10 needs large amount of CaO in the converter slag to form the stable calcium phosphate

11 for preventing phosphorus back to molten steel above 1500 °C. Considering these

12 factors, the experimental temperature of lime dissolution is designed as 1400 °C. 20 g

13 synthesized slag was put into an iron crucible with the inner diameter of 30 mm and

14 heated to 1400 °C under argon atmosphere. After the slag was melted completely, the

15 lime sample was heated at the top of the furnace for 10 s, then dipped into slag. After

16 the different reaction times, the crucible was immediately taken out from furnace and

17 quenched. Figure 3 shows the slag cooled on the copper plate. This procedure was

7
 1 then repeated for limestone and partially calcined limestone.

2 To avoid the destruction of the sample structure during cutting, the quenched

3 sample was enclosed in epoxy resin. After cutting the remaining sample, the

4 cross-section of the sample was carefully ground by sandpapers and polishing

5 machine. The dimensions of the residual lime sample were measured by the vernier

6 caliper. The microstructure and the element distribution were analyzed by scanning

f
7 electron microscope (SEM) equipped with energy dispersive spectrometer (EDS).

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9 Figure 2. Experimental set-up for evaluating dissolution rate of lime

10

8
 1

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2 Figure 3. The slag cooled on the copper plate

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3
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4 2.3 Decomposition of limestone samples
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5 The calcination of limestone was carried out at 1400 °C to evaluate the

6 decomposition behavior of limestone during dissolution. The experimental device was

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7 the same as that used in section 2.2, and the only difference was that no synthetic slag
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8 was added. The limestone was weighed and then placed in an iron crucible at 1400 °C.
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9 After holding for a certain period, the limestone was taken immediately from the iron

10 crucible and quenched, and the mass change of sample was measured.

11 3. Results and discussion

12 3.1 TG-DSC analysis

13 Figure 4 shows the TG-DSC curve of the limestone raw material. It indicates that

14 the weight loss of the limestone raw material reaches 43.5%, and the maximum

15 decomposition rate is obtained at 872 °C. Based on the weight loss, it can be inferred

16 that the CaCO3 content in limestone used in present study is ~98.86 wt%. In order to

9
 1 control the CO2 content more easily and accurately, the partially calcined limestone

2 samples were prepared by calcining limestone sample at 800 °C.

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4 Figure 4. DSC-TG curves of limestone raw material with a heating rate of

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5 10 °C·min-1 under Ar atmosphere
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6
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7 3.2 Dissolution rate

8 Figure 5 shows the average size of the three samples as a function of reaction
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9 time at the slag temperature of 1400 °C. The dissolution rate of lime samples can be
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10 calculated by equation (2) [26,30]:

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dl kCaO slag
   (%CaO) (2)
dt 100 CaO

11 where l is the average size of samples, t is time, kCaO is the mass transfer coefficient of

12 CaO in the liquid slag, and Δ(%CaO) is the driving force of diffusion assumed to be

13 the difference between the solubility of CaO in slag and the content of CaO in bulk

14 slag. By linear fitting, the data in Figure 5, the values of -dl/dt can be obtained. Finally,

15 the kCaO can be obtained by substituting the relevant data into equation (2), as shown

16 in Table 2. The mass transfer coefficients in the tests of lime and limestone show the

10
1 same order of magnitude as those reported by previous researchers [23,26,30], which

2 implies that the values obtained in this study are reasonable. The mass transfer

3 coefficient in the test of partially calcined limestone is three times that of limestone,

4 and the mass transfer coefficient in the test of limestone is twice that of lime.

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5
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6 Figure 5. Change on average size of sample with reaction time at 1400 °C
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7
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11
1

2 Table 2. Values of calculated the mass transfer coefficient of three kinds of lime

Parameter Limestone Partially calcined limestone Lime

-dl /dt (mm·s-1) 0.0123 0.0359 0.0057

kCaO (mm·s-1) 0.030 0.087 0.014

f
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4 To quantitatively evaluate the solubility of samples from the volume change,

5 dissolution degree (X) was calculated by equation (3) as follows:

r
l2 3
X  1 3
-p(3)
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l1
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6 where X is the dissolution degree (%), l1 and l2 represents the average size of the
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7 sample before and after the reaction (mm), respectively.

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9 Figure 6. Dissolution degree of three samples

12
1

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2 Figure 7. Cross-section of partially calcined limestone sample processed by

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3 thymolphthalein (lime is colored by thymolphthalein and the gray part surrounded by

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4
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lime is undecomposed limestone)
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na
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6 Figure 8. SEM micrographs of the interface between the samples and slag at 1400 °C

7 for 60 s: (a) limestone; (b) partially calcined limestone

13
 1 Figure 6 shows the changes in dissolution degree of samples with reaction time at

2 1400 °C. It is interesting that the dissolution degree of limestone is almost zero from

3 the start time to 60 s, implying that this stage is mainly the decomposition of

4 limestone to form CaO. It is consistent with the previous study [24], and only

5 decomposition reaction occurs in this stage, which is the so-called stagnation stage.

6 The dissolution rate of partially calcined limestone is almost the same as that of lime

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7 in the first 60 s, much faster than that of limestone. This implies that the

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8 decomposition of partially calcined limestone does not affect its dissolution. Namely,

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9
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the dissolution process of partially calcined limestone does not contain the stagnation
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10 stage, only including the coexistence stage of decomposition and dissolution, and sole
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11 dissolution stage, as shown in step 2 of Figure 1. This is because there is a layer of

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12 decomposed lime on the surface of partially calcined lime, as shown in Figure 7. After
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13 60 s, partially calcined limestone dissolves faster. Figure 8 shows the SEM

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14 micrographs of the interface between the samples and slag at 1400 °C for 60 s in the

15 tests of limestone and partially calcined limestone. During lime dissolution, FeO in

16 the slag penetrates and diffuses to the inside of lime, forming the low melting point

17 CaO-FeO phase. It can be seen from Figure 8a that only narrow CaO-FeO layer is

18 formed at the interface between slag and limestone at 60 s, and the size of limestone

19 hardly changes (Figure 5). In contrast, it can be found that the width of CaO-FeO

20 layer formed at the interface between slag and partially calcined limestone is about

21 320 μm at 60 s. This indicates that FeO penetrates into the partially calcined limestone

14
1 more seriously than limestone. In the initial stage of dissolution, the lime shell of

2 partially calcined limestone directly contacts with the molten slag, and the dissolution

3 starts. As a result, the partially calcined limestone dissolves faster than limestone in

4 the initial 60 s holding.

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na
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6 Figure 9. SEM micrographs of the interface between the samples and slag at 1400 °C

7 for 180 s: (a) limestone; (b) lime

15
 1
2 Figure 10. Phase diagram of FeO-CaO-SiO2 system

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-p
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3
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4 Figure 11. The schematic diagram of distribution of slag components near the
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5 interface
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7 After 60 s holding, the dissolution of limestone is greatly accelerated (Figure 6).

8 Lime dissolves quickly in the first 60 s, but the subsequent dissolution rate decreases

9 significantly (Figure 6). Relevant researches have reported that the dicalcium silicate

10 formed on the surface of lime during the dissolution process limits the dissolution of

11 lime [2,6]. To better understand the effect of differences in interface structure resulted

12 from lime sources on the dissolution of lime, the interface between sample and slag

13 was observed by SEM equipped with EDS. Figure 9 shows SEM micrographs of the

16
 1 interface between the lime samples and slag at 1400 °C for 180 s in the tests of

2 limestone and lime. It indicates that 2CaO·SiO2 phase exists at the interface between

3 lime and slag in both tests. To clarify the formation mechanism of the microstructure

4 (Figure 9), the ternary phase diagram of the CaO-FeO-SiO2 system was calculated, as

5 shown in Figure 10. The initial composition of synthetic slag is in the primary crystal

6 zone of CaO·SiO2. With the dissolution of CaO, the slag position gradually

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7 approaches the primary crystal region of 2CaO·SiO2. The calculation results show

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8 that even if all the CaO in the sample is dissolved into the slag, the composition point

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9
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of slag is still not located at the 2CaO·SiO2 primary crystal region. However, the
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10 2CaO·SiO2 phase is found at the interface between lime sample and slag (Figure 9).
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11 The reasonable explanation is that the diffusion of Ca element in the slag is limited by
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12 the mass transfer, and the content of CaO in molten slag near the surface of the
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13 sample is relatively high. As shown in Figure 11, during the lime dissolution process,
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14 FeOx and SiO2 in the slag penetrate into the surface and interior of the lime to form

15 (Fe, Ca)O solid solution and 2CaO·SiO2 [31]. At the same time, Ca diffuses from the

16 lime surface into the slag, so the 2CaO·SiO2 layer is formed near the lime surface.

17 The formation of 2CaO·SiO2 layer at the interface in the test of limestone implies that

18 the limestone has been completely decomposed and reaction entered the dissolution

19 stage without decomposition. The result is consistent with the end time of the

20 decomposition reaction of limestone at 1400 °C in Figure 12. There are notable

21 differences in the thickness of the CaO-FeO layer at the interface in the test of

17
 1 limestone and lime (Figure 9). It can be roughly measured that the thickness of

2 CaO-FeO layer in limestone experiment and lime experiment is 462 μm and 153 μm,

3 respectively. The FeO penetration towards lime is hindered by the dense 2CaO·SiO2

4 layer. The previous studies have confirmed that CO2 produced by limestone

5 decomposition reaction can destroy 2CaO·SiO2 layer [23-26], which accelerates the

6 dissolution. In present study, the CO2 gas can be generated in the test of limestone and

f
7 partially calcined limestone. During the dissolution of limestone, the formation of

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8 2CaO·SiO2 layer should be after the complete decomposition of limestone, which is

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9
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later than that in the test of lime. After 180 s, the dissolution degree of limestone is
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10 larger than that of lime. It implies that the formation of 2CaO·SiO2 layer has less
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11 effect on the dissolution rate of limestone. In addition, Mao et al. [23] found that in
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12 the same slag the dissolution rate of limestone without stirring is faster than that of
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13 lime with stirring, so the formation of reaction layer is the main factor to hinder lime
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14 dissolution.

15

16 Figure 12. The decomposition rate of limestone at 1400 °C

17

18
 1 Furthermore, the dissolution degree of partially calcined limestone always keeps

2 the largest after 60 s, which proves that the CO2 produced by the decomposition of

3 limestone core in partially calcined limestone can also accelerate the dissolution

4 (Figure 6). The dissolution degree of partially calcined limestone reaches

5 approximately 94% after 180 s holding, while that of limestone and lime is about 42%

6 and 40%, respectively. The dissolution rate of partially calcined limestone in BOF

f
7 slag is fastest in all tests due to the presence of the surface lime layer and the CO2

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8 emission formed by the decomposition of CaCO3 core.

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9 3.3 Slag temperature drop rate
-p
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10 During limestone dissolution, the slag temperature near the limestone surface will
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11 decrease due to the decomposition of limestone [23,24]. The decomposition degree of

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12 limestone can be calculated by equation (4) as follows:

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m0  mre
X dec  (4)
44%  98.86%  m0
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13 where Xdec is the decomposition degree of limestone (%), m0 and mre is the quality of

14 limestone before and after the reaction (g), respectively. Figure 12 shows the change

15 of the decomposition degree of limestone with time at 1400 °C. According to the

16 change in decomposition degree, the drop rate of the slag temperature near the surface

17 of limestone can be roughly estimated. It was assumed that all the heat absorbed by

18 the decomposition comes from the slag near the surface of the limestone, and the

19 temperature of this part of the slag is the same. The detailed calculation steps and

20 calculation equations are as follows.

19
 1 Heat consumption rate of limestone decomposition reaction

q  H  rCaCO3 (5)

dX dec
rCaCO3   nCaCO3 (6)
dt

2 where q is the rate of heat consumption by limestone decomposition (J·s−1), ΔH is the

3 enthalpy of decomposition reaction (J·mol−1), rCaCO3 is the reaction rate of limestone

4 decomposition reaction (mol·s−1), Xdec is the decomposition degree of limestone (%),

f
5 and nCaCO3 is the amount of CaCO3 in limestone sample (mol).

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6 Drop rate of the slag temperature near the surface of limestone

r
d (T )

q
-p (7)
Cp  mslag
re
dt
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7 where d(ΔT)/dt is the drop rate of the slag temperature near the surface of limestone

8 (°C·s-1), mslag is the mass of molten slag near the limestone surface in the
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9 assumption(kg), CP is the constant-pressure capacity of molten slag (J·kg-1·°C-1).

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10 According to equations (5)-(7), the drop rates of slag temperature can be

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11 calculated, as shown in Figure 13. The drop rate equations are also obtained by fitting

12 these calculated results, as expressed by equations (8)-(12) as follows:

d (T )
 31.37  0.97t  0.20 (2 g slag) (8)
dt
d (T )
 15.68  0.97t  0.10 (4 g slag) (9)
dt
d (T )
 10.46  0.97t  0.07 (6 g slag) (10)
dt
d (T )
 7.84  0.97t  0.05 (8g slag) (11)
dt
d (T )
 6.27  0.97t  0.04 (10 g slag) (12)
dt

20
 1

2 Figure 13. Drop rate of slag temperature near limestone for varying slag amount

f
3 Table 3. Values of slag temperature drop rate near limestone under different slag

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4 amount

r
Reaction Time (s)
-p 0 30 60 90
re
2 grams of slag 31.17 11.24 3.97 1.32
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4 grams of slag 15.58 5.62 1.99 0.66

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6 grams of slag 10.39 3.75 1.32 0.44

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8 grams of slag 7.79 2.81 0.99 0.33

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10 grams of slag 6.23 2.25 0.79 0.26

5 Figure 13 shows that the drop rate of slag temperature is the largest as the

6 limestone starts to decompose, subsequently the drop rate decreased rapidly in 60 s.

7 After 60 s, the effect of decomposition of limestone on the drop rate of slag

8 temperature is greatly weakened. This is because that the amount of limestone

9 decreases as the decomposition reaction proceeds. According to Figure 12, the CO2

10 content in the partially calcined limestone corresponds to that in limestone treated at

11 1400 °C for 30 s. The slag temperature drop rate has dropped by more than 60% at

21
 1 about 30 s, which implies that drop rate of the slag temperature near the surface of

2 partially calcined limestone is much lower than that of limestone (Figure 13, Table 3).

3 Although the temperature drop of slag near the limestone surface can be compensated

4 quickly, the short-term low slag temperature still has a great impact on the dissolution

5 of limestone [23,24]. The larger drop in slag temperature does not favor the

6 decomposition reaction of limestone. This is another reason why limestone hardly

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7 dissolves in the first 60 s during the dissolution test (Figure 6). Compared with

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8 limestone, the effect of decomposition of partially calcined limestone on slag

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9
-p
temperature is greatly reduced. It also provides better thermodynamic conditions for
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10 the dissolution of partially calcined limestone, especially in the first 60 s.
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11 3.4 Dissolution mechanism of partially calcined limestone

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12 In present study, it can be concluded that lime immediately begins to dissolve

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13 rapidly after added into the converter slag, subsequently the dissolution rate decreases
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14 greatly with the formation of calcium silicate layer. CO2 bubbles generated by

15 limestone decomposition can destroy the calcium silicate layer, but limestone needs to

16 be decomposed to form CaO before dissolution. The limestone hardly dissolves at this

17 stage. Compared with lime and limestone, the partially calcined limestone with

18 core-shell structure combines the advantages of lime and limestone. At the initial

19 stage of dissolution, the lime shell directly contacts with the slag, and dissolves

20 rapidly. Meanwhile, the CO2 emission by decomposition of the limestone core also

21 can destroy the calcium silicate layer, and accelerate the dissolution of partially

22
 1 calcined limestone. Furthermore, it is well known that the decomposition of limestone

2 is affected by heat transfer. According to the calculation in section 3.3, the slag

3 temperature drop near the lime surface caused by the decomposition of partially

4 calcined limestone core is 63~65% lower than that of limestone. Compared with

5 limestone, the heat transfer has less influence on the decomposition of limestone core

6 in partially calcined limestone. As a result, the partially calcined limestone dissolves

f
7 fastest in the converter slag.

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8 3.5 Industrial Significance

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9
-p
During converter steelmaking, the heat consumption of limestone slagging is more
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10 than that of lime slagging in two aspects: more heat consumption is need for heating
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11 limestone than lime; more heat consumption is need for the decomposition of
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12 limestone. To realize limestone slagging, it is necessary to reduce the amount of scrap

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13 in converter, which limits the lime substitution rate of limestone slagging. The
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14 differences among heat consumption of lime, partially calcined limestone and

15 limestone can be roughly estimated [32]. To provide 1 kg CaO for converter, the heat

16 consumption for limestone slagging is 1099 kJ more than for partially calcined

17 limestone slagging. Taking the smelting of Q-235 steel in 200 t converter as the

18 example, according to the heat income items and heat expenditure items of the

19 converter [33], the calculated maximum substitution ratio for partially calcined

20 limestone slagging is 62.8%, which is higher than that for limestone slagging (45.9%).

21 More importantly, the dissolution rate of partially calcined limestone in BOF slag is

23
 1 also larger than that of limestone. The higher substitution ratio and dissolution rate for

2 partially calcined limestone slagging will contribute to the rapid increase of CaO

3 content in BOF slag. In the traditional lime preparation process, to ensure complete

4 calcination, the outer layer of lime appears overburnt in varying degrees, which not

5 only decreases the product quality, but also wastes lots of heat. Due to the slow

6 dissolution of low activity lime in the slag, the outer lime is further overburnt,

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7 resulting in the reduction of activity again. This vicious cycle slows down the

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8 dissolution rate of lime [23]. Partial calcined limestone does not need to be calcined

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9
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completely, which reduces the heat consumed in the preparation process and reduces
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10 carbon emission. Compared with limestone and lime slagging [34,35], partially
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11 calcined limestone slagging combines their advantages and overcomes their defects to
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12 a certain extent. Therefore, partially calcined limestone slagging mode would be more
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13 promising.
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14 4. Conclusions

15 The following conclusions can be drawn out:

16 (1) Once limestone decomposition is completed, 2CaO·SiO2 layer can be formed

17 at the interface between decomposed lime and molten slag. But the CO2 generated by

18 limestone decomposition makes the formation time of 2CaO·SiO2 layer in the case of

19 limestone is later than that of lime. As a result, the severer FeO penetration into

20 decomposed lime occurs during the dissolution of limestone, and the limestone

21 dissolves faster than lime.

24
 1 (2) Compared to limestone, there is no stagnation stage in the dissolution of

2 partially calcined limestone due to the presence of the surface lime layer and the

3 lower temperature drop of slag. Meanwhile, CO2 emission by the decomposition of

4 limestone core in partially calcined limestone can also promote the peeling of calcium

5 silicate reaction layer and accelerate dissolution. Thus, the dissolution rate of partially

6 calcined limestone in BOF slag is faster than that of lime and limestone.

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7 (3) The substitution ratio of lime for partially calcined limestone slagging is

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8 higher than that for limestone slagging. The dissolution rate of partially calcined

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9
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limestone in converter slag is also faster. It implies that the partially calcined
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10 limestone slagging mode would be more promising.
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Declaration of interests

☒ The authors declare that they have no known competing financial interests or personal relationships
that could have appeared to influence the work reported in this paper.

☐The authors declare the following financial interests/personal relationships which may be considered
as potential competing interests:

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