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Invited Review

A review of carbon dioxide disposal technology in the converter steelmaking process

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  • Corresponding author:

    Bao-chen Han    E-mail: ustbhbc@163.com

  • Received: 23 January 2020Revised: 14 April 2020Accepted: 15 April 2020Available online: 16 April 2020
  • In last decade, the utilization of CO2 resources in steelmaking has achieved certain metallurgical effects and the technology is maturing. In this review, we summarized the basic reaction theory of CO2, the CO2 conversion, and the change of energy-consumption when CO2 was introduced in converter steelmaking process. In the CO2–O2 mixed injection (COMI) process, the CO2 conversion ratio can be obtained as high as 80% or more with a control of the CO2 ratio in mixture gas and the flow rate of CO2, and the energy is saving and even the energy consumption can be reduced by 145.65 MJ/t under certain operations. In addition, a complete route of CO2 disposal technology is proposed combining the comparatively mature technologies of CO2 capture, CO2 compression, and liquid CO2 storage to improve the technology of CO2 utilization. The results are expected to form a large-scale, highly efficient, and valuable method to dispose of CO2.
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A review of carbon dioxide disposal technology in the converter steelmaking process

  • Corresponding author:

    Bao-chen Han    E-mail: ustbhbc@163.com

  • 1. School of Metallurgical and Ecological Engineering, University of Science and Technology Beijing, Beijing 100083, China
  • 2. Beijing Key Laboratory of Research Center of Special Melting and Preparation of High-end Metal Materials, University of Science and Technology Beijing, Beijing 100083, China

Abstract: In last decade, the utilization of CO2 resources in steelmaking has achieved certain metallurgical effects and the technology is maturing. In this review, we summarized the basic reaction theory of CO2, the CO2 conversion, and the change of energy-consumption when CO2 was introduced in converter steelmaking process. In the CO2–O2 mixed injection (COMI) process, the CO2 conversion ratio can be obtained as high as 80% or more with a control of the CO2 ratio in mixture gas and the flow rate of CO2, and the energy is saving and even the energy consumption can be reduced by 145.65 MJ/t under certain operations. In addition, a complete route of CO2 disposal technology is proposed combining the comparatively mature technologies of CO2 capture, CO2 compression, and liquid CO2 storage to improve the technology of CO2 utilization. The results are expected to form a large-scale, highly efficient, and valuable method to dispose of CO2.

    • Various auxiliary gases (e.g., O2, Ar, and N2) are used for decarburization, stirring liquid steel, homogenizing the liquid steel temperature, and providing conditions for reactions in the steelmaking process. Metallurgists introduced CO2 to the field of steelmaking since the 1970s. Some researchers studied the decarburization mechanism and interfacial reaction kinetics with CO2 or CO2 containing mixing gas in molten steel and proved that CO2 can be effectively utilized in the decarburization of molten steel and established the related reaction model [16]. Some other researchers [716] studied the application mechanism and effect of bottom blowing CO2 in molten steel and found the potential of CO2 as a stirring gas. However, the technology has not been widely used in steel factories due to issues of the lifetime of bottom blowing elements in that period.

      In last decade, our team also carried out research on the application of CO2 in the steelmaking process and invented the CO2–O2 mixed injection (COMI) process. We found that top blowing CO2–O2 mixing gas can remove the dissolved carbon in the molten steel ([C]) and achieve a smelting effect [1718]. And then we carried out industrial experiments of the COMI process in the basic oxygen furnace (BOF) and found that the average ratio of dust generation was reduced by 19.3% [1925]. In addition, Lv et al. [2627] concluded that compared to the conventional process, the dephosphorization ratio was increased by 7.53%–13.39% when the COMI process was used in a BOF. Li et al. [2830] used limestone instead of lime for smelting in the BOF steelmaking process to obtain better metallurgical effects. Wang et al. [3134] found that pure CO2 injection can meet the decarburization requirements of the stainless-steel smelting and the loss of chromium can be greatly reduced. When pure CO2 is injected, the carbon content is reduced from 3.0wt% to approximately 1.0wt%, and there is nearly no loss of chromium. Alternatively, the loss of chromium is approximately 1.5wt% when pure oxygen is injected. We also extended the related technology to electric arc furnace (EAF), ladle furnace (LF), Rheinstahl–Heraeus (RH) furnace, and other vacuum degassing refining process [3538].

      Combined with the excellent high-temperature characteristics of CO2, we systematically studied the COMI process and realized its industrial application. This paper aims to review the basic theory of CO2 utilization in converter steelmaking, which includes the principles of CO2 participating in steelmaking reactions, CO2 conversion, and evaluation of the energy consumption in Section 2. A technical route integrating CO2 recovery, CO2 utilization, and preparation of ethanol by CO is proposed in Section 3.

    2.   Basic theory of CO2 utilization in COMI steelmaking process
    • In order to partially or completely solve the problem of dust generation from steelmaking, we replaced partial top blowing O2 and all bottom blowing gas with CO2 in steelmaking, called the COMI process. Through relevant experiments and theoretical research, more metallurgical effects were produced when CO2 gas was used in top and bottom blowing, such as promoting dephosphorization and denitrogenation. The utilization of CO2 in BOF was reviewed in a previous paper from a technical perspective, including advantages and shortcomings [39]. Fig. 1 shows the COMI process of the CO2 dynamic injection in the converter. The COMI process was developed and expanded into a real-time dynamic injection method for different steel grades, including a series of different operations and control models.

      Figure 1.  Process of CO2 dynamic injection in a converter [39]. Reprinted from J. CO2 Util., 34, B.C. Han, G.S. Wei, R. Zhu, W.H. Wu, J.J. Jiang, C. Feng, J.F. Dong, S.Y. Hu, and R.Z. Liu, Utilization of carbon dioxide injection in BOF–RH steelmaking process, 53, Copyright 2019, with permission from Elsevier.

    • The Gibbs free energy of the reactions can be used to determine whether the reactions between CO2 and elements occur. However, only the standard Gibbs free energy ($\Delta {G^ \ominus }$) can be calculated under steelmaking condition given the uncertainty of the CO partial pressure. Table 1 shows the detailed results of the standard Gibbs free energy between CO2 and [C], [Fe], [Si], [Mn], [Cr], or [V] ([i] means the element i in molten steel), and the degree of the oxidation reactions can be analyzed at equilibrium according.

      ElementReaction$\Delta {G^ \ominus }$ / (J·mol−1)\setlength{\voffset}{0pt}$\ln {K^ \ominus } = - \dfrac{ {\Delta {G^ \ominus } } }{ {RT} }\;(T=1873\;K)$
      C[C] + CO2(g) = 2CO(g)$\Delta {G^ \ominus } = 137890 - 126.52T$6.363
      FeFe(l) + CO2(g) = (FeO) + 2CO(g)$\Delta {G^ \ominus } = 48980 - 40.62T$1.740
      Si1/2[Si] +CO2(g) = 1/2(SiO2) + CO(g)$\Delta {G^ \ominus } = - 123970 + 20.59T$5.484
      Mn[Mn] + CO2(g) = (MnO) + CO(g)$\Delta {G^ \ominus } = - 133760 + 42.51T$3.477
      Cr2/3[Cr] + CO2(g) = 1/3(Cr2O3) + CO(g)$\Delta {G^ \ominus } = - 107179 + 26.31T$3.718
      V2/3[V] + CO2(g) = 1/3(V2O3) + CO(g)$\Delta {G^ \ominus } = - 107993 + 21.29T$4.374
      Note: R and T are the ideal gas constant (J·mol−1·K−1) and the reaction temperature (K), respectively.

      Table 1.  Standard Gibbs free energy ($\Delta {G^ \ominus }$) and equilibrium constant (${K^ \ominus }$) of reactions between elements and CO2 in the molten steel

      As shown in Table 1, the reactions can occur at the steelmaking temperature because the partial pressure of CO is close to zero before the reactions occur [36], and CO2 has the ability to oxidize under steelmaking conditions. Therefore, it is possible to use CO2 as an oxidant in the steelmaking process. Furthermore, the values of ln ${K^ \ominus }$ indicate that CO2 reacts more completely with [C] than other elements at 1873 K. In the actual steelmaking process, the amount of Fe oxidized by CO2 could be negligible because FeO will provide oxygen atoms for the oxidation of other elements in molten steel [23,40].

      The reactions of CO2 with [C] and [Fe] are endothermic, and are opposite with [Si], [Mn], [Gr], and [V]. In addition, the heat release or absorption of reactions between CO2 and [Si] or [Fe] only corresponds to 1/3 of that between O2 and [Si] or [Fe] [19]. According to the actual measurement proposed by Ohno et al. [41], the temperature changes of the fire-spot reaction zone with COMI were calculated by Wei et al. [35], as shown in Fig. 2, where x in the formula in Fig. 2 refers to the volume proportion of CO2 in the top blowing gas. It shows that with a CO2 injection of 15vol%, the temperature of hot spot can be reduced to below 2377 K that is significantly lower than the evaporation temperature of Fe (3023 K). Concurrently, the injection proportion may affect the heat balance of the converter when a large amount of CO2 is input into the converter. Lv [42] found that the surplus heat in the molten pool will be equal to 0 when the proportion of CO2 mixed in O2 is 23.5vol%, which causes the steelmaking to fail. Therefore, we should strictly control the CO2 mixing ratio and adjust the amount of scrap and coolant when the COMI process is used, which will involve a more complex operation model and injection mode.

      Figure 2.  Calculated temperature of the hot spot in the converter with different proportion of CO2. Reprinted by permission from Springer Nature: JOM, Technological innovations of carbon dioxide injection in EAF–LF steelmaking, G.S. Wei, R. Zhu, X.T. Wu, K. Dong, L.Z. Yang, and R.Z. Liu, Copyright 2018.

    • A specific proportion of CO2 instead of O2 will change the oxidation conditions of the steelmaking system, which will affect the oxidation reaction sequence of elements in the molten pool, and potentially control the selective oxidation of steelmaking reactions. Thus, CO2 can be used as the partial oxidant in the steelmaking process to complete the metallurgical functions, such as decarburization, while simultaneously being conducive to the control of the heating rate of the molten pool. Using selective oxidation of carbon and phosphorus by CO2 as an example, the reactions between CO2 and [C] or [P] are shown in reactions (1) and (2), respectively.

      The Gibbs free energy of the reactions (1) and (2) under steelmaking conditions is calculated as Eqs. (3) and (4), respectively.

      where PCO and $P_{{\rm CO}_2} $ are partial pressures of CO and CO2; ${P^ \ominus }$ is the standard atmospheric pressure; fC and fP are the activity coefficients of carbon and phosphorus in the molten steel; [%C] and [%P] mean the carbon and phosphorus mass fraction times 100; ${a_{{\rm{CaO}}}}$ and $ {a}_{\rm{4CaO}}{}_{\cdot{\rm{P}}_{\rm{2}}{\rm{O}}_{\rm{5}}}$ are activities of CaO and 4CaO·P2O5.

      Since $\Delta G_1^ \ominus = {\rm{137890}} - {\rm{126}}{\rm{.52}}T$ and $\Delta G_2^ \ominus = - 144446\;+ 43.22T$, Eq. (5) can be derived.

      The temperature is the conversion temperature of the selective oxidation of [C] and [P] when ΔG1 equals ΔG2. When the temperature of molten steel is less than the conversion temperature, reaction (2) dominates reaction (1) with ΔG1 > ΔG2, illustrating [P] is preferentially oxidized. Similarly, Wang et al. [32,34,43] and Du et al. [4445] investigated Cr retention and V extraction using CO2 in the steelmaking process, respectively. Han et al. [37] concluded that the selective oxidation of carbon and aluminum by CO2 influenced the formulation and control of the RH refining process.

      In addition, the reactions of CO2 with carbon, silicon, manganese, chromium, vanadium, and other elements can produce CO gas; reaction (1) especially increases the volume of gas in molten steel. The generation of gas can improve the stirring conditions of the molten pool and provides a better dynamic condition for the reactions. In summary, CO2 gas has characteristics of weak oxidation, temperature control, and bubble proliferation, which contribute to solving common problems in steelmaking such as dust generation, dephosphorization, and denitrogenation.

    • In the COMI steelmaking process, CO2 and O2 are mixed evenly and blown to the molten pool using an oxygen lance. As shown in Fig. 3, the gas jet flow impacts the surface, produces impact craters, and reacts violently with molten steel in the fire spot area. It is extremely important to investigate the CO2 conversion in this process to determine the CO2 mixing ratio and injection flow rate.

      Figure 3.  Diagram of top blowing CO2–O2 gas in the converter.

      The carbon isotope exchange method was first used in the metallurgical field by Grabke to study the migration process of oxygen on the surface of metal [46], oxide [47], and graphite [48]. Belton and his team [4951] then applied it to the research of the reaction kinetics of CO2–CO and a slag system. In recent years, this method has been widely used to study the reaction kinetics of CO2–CO and the iron oxide system, and to determine the reaction rate constant of the iron oxide system in the reaction system. The authors’ group [5254] studied the CO2 conversion in the COMI steelmaking process using online analysis and the measurement of isotopes; the experimental equipment and principles are shown in Fig. 4 [54]. The experiment results of the CO2 conversion ratio with CO2–O2 reacting with Fe–C melts are shown in Fig. 5 [55]. When the mixing ratio of CO2 was in the range of 0vol%–60vol%, the CO2 conversion ratio decreased with an increase of the CO2 mixing ratio. When the mixing ratio is in the range of 70vol%–100vol%, the CO2 conversion ratio increased because the decarbonization reaction was dominated by O2 when with 0vol%–60vol% CO2, but was dominated by CO2 when with 70vol%–100vol% CO2.

      Figure 4.  Online isotope analysis and measurement platform [54]. Reprinted with permission from University of Science and Technology Beijing, Copyright 2015.

      Figure 5.  Relationship of CO2 conversion ratio and CO2 fraction in CO2–O2 gas when CO2–O2 gas top blowing in Fe–C melts [55]. Reprinted with permission from Science press, Copyright 2019.

      CO2 can react with elements in molten steel and generate a significant amount of CO by utilizing part of the originally wasted energy. The CO content in converter gas is an important index to measure the recovery efficiency of converter gas, which is also closely related to the CO2 conversion. Table 2 [56] shows the main indexes of the converter gas with the COMI and conventional processes. The industrial tests were carried out in a 300-t converter. During the tests, the CO2 proportion in top blowing gas was 5vol%, the bottom blowing N2/Ar was replaced by CO2, and the other conditions were consistent with the conventional process. The resulting calorific value of the converter gas can be promoted by this technology because the CO concentration in converter gas and the converter gas recovery amount was greater than that of the conventional process. Compared with pure O2 injection in steelmaking, CO2–O2 mixed blowing is more beneficial to improving the recovery efficiency of converter gas.

      ProcessComposition / vol%Recovery amount / (m3·t−1)Calorific value / (MJ·m−3)
      COCO2
      Conventional55.6614.51109.207.035
      COMI58.3213.86114.447.372
      Differences 2.66−0.65 5.240.337

      Table 2.  Main indexes of converter gas [56]. Reprinted with permission from University of Science and Technology Beijing, Copyright 2018.

    • The significance of the bottom blowing gas in the converter is to promote the reaction dynamic conditions of the molten pool. Therefore, it is also important to study the CO2 conversion inside the molten steel. As shown in Fig. 6 [39], the CO molecules generated by the reactions between CO2 and elements entering the bubble; therefore, the bubble is generally a mixture of CO2 and CO gas. Li [57] performed experiments to study the CO2 conversion in low carbon and high carbon molten steel. In the experiments, the influence of other elements was not considered since the molten steel was a Fe–C binary system, and the furnace gas contained three parts: protective Ar gas, CO generated by reactions, and unreacted CO2. Therefore, the CO2 conversion ratio can be calculated by the following reaction:

      Figure 6.  Reactions of CO2 with elements inside the molten steel. Reprinted from J. CO2 Util., 34, B.C. Han, G.S. Wei, R. Zhu, W.H. Wu, J.J. Jiang, C. Feng, J.F. Dong, S.Y. Hu, and R.Z. Liu, Utilization of carbon dioxide injection in BOF–RH steelmaking process, 53, Copyright 2019, with permission from Elsevier.

      where ${\eta _{{\rm{C}}{{\rm{O}}_{\rm{2}}}}},\;{q_{{\rm{Ar}}}},\;{q_{{\rm{C}}{{\rm{O}}_2}}},\;{V_{{\rm{Ar}}}},\;{\rm{and}}\;{V_{{\rm{C}}{{\rm{O}}_{\rm{2}}}}}$ are the CO2 conversion ratio, volume flow rate of protective Ar, volume flow rate of CO2, volume fraction of Ar, and volume fraction of CO2 in furnace gas, respectively. The results of the CO2 conversion ratio in the Fe–C melts are shown in Fig. 7.

      Figure 7.  Reaction rate of CO2 in the Fe–C melts during bottom blowing process.

      As shown in Fig. 7, the CO2 conversion ratio inside the melts was mainly related to the temperature of the molten steel and carbon content. The CO2 conversion ratio gradually increased with increasing carbon content because the mass transfer of carbon in the molten steel was easier when the carbon content was higher. Furthermore, the higher temperature promoted the reaction rate between CO2 and elements in molten steel. Notably, the CO2 conversion ratio would be greater than 80% with a smelting medium and high carbon content steel.

    • The metallurgical effect of the COMI technology in the converter steelmaking process was previously reviewed [39]. With a 300-t converter as an example, the energy consumption of the technology can be analyzed, which is summarized in Table 3. The corresponding energy consumption evaluation is calculated as shown in Table 4. The energy consumption of iron loss is decreased by 58.42 MJ/t, which contains the reduction of total iron in the dust and slag. The energy of the dust treatment can be also saved due to the reduction of the generated dust. The quality improvement of the converter gas increases the energy recovery efficiency. Additionally, the improvement in liquid steel cleanliness, such as dephosphorization, denitrogenation, and other metallurgical effects, is also conducive to iron and steel production, but is not easily converted to energy consumption. Therefore, utilization of CO2 in the converter steelmaking process is beneficial to save energy, reduce consumption, and improve product quality.

      TechnologyDust amount /
      (kg·t−1)
      w(Fe)t /
      wt%
      Vc /
      (m3·t−1)
      φCO /
      vol%
      Conventional20.0021.00109.2055.66
      COMI18.0118.49114.4458.32
      Note: w(Fe)t means the total iron content in slag; Vc means the converter gas volume; φCO means the CO concentration in the converter gas.

      Table 3.  The metallurgical effect of the COMI technology

      Energy consumption partEnergy consumption change
      Iron loss−58.42
      Dust treatment−3.81
      Sensible heat of converter gas−8.28
      Chemical calorific value−75.14
      Total−145.65

      Table 4.  Energy consumption change in different energy consumption parts when replacing conventional process with COMI process (MJ·t−1)

    3.   New approach for large-scale disposal of CO2
    • Fig. 8 depicts the process route of the new approach for the disposal of CO2 in a steel factory that includes four parts: industrial tail gas, CO2 recovery system, CO2 consumption and transformation, and high-quality utilization of CO. Industrial tail gas that is rich in CO2 that can be obtained from a power plant, chemical plant, cement plant, and the steel factory itself. In the present project, the liming kiln in a steel factory was chosen as a large point source of CO2. Additionally, the application technology of the CO2 separation, compression, and liquid CO2 storage is relatively mature [5861]. In this way, it consumes the CO2 emitted by iron and steel enterprises, and also saves CO2 transportation costs due to the short distance between liming kiln and steelmaking works. Therefore, the investment cost of CO2 capture will be much lower than that of other CO2 capture and storage (CCS) projects.

      Figure 8.  Process route of the new approach for the disposal of CO2 in a steel factory.

      In this route, CO2 consumption and transformation in a converter is the most important core segment. The cost of steelmaking can be reduced due to the advantages of CO2 used in the converter, which can consume 10–13 kg CO2 per ton steel when 10vol% CO2 is mixed into top blowing O2 and pure CO2 is injected by bottom blowing elements. As analyzed in Section 2.3, if the energy consumption is converted to CO2 emission, the CO2 emission will be reduced by 12.41 kg per ton steel. Therefore, the amount of CO2 disposed in the converter can be more than 20 kg per ton steel synthesizing the amount of CO2 consumption and energy consumption reduction. The utilization of CO2 in converter steelmaking will produce advances in environmental protection and economic benefits as engineering application problems solved.

      The transformation of CO into a high-valued product [6269] has been incorporated in order to further improve the route. In combination with the characteristics of the COMI process that can produce extra CO gas (Table 3), coupling with a CO chemical synthesis technology will continue to improve the economic benefits of iron and steel enterprises. This route uses the steelmaking plant as the hub and provides a method for the joint production of power, cement, and other fields within the steel and chemical industry [7071]. This route is expected to become a large-scale, highly efficient, and valuable method to dispose CO2. The pilot project has been completed and the officially applied project shown in Fig. 8 is under construction.

    4.   Conclusions
    • Based on decades of research, the authors’ team has completed the industrial application of the utilization technology of CO2 as a resource in converter steelmaking. The study reviewed the basic theory of CO2 participating in steelmaking reactions, CO2 conversion, and the energy consumption of the COMI process. A CO2 disposal technology in the steel factory was proposed to improve the original COMI process.

      The potential of CO2 applied in the steelmaking process can be verified and confirmed using theoretical research of CO2 participating in reactions. Various characteristics of CO2 reactions can be combined to solve common problems in the steelmaking process. The CO2 conversion can be controlled with the composition of molten steel at a relatively high level by adjust the steelmaking process. Furthermore, compared to conventional technology, the utilization of CO2 can reduce the energy consumption of the converter steelmaking process, which can be reduced up to 145.65 MJ/t by incomplete statistics. As a result, a route for a new CO2 disposal technology is proposed, which is expected to become a large scale, highly efficient, and valuable method to dispose CO2.

    Acknowledgements
    • This work was financially supported by the National Natural Science Foundation of China (Nos. 51334001, 51674021, 51574021, and 51734003).

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