Contact

Contact name: Jiang Jianguo

Organisation: School of Environment, Tsinghua University, Beijing, PR China
Postal address: Room 806, School of Environment, Tsinghua University, Haidian District, Beijing,
100084, P.R.China
Telephone: 86-10-62783548
Facsimile: 86-10-62783548
Email: jianguoj@mail.tsinghua.edu.cn

Executive Summary
Anthropogenic CO2 which is mainly emitted from the combustion of fossil fuels, is generally
acknowledged to be the primary factor for global climate change. So it is of significant importance
to study and develop effective technology to cut CO2 emission. Steel slag is considered as an
economic material with potential for CO2 sequestration, the use of accelerated carbonation with
steel slag in steel production plant may not only facilitate CO2 capture from the initial source but
also improve resource utilization of steel slag, thereby achieving the goal of ‘waste control by
waste’. This paper aims to help create an experimental and theoretical foundation for the applied
use of accelerated carbonation of steel slag for CO2 capture. In this study, direct gas-solid
carbonation reactions between steel slag and CO2 were conducted with TGA-MS analysis to
investigate the CO2 sequestration effect of steel slag, and also to research the reaction mechanism
and influencing factors in this process. Results showed that, the carbonation reaction between CO2
and steel slag obeyed a two-stage reaction mechanism, namely a several seconds to minutes of fast
sequestration process which was controlled by reaction kinetics, followed by a several hours of
slow sequestration process which was controlled by product layer diffusion. Considering the factor
of total sequestration amount and reaction rate, the ideal CO2 sequestrating temperature of the slag
sample was 450-550°C. The reaction mechanism and CO2 sequestration effect of the slag sample
was almost not influenced when the CO2 content decreased from 100% to 12% (simulated flue gas),
the carbonation conversion of steel slag in the atmosphere of simulated flue gas could also exceed
60%. The maximum CO2 uptake by the steel slag sample could reach 6.93% of its own dry weight
(69.3g CO2/kg slag) in one hour under our experiment conditions. Some conclusions of this paper
are as follows: The existence of Ca(OH)2 is detected in the steel slag sample, this result
theoretically verifies the CO2 sequestration potential of steel slag; Sufficiently high temperature is
required for the start and rapid reaction of direct gas-solid carbonation; Reacting temperature is the
main influencing factor of direct gas-solid carbonation by steel slag, the influence of CO2 content is
not as strong as that of temperature.

Study On The CO2 Sequestration Effect Of

Steel Slag By Direct Gas-Solid Carbonation

Tian, Siconga, Jiang, Jianguoa,b

a
School of Environment, Tsinghua University, 100084 Beijing, PR China
b
Key Laboratory for Solid Waste Management and Environment Safety, Ministry of
Education of China, PR China
ABSTRACT

Direct gas-solid carbonation reactions between steel slag and CO2 were conducted to study the CO2
sequestration effect of steel slag. Elemental and mineral compositions of the solid sample were
analyzed with XRF and XRD, whose contents of calcium and Ca(OH)2 were 28.34% and 17.8%
respectively. Reaction temperature and CO2 content, two factors which influence the CO2
sequestration effect most were researched in this study. Results showed that, the fast reaction
kinetics-controlled process which contributed to 43.1%-64.3% of the total CO2 uptake, would
generally last for a few tens of seconds, then it came to a slower product layer diffusion-controlled
process for several hours; When the reacting temperature was increased to 270°C, the CO2
sequestration rate of the slag sample would accelerate sharply with 400-450°C achieving the
maximum rate, and the relatively ideal sequestrating temperature of the slag sample was 450-550°C;
The CO2 sequestration effect of the slag sample was not obviously influenced when the CO2 content
was decreased from 100% to 12% (simulated flue gas). The maximum CO2 uptake by the steel slag
sample could reach 6.93% of its own dry weight (69.3g CO2/kg slag) in one hour under our
experiment conditions. The use of steel slag to sequestrate CO2 in flue gas by accelerated
carbonation may not only enhance the resource utilization of steel slag but also reduce greenhouse
gas emissions, thereby achieving the goal of ‘waste control by waste.’ This study helps create an
experimental and theoretical foundation for the applied use of accelerated carbonation to cut CO2
emission.

Keywords: Steel slag, Direct gas-solid carbonation, CO2 sequestration, temperature, CO2 content

INTRODUCTION

Anthropogenic CO2 emission, mainly caused by fossil fuel combustion, is generally acknowledged
to be the primary factor for global climate change. And the atmospheric CO2 concentration has been
rapidly increased from 280 ppm in the pre-industrial era to 380 ppm at present (Pachauri et al.,
2007). Thus, it is of significant importance to study and develop effective technology to cut CO2
emission.

Among the different options of “carbon capture and storage”, mineral carbonation which is
originally proposed by Seifritz (1990) is a promising technology that can contribute to the reduction
of CO2 emission. In this process, CO2 reacts with certain alkaline minerals which are rich in
calcium or magnesium to make it sequestrated. Mineral CO2 sequestration has a potential advantage
of forming thermodynamically stable carbonates to make the storage of CO2 permanent and
inherently safe. As the proceed of natural mineral carbonation is too slowly to effectively mitigate
CO2 emission, alkaline industrial residues, such as steel slag, pulverized coal ash, MSWI fly ash
and bottom ash, and tailings in the smelting process of certain metals (Goldberg et al., 2001), which
are available in relatively large amounts and are generally rich in Ca or Mg, can be presented as an
alternative feedstock for mineral CO2 sequestration. Their major advantages compared to natural
minerals are their extensive availability and cheap costs, and these residues tend to be more reactive
for carbonation than natural minerals due to their chemical instability and thus their use might
enable a reduction of the energy consumption and costs for CO2 sequestration (Sun et al., 2008).
Moreover, studies have found that the natural carbonation process can be accelerated using different
sources of CO2 and various methods (Gerven et al., 2005; Bertos et al., 2004; Gerven et al., 2004).
Gunning et al. (2010) have investigated the CO2 sequestration capacity of seventeen industrial
wastes, such as cement kiln/bypass dusts, paper sludge incineration ash, and MSWI fly ash, by
accelerated carbonation on the conditions of adding certain water, Results show that many industrial
residues have the potential to sequestrate CO2.

Stainless steel slag is one of the major, growing, waste streams, so it has been considered as an
economic material with potential for CO2 sequestration. Thus, the use of accelerated carbonation
with steel slag may not only reduce greenhouse gas emissions but also improve resource utilization
of steel slag, thereby achieving the goal of ‘waste control by waste’. Although the total CO2
sequestration capacity of industrial residues, such as stainless steel slag, is limited, this alternative
technical route could facilitate the CO2 capture from initial source at sites where both large
quantities of CO2 and suitable solid residues are produced, such as steel production facilities and
municipal waste incineration plants. This paper presented the material characterization of steel slag,
studied the influence of possible process variables during the gas-solid carbonation reaction, and
evaluated the CO2 sequestration capacity of this sort of residue.

MATERIALS AND METHODS

Steel Slag Sample

The slag used in this experiment was obtained from the steel converter of the capital steel plant in
Beijing, China. The fresh slag which was sampled after water-washing, crushing, and magnetic
separation was grinded into smaller particles that could pass through a 200-mesh screen (particle
size＜74 um) at ambient temperature in closed environment, and then was kept in the dark in
air-emptied, sealed containers until use.

Materials Characterization
Characterization of the steel slag sample involved the surface microstructure, elemental content, and
mineralogical composition. The morphologies of the slag sample were observed under
JSM-6460LV scanning electron microscope. Main parameters of the apparatus were 20KV, 3nm,
Be4-U92, 133ev; X-Ray Fluorescence (XRF) was performed to analyze the composition and content
of elements in the slag sample by XRF-1800 Analyzer. The mineral phases in the fresh slag were
identified by X-Ray Diffraction (XRD), using O8DISCOVER Analyzer. The equipment’s
operational conditions were 40 kV, 40mA, 0.02°. The 2θ range between 5o and 100o was scanned
and the database from the software JADE5 was used for the identification of the crystalline phases.

Carbonation Experiments
The fresh slag was firstly heated continuously using METTLER TGA/DSC 1 from 50°C to 650°C
in 100% CO2 atmosphere at the rate of 10°C/min. Then TGA-MS analysis was used to investigate
the direct gas-solid carbonation reactions between CO2 and steel slag at 350°C, 400°C, 450°C,
500°C, and 550°C separately under the conditions of 100% CO2 atmosphere and atmospheric
pressure for 1 hours. Lastly, the conditions of 100% CO2 and 12% CO2 + 10% O2 +78% N2
(simulated flue gas) at 550°C were compared to study the influence of CO2 content on the CO2
sequestration effect of steel slag.

CO2 sequestration amount of the steel slag sample was determined with the thermal gravimetrical
analysis method. The uptake of CO2 was calculated from the sum between the percentage of weight
gain in CO2-containing atmosphere of the slag sample and its percentage of weight loss in Nitrogen
at the same temperature and other operating conditions. The carbonation conversion ηCa was
determined from the available Ca content of the fresh slag (Caavailable), the molar weights of Ca
(MWCa) and CO2 (MWCO2), and the uptake of CO2 by dry weight. In eq. 1, it is assumed that only
Ca is carbonated during the carbonation process.
MWCa (g / mol)
CO 2 (wt %) ×
MWCO2 (g / mol)
ηCa (%) ×100 (1)
Ca available (g / g)

RESULTS AND DISCUSSION

Physical And Chemical Properties Of The Steel Slag Sample

Surface microstructure
The morphologies of the fresh and carbonated slag samples were showed in Fig. 1. The image of
the fresh sample (Fig. 1(a)) showed the existence of layer-like crystals which was the characteristic
shape of Ca(OH)2. After the carbonation experiments, sample particles (Fig. 1(b)) were more
rounded and the layer-like structure disappeared generally, some granular-textured crystals
precipitated between the platy particles of the initial mineral. Such a variation can be attributed to
carbonation, that is, the formation of CaCO3, whose typical crystal shape is hexagonal and
rhombohedral.

(a) Fresh slag sample (b) Carbonated slag sample

Fig. 1. SEM image of the steel slag sample (5000 times amplified)

Elemental composition
It can be concluded from Table 1 that, the concentrations of Ca (28.34%) and O (44.81%) were
quite high, and other major elements included Al, Mg, Fe, Si, and F, whose content were all above
1%; carbon content of the fresh slag was 0.95%. The slag sample derived from the steel converter
residues after the process of water-washing, crushing, and magnetic separation, so the concentration
of Fe was not high due to its being sufficiently recycled. And the dominantly high contents of O, Ca,
Al, Mg, and Fe indicated that the slag was mainly composed of various metal oxides.

Table 1. Elemental composition of the steel slag sample (mean, n = 3)

Element Content（%） Element Content（%） Element Content（%）

O 44.812 C 0.95 Cr 0.0833
Ca 28.3448 Mn 0.6128 Ba 0.0745
 Al 6.4143 Ti 0.3824 Cl 0.0333
Mg 6.0316 S 0.2543 Sr 0.0163
Fe 5.3428 K 0.2046 Zn 0.0148
Si 5.0845 Na 0.1724 Zr 0.0095
F 1.023 P 0.1309 Nb 0.0077

Mineral composition

3000
◆
◆ Ca(OH)2
2400
Intensity (Counts)

1800
◆

1200
◆ ◆
◆

600

0
10 20 30 40 50 60
2θ (o)

Fig. 2. XRD analysis of the available Ca in the steel slag sample

XRD analysis of the slag sample showed that its main mineral composition was Ca(OH)2, CaCO3,
Ca3Fe2(SiO4)3, Ca2SiO4, and (CaO)12(Al2O3)7 after compared with the standard pdf-2 of ICCD using
JADE 5. The XRD spectrum between 10o to 65o was specially analyzed for the component and
content of Ca which is available for the carbonation reaction to sequestrate CO2 (Fig. 2). It showed
the existence of Ca(OH)2 whose content was 17.8% calculated from the area integral of the main
components in the entire XRD spectrum in the slag sample. This result theoretically verified the
CO2 sequestration potential of the steel slag sample.

Reaction Temperature
Fig. 3 showed the influence of temperature on the CO2 sequestration rate of the slag sample. It can
be inferred from the net weight range curve (bold solid) which was derived by the subtraction of the
percentage of weight range in CO2 atmosphere and in N2 atmosphere that, the slag sample almost
had no capture effect on CO2 below 270°C, and then the CO2 sequestration rate began to accelerate,
with 400-450°C achieving the maximum rate. Then the reaction rate all along kept at a relatively
high level till the temperature was continuously increased to 650°C, indicating that the surface
adsorption of CO2 has not came to saturation.
 In N2 atmosphere In CO2 atmosphere Subtraction curve

100
8

98
Percentage of weight (%)

Net weight range (%)

6
96

94 4

92
2
90

88 0
100 200 300 400 500 600
Temperature (℃)

Fig. 3. CO2 sequestration curve of the steel slag sample under continuous change temperatures

The direct gas-solid carbonation reactions between CO2 and the slag sample under isothermal
temperatures were showed in Fig. 4. It can be concluded that the sequestration of CO2 by steel slag
obeyed the same reaction mechanism under different temperatures, namely a several seconds to
minutes of fast sequestration process which was controlled by reaction kinetics, followed by a
several hours of slow sequestration process which was controlled by product layer diffusion. The
sequestration amount of CO2 increased from 0.84% at 350°C to 6.93% at 550°C in one hour.
Considering the factor of total sequestration amount and reaction rate, the ideal sequestrating
temperature of the slag sample was 450-550°C.
 7.5
550℃

Sequestration amount (%) 6.0

4.5 450℃

3.0 500℃

400℃
1.5

350℃
0.0
0 10 20 30 40 50 60
Time (min)

Fig. 4. CO2 sequestration curve of steel slag at different isothermal temperatures

CO2 Content
Carbonation reactions of steel slag with two different combinations of gases, 100% CO2 and 12%
CO2 + 10% O2 +78% N2 (simulated flue gas) were compared in Fig. 5. It was showed that, in the
whole reacting process of one hour, the two curves were all long quite close, with the total
sequestration amount of CO2 reaching 6.93% and 6.49%, respectively. The reaction mechanism and
CO2 sequestration effect of the slag sample was almost not influenced when the CO2 content
decreased from 100% to 12%, the carbonation conversion of steel slag in the atmosphere of
simulated flue gas could also exceed 60%. In terms of the direct gas-solid carbonation reaction, the
influence of CO2 content was not as strong as that of temperature.
 7.5
12% CO2+10% O2+78% N2
100% CO2
Sequestration amount (%) 6.0

4.5

3.0

1.5

0.0
0 10 20 30 40 50 60
Time (min)

Fig. 5. CO2 sequestration curve of steel slag under different CO2 contents at 550°C

Characterization Of The Sequestration Effect

CO2 sequestration effect of steel slag by direct gas-solid carbonation was analyzed in Table 2. It can
be inferred that, in the reaction kinetics-controlled process, the CO2 sequestration amount and rate
of the slag sample were both increased with the increase of reacting temperature from 350°C to
550°C; when the temperature was over 450°C, the sequestration rate would accelerate rapidly, and
the reaction time would also decreased sharply; the sequestration contribution of the reaction
kinetics-controlled process accounted for 43.1%-64.3% of the total sequestration amount in this
experiment, and was nearly not influenced by reacting temperature. The total CO2 sequestration
amount of the slag sample was also obviously influenced by temperature in one hour’s reaction time,
and has been improved by a factor of 8.25 from 350°C to 550°C, with the maximum carbonation
conversion reaching 65.5% at 550°C.

Table 2. Analysis of CO2 sequestration effect of steel slag at different reacting temperatures

Reaction kinetics-controlled process Total

Sequestration Reaction Sequestration Sequestration sequestration Carbonation
Temperature amount time rate contribution amount conversion
(°C) (g/Kg slag) (s) (g/Kg slag·s) (%) (g/Kg slag) (%)
350 5.4 174 0.03 64.3 8.4 8.0
400 7.1 57 0.12 55.9 12.7 12.1
450 23.0 118 0.19 52.6 43.7 41.3
500 17.6 17 1.0 43.1 40.9 38.7
550 34.8 32 1.1 50.2 69.3 65.5

CONCLUSION
The existence of Ca(OH)2 is detected in the steel slag sample, this result theoretically verifies the
CO2 sequestration potential of steel slag.

Sufficiently high temperature is required for the start and rapid reaction of direct gas-solid
carbonation. For the steel slag sample in this experiment, the relatively ideal sequestrating
temperature is 450-550°C.

Reacting temperature is the main influencing factor of direct gas-solid carbonation by steel slag, the
influence of CO2 content is not as strong as that of temperature.

The reaction mechanism and CO2 sequestration effect of steel slag is almost not influenced when
the CO2 content decreased from 100% to 12% (simulated flue gas). This helps create an
experimental foundation for the applied use of accelerated carbonation of steel slag for CO2 capture.

ACKNOWLEDGMENTS

The authors gratefully acknowledge the National Natural Science Foundation of China for financial
support (Grant No. 50778099).

REFERENCES

Bertos, M. F., Simons, S.J.R., Hills, C.D., & Carey, P.J. (2004): A review of accelerated carbonation
technology in the treatment of cement-based materials and sequestration of CO2. Journal of
Hazardous Materials B112, pp. 193-205.
Gerven, T. V., Geysen, D., & Vandecasteele, C. (2004): Estimation of the contribution of a
municipal waste incinerator to the overall emission and human intake of PCBs in Wilrijk,
Flanders. Chemosphere 54, pp. 1303-1308.
Gerven, T. V., Keer, E. W., Arickx, S., Jaspers, M., Wauters, G., & Vandecasteele, C. (2005):
Carbonation of MSWI-bottom ash to decrease heavy metal leaching, in view of recycling.
Waste Management 25, pp. 291-300.
Goldberg, P., Chen, Z. Y., O’Connor, W. K., Walters, R. P., & Zoick, K. (2001): CO2 mineral
sequestration studies in US. Journal of Energy and Environmental Research 1(1), pp. 117-126.
Gunning, P. J., Hills, C. D., & Carey, P. J. (2010): Accelerated carbonation treatment of industrial
wastes. Waste Management 30, pp. 1081-1090.
Pachauri, R. K., & Reisinger, A. (2007): Climate Change 2007 Synthesis Report of the IPCC Fourth
Assessment Report. From IPCC, Publications (2007):
http://www.ipcc.ch/pdf/assessment-report/ar4/syr/ar4_syr_cn.pdf
Seifritz, W. (1990): CO2 disposal by means of silicates. Nature 345, pp. 486.
Sun, J., Bertos, M. F., & Simons, S. J. R. (2008): Kinetic study of accelerated carbonation of
municipal solid waste incinerator air pollution control residues for sequestration of flue gas
CO2. Energy & Environmental Science 1, pp. 370-377.