Materials Science Forum Submitted: 2017-04-13

ISSN: 1662-9752, Vol. 904, pp 162-166 Revised: 2017-04-14

doi:10.4028/www.scientific.net/MSF.904.162 Accepted: 2017-04-24
© 2017 Trans Tech Publications, Switzerland Online: 2017-08-22

Influence of Pretreatment on the Free CaO in Steel Slag

Longhua Wei1,a, Xianjin Qi1,b, Xing Zhu,2,3,c,*, Hua Wang2, Bin Hu3, Yuan Xu1,
Yong Li2, Xun Li1
1
Faculty of Chemical Engineering, Kunming University of Science and Technology,
Kunming 650504, China
2
State Key Laboratory of Complex Nonferrous Metal Resources Clean Utilization/Faculty
of Metallurgical and Energy Engineering, Kunming University of Science and Technology,
Kunming 650093, China
3
Kunming Iron & Holding Co.,Ltd.
a
546817308@qq.com, b229844938@qq.com, czhuxing2010@hotmail.com

Keywords: Steel slag, Free CaO, Cooking, Autoclave

Abstract. An experimental program was carried out to investigate how to improve the characteristics
of steel slag. Mainly the pretreatment methods of cooking and autoclave were used to detect such as
free CaO content in the steel slag. The physical and chemical characteristics of steel slag were
measured by X-ray diffraction (XRD) and fluorescence (XRF) analysis. The aim of improving the
slag utilization is an important way to resolve large production problem, and then the research
progress of steel slag utilization at home and abroad are recycled as raw material to be applied. By
means of those ways to manage steel slag we have received the following conclusions: With the
increase of cooking temperature the content of free CaO is gradually reduced. When temperature
higher than 90oC the means could greatly reduce the free CaO content from about 7% wt. to less than
2.5% wt. in 3 h. By means of autoclave pressure upto 1.5MPa could greatly reduce the free CaO
content from about 7% wt. to less than 3.2% wt. in 3 h. Through the study of the relevant of steel slag
after pretreatment can effectively reduce the free CaO content in the steel slag, improving the stability
of the steel slag is advantageous to the seven used in the construction field.

1. Introduction
China is the world's first big iron and steel production country, steel slag produced every year is
about 10%~12% of steel production, steel slag in China has nearly one hundred million tons of
emissions, the simple disposals of these wastes are becoming less attractive which not only occupies
plenty of land but also increases the disposal costs[1]. The main composition of steel slag and cement
are similar, have certain gelling property, so it is a kind of potential resources. If it can be fully used, it
will not only solve the problem of environment, but also bring certain economic benefits. Therefore, it
is desirable to recover the valuables and utilize these wastes.
Although the several main chemical composition of steel slag and cement is the same as the
gelling of cement activity because of the several kinds of main components. Due to the low activity of
steel slag and contains some unstable free CaO and free MgO[2-3]. These ingredients fully hydrated
need to experience a very long time, and with the volume expansion, large dosage of steel slag will
cause severe cracking of building materials[4] products volume stability problems lead to the failure
to a large number of applied in construction industry. As a result, in order to improve the utilization of
steel slag, improve activity and reduce the content of free CaO is one of the effective ways to solve the
problem. Han Jiaxing etc[5]. in steel slag steam pressure stabilization pretreatment technology
research mentioned through the study of the steam pressure of steel slag processing, significantly
lower content of free CaO, free CaO generated after reaction with water in the process of Ca(OH)2,
improves the stability of steel slag. Zhang zhiguo etc[6]. was waiting in the pretreatment of steel slag
autoclaved brick making study of the mentioned after different temperature wet process found that the
temperature in more than 55oC, can significantly improve its stability. In this paper, we use the

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 Materials Science Forum Vol. 904 163

autoclave and cooking different pretreatment methods, understanding of steel slag free CaO content
changes.

2. Materials and Methods

2.1. The Raw Material
Chemical and mineral composition of steel slag are influenced by steelmaking process, raw
materials, and varieties of steelmaking process. This experiment using steel slag from southwest and
fever of a steel mill steel slag samples, X-ray fluorescence (XRF) analysis, tested the chemical
composition of steel slag are listed in table 1.
Table 1. Chemical composition of steel slag(/wt%).
Element O Ca Fe Si Mn Mg C P Ti V Al
Content 43.29 28.55 15.24 2.91 2.41 2.41 1.43 0.96 0.93 0.81 0.51

The main chemical composition of steel slag is CaO, SiO2, Fe2O3 and MgO style, account for
more than 80% of composition. At the same time steel slag contains a small amount of free CaO and
free MgO. In the trace elements, P2O5 is larger influence on the activity of steel slag, it can combined
with CaO and SiO2 can generate active poor guy Schmidt stone, hinder the formation of tribalism
silicate.
(A) (B) 0.8
 Ca2SiO4 200-300 purpose
 Ca2Fe2O5 100
 Ca(OH)2
Intensity(Counts)

FeO 0.4
DSC(mW/mg)


RO
98

Mass (%)


0.0

96


 

-0.4 94
20 40 60 80 0 200 400 600 800 1000
o
2/( ) o
Temperature( C)
(C) 8
7

6
Weight/kg

4
4 3.7
3
2
2
1.2
0.9
0.6
0
0.037 0.15 0.25 0.42 0.84 2 4.75 9.5 13.2
Size/mm
Fig. 1. The XRD patterns (A) the TG-DSC curve (B) temperature from 25oC up to 1000oC particle
size distribution(C) of steel slag fever sample.
Fig.1.A shoes the XRD diagrams of steel slag which size in 200-300 purpose particle. From the
XRD we can see that steel slag is the main crystal type Ca2SiO4, Ca2Fe2O5, Ca(OH)2, FeO and RO.
Among them the highest peak characteristics is Ca(OH)2, it can correspond the content of table.1
pointed out that the most part containing in steel slag is Ca(OH)2. From Fig.1.B TG-DSC which
temperature is from 25oC up to 1000oC when the thermo gravimetric curve. When the temperature at
100oC and 450oC heat absorption peak appears, the corresponding weightlessness curve from
400~450oC slope great weightlessness is obvious, the reason is that water at 100oC evaporation
absorbs heat, and during 400~450oC is the Ca(OH)2 endothermic decomposition H2O and CaO. As
164 Metallurgy Technology and Materials V

can be seen from the Fig.1.C, the steel slag particle size are mainly distributed in the range of
0.84~13.2mm, as many as 79.02%, the most abundant in 0.84~2mm, up to 31.25%. To see our
selection of test sample, needs to be broken after screening, to maintain the uniformity of the sample.
2.2. Pretreatment of Steel Slag
Treatment of cooking[7], random said take 200g steel slag samples, add 0.12 times the mass
ratio of water, stir evenly into the sample cup after seal preservation. Into the YH-40B standard
sample of the constant temperature and humidity curing box, cooking with different temperatures,
respectively. According to the experiment method of table.2. for more groups of experiments under
different temperature for 3 hours.
Table 2. Steel slag cooking test.
Steel slag quantity(g) 200 200 200 200
Water(mL) 24 24 24 24
o
Temperature( C) 30 50 70 90
Time(h) 3 3 3 3
Treatment of autoclave, weighing 100g steel slag in the middle of 100mL small beaker, the
beaker for type YZF-2Acement pressure steaming kettle in the autoclave experiment under different
pressure. According to the experiment method of table.3. for more groups of experiments under
different pressure for 3 hours.
Table 3. Steel slag autoclave test.
Pressure(MPa) 0.6 1.0 1.5
Time(h) 3 3 3
o
Temperature( C) 162 183 203

3. Results and Discussion

3.1 Effect of Cooking Temperature

Fig. 2. The XRD patterns (A) the TG-DSC curve (B) temperature from 25oC up to 1000oC and free
CaO content (C) temperature from 30oC to 90oC of steel slag fever sample.
 Materials Science Forum Vol. 904 165

The general observation concerning X-ray diffraction analyses in the final samples was show in
Fig.2.A, by Fig.2.A can be seen in 18 degrees when object characteristic peak for Ca(OH)2, under the
condition of different temperatures of 90oC when the Ca(OH)2 has the highest characteristic peak, it
shows that steel slag at 90oC crystalloid is best, it is easier to form the Ca(OH)2. In 35 degree angle
when the temperature is a special object is disclaim silicate peak, when the temperature is 90oC the
diffraction peak is better than other temperature, crystalloid that 90 degrees is the best. Combining
with the Fig.2.B TG-DSC curve for steel slag, the thermal decomposition process can be roughly
divided into three stages[8], first stage: 25~100oC, 100oC of exothermic peak because of steel slag at
100oC water evaporation. The second stage 100-450oC, at 450oC endothermic peak and evident in the
weightlessness trends, it is because in the 400-450oC the Ca(OH)2 endothermic decomposition
reaction of water and calcium oxide. The third stage 450~1000oC, for the exothermic peak of around
1000oC should be attributed to the crystallization process of steel slag. With the increase of
temperature of smooth weightlessness curve appeared more obvious stepped down process. From
DSC curve, the different temperature of the sample is very similar to the DSC, at 90oC under the
conditions of cooking 450oC peak area is the largest, curve weightlessness is also the most.
Instructions under this temperature free CaO turn into Ca(OH)2. From Fig.2.C we could, as well as,
find that when temperature elevated up to 90oC, steel slag has the lowest free CaO content. This can
completely corresponding to the Fig.2.A, B mentioned.
3.2 Effect of Autoclave Pressure
(A) (B) 0.6 102
Ca2Fe2O5 0.6MPa
 Ca2SiO4 1.0MPa
 Ca(OH) 0.4 1.5MPa 96
2
Intensity(Counts)


   0.6(MPa) 0.2
DSC(mW/mg)

90

Mass(%)

   1.0(MPa) 0.0
84

-0.2
   1.5(MPa) 78
-0.4
20 40 60 80 0 200 400 600 800 1000
o
2/° Temperature（ C）
(C)6
Free CaO Content/%

2
0.8 1.2 1.6
Pressure/MPa
Fig. 3. The XRD patterns (A) the TG-DSC curve (B) temperature from 25oC up to 1000oC and free
CaO content (C) pressure from 0.6 to 1.5MPa of steel slag fever sample.
The XRD patterns of the treated steel slag, the residual parts of the steel slag after for autoclave
3 h are presented in Fig. 3.A. The mineralogy of the steel slag was somewhat similar to that of the
cement clinker, exhibiting a predominance of Ca phases. The calcium which exists as various forms
of compounds like Ca2SiO4. After the autoclave treatment, the intensity of portlandite peaks
decreased significantly while the ratio between calcite and portlandite peaks increased, indicating the
reaction of Ca(OH)2 with CO2. Under the condition of 1.5MPa pressure peak strength are stronger
than the other, for the residual parts of the steel slag after milling wherein the active minerals were
166 Metallurgy Technology and Materials V

relatively less than other parts, and the contents of RO phases such as Calcium Manganese Oxide.
Fig. 3. B showed the weight loss of the samples obtained by TGA after 3 h carbonation. This weight
loss occurred following two phases: the first one corresponds to the Ca(OH)2 content, which followed
by the second one that carbon dioxide lost and resulted from the decomposition of CaCO3 . It was
clearly that Ca(OH)2 in steel slag was almost carbonated to CaCO3[9], additionally, about 3% of the
clinker minerals was carbonated by calculation. Fig. 3. C shows the free CaO content change under
different pressure. 1.5MPa has lower free CaO than other condition , however. Thus, Combined with
Fig. 3. A, B, elevated pressure can effectively reduce the content of free CaO.

4. Conclusion
Based on the study presented in this paper, the following conclusions are drawn:
1. Cooking temperature higher than 90oC could greatly reduce the free CaO content from about
7% wt. to less than 2.5% wt. in 3 h.
2. The use of autoclave in concrete mixes was useful in reducing the environmental problems
created by dumping steel slag, and was also helped to maintain sustainability of the environment by
reducing the carbon dioxide levels in the atmosphere. By means of autoclave pressure upto 1.5MPa
could greatly reduce the free CaO content from about 7% wt. to less than 3.2% wt. in 3 h.
In short, the successful utilization of steel slag as aggregate in pavement construction provided a
new and more cost effective approach for aggregate resources, and decrease the threats of solid wastes
to environment[10]. However, more studies should be carried out on its durability in future.

Acknowledgement
This work has been supported by the Applied Basic Research Program of Yunnan Province
(project Nos. 2016FB090, 2014FB123), Scientific and Technological Leading Talent Projects in
Yunnan Province (No. 2015HA019), the candidate talents training fund of Yunnan Province
(No.2014HB006), and the College and enterprise funds (Grant No. KKZ4201552002).

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