Alite modification by SO3 in cement clinker – an industrial trial

Li Xuerun, Ma Bing, Chen Wenping, Shen Xiaodong*

State Key Laboratory of Materials-Oriented Chemical Engineering, College of Materials Science and
Engineering, Nanjing Tech University, Nanjing 210009, China

Abstract
Alite in industrial clinker is usually M3 type as the presence of MgO. It is also reported that the M3 type of alite
performs not as good as the M1 type. A promised 10% increment of the strength by the modification of M3 to M1
was reported. SO3 can modify alite polymorph in the MgO contained clinker.
In this paper, the modification of alite by SO3 was performed in an industrial production line with the production
of 2000 t per day. The mineral composition of the clinker and the formation of clinker were investigated. The
modification of the alite polymorph on industrial line was made by addition of desulfurized gypsum into the raw
meal. 1.15~1.39% of SO3 in the clinker could yield M1 alite for clinker with ~2.66% MgO. Within the gypsum
amount added, clinker can be produced, but more attention should be paid to maintain a steady production of the
clinker.
Alite content decreased as the existence of extra SO3 in the clinker, which complicated the relationship between
the alite polymorph and the compressive strength. All the mechanical properties fall in the demand of the standard.

Originality
We obtained the modification method of M3 to M1 alite by simply introducing SO3 in the form of gypsum for
industrial trial, which proved the potential for the application of technique in large scale. The industrial trial
provided details of the advantages and disadvantages of SO3 dosage in the real production situation. More
characteristics of the M3 and M1 alite were confirmed by high resolution XRD, providing more evidence for the
identification of alite polymorph.

Key words: alite polymorph, modification, industrial trial

* Corresponding author: xdshen@njtech.edu.cn; tel: 86-25-83587234

1. Introduction
Alite in works clinker is mainly M3 polymorph (Maki and Goto 1982, Maki and Kato 1982, Taylor 1997) as
the present of MgO which cannot be avoided as the co-growth of dolomite and calcite. It was reported that
M3 alite performed not as well as M1 alite which can be stabilized with SO3, yielding a 10% increment of
the strength (Staněk and Sulovský 2002). The MgO/SO3 governs the alite polymorph relationship based on
statistic testing of a series of works clinker as shown in Figure 1 (Maki and Goto 1982).

Figure 1 Relationship between MgO/SO3 in the clinker and alite polymorphs, reproduced figure according to Ref (Maki and
Goto 1982, Taylor 1997)

The characterization of alite polymorph is mostly done with the XRD patterns. A closer look into the
characteristic windows/range would provide valuable information of the polymorphism of alite. There are
two widely used windows for identification of M1 and M3, 29~32°and 51~52°(Cu Kα radiation) (Maki and
Kato 1982, Taylor 1997), besides these two windows, Courtial (Courtial, de Noirfontaine et al. 2003) found
three additional windows for the identification of M1 and M3 alite, which make the identification more
reliable and efficient recently confirmed by Wang (Wang, Li et al. 2014) using high resolution powder XRD
equipment.
However, there are also some potential risks for adding SO3 into the raw meal: i) an over dosage of SO3
would harm for the kiln system by forming kiln rings (Taylor 1997); ii) SO3 itself would be harmful for the
formation of alite (Li, Xu et al. 2014); iii) an elevated SO3 was not good for the dimension stability of the
cement (Horkoss, Lteif et al. 2011); iv) instabilities for the kiln operation.
In this paper, the modification of alite by SO3 was performed in an industrial production line with the
production of 2000 t per day. The mineral composition and formation of clinker were investigated. The
influence of the alite modification on the compressive strength was tested. We also try to confirm the
documented risks caused by SO3.

2. Experiment
Approximate 0.9~1.5% SO3 in clinker was introduced by adding desulfurize gypsum in the raw meal
on production line of 2000 t clinker per day. Clinker samples were collected with 1 hour interval on the
production line, and then the data were averaged by mixing 24 hours in the ball mill to represent the clinker
for a whole day. Once the composition of the raw meal was modified, mixed sample was done for 8 hours
(i.e. within one day, there were three averaged samples: night, day and middle). The resulting testing was
performed on the homogeneous samples.
All the production parameter were monitored continuously. Special attention was paid on the amount of
clinker produced, total usage of coal (this was also related to the energy consumption), temperature of
secondary wind and the electricity used for the kiln. All these parameters were used to evaluate the overall
production process and the energy consumed for the industrial production for the clinker.
The mortar compressive strength of the clinker was tested according Chinese standard (GB/T 17671-
1999). The chemical composition of the clinker was done using XRF by PANalytical spectrometers.
XRD data were collected using Rigaku Smartlab working at 45 kV 200 mA and Rigaku Miniflex 600
working at 40 kV, 15 mA. Mineral composition of the clinker was obtained using the Rietveld analysis. More
detailed experimental process and the parameter related to the XRD data can be fine in Ref (Li, Xu et al.
2014, Wang, Li et al. 2014).
The overall trial was done for 11 days from the initial time gypsum was added into the raw meal to the
SO3 content in the clinker dropped back to the normal amount. The corresponding samples were labelled
with the date.

3. Results and discussion

3.1. Operation parameters for the kiln
The SO3 addition did show disturbance of the operation system for the production line. The operation
parameters during the industrial trial were monitored. Total amount for the coal used in the kiln and the
temperature for the secondary wind were shown in Table 1. SO3 addition into the raw meal (began at 21)
disturbed the steady coal used and the temperature of the secondary wind. The resulted clinker nodules were
not as big as the normal production (see Figure 2), which would cause storage difficulties.
The expected risk of kiln rings caused by the deposition of alkali sulfates was not occurred during the
trial. No extra amount of deposition materials in the kiln system and the pipes were observed. The SO3
emission was also within the limit of the standard.
Table 1 Kiln parameter during the industrial trial

Labels Coal used Temperature of the secondary wind SO3

(kg per ton clinker) (℃) (% in clinker)
16a 137.0 1108.9 0.37
18 136.7 1106.3 0.42
19 140.0 1097.6 0.46
20 143.5 1078.9 0.40
21 130.6 1057.3 0.55
22b 115.2 953.1 0.92
23 113.0 889.5 1.15
24 125.5 940.8 1.37
25 130.3 946.8 1.36
26 130.0 1023.7 1.22
27 135.5 1087.8 1.28
28 night 140.0 1110.4 1.27
28 day 140.0 1097.3 1.29
28 middle 140.0 1102.4 1.27
Notes: a. normal production of clinker from 16-21.
b. addition of gypsum into the raw meal.
 Figure 2 Clinker nodules for (a) ordinary production and (b) industrial trial with SO3

3.2. Mineral composition

The mineral composition of the produced clinker showed a decreasing trend for the C3S content with
the increase of the SO3 content in the clinker (see Figure 3), which is in agreement with the previous results
(Horkoss, Lteif et al. 2011, Li, Xu et al. 2014). The underlying reason could also be the drop of the sintering
temperature in the kiln (see Table 1).

80 C3S % C2S %
C3A % C4AF %
70
60
Content (%)

50
40
30
20
10
0
21 22 23 24 25 26 27 28 29 30 31 32
Date

Figure 3 Mineral composition for the clinker produced during the trial

3.3. Alite polymorphism

SO3 in the high MgO content clinker could modify the alite polymorphs. When SO3 content lower than
0.65%, M3 alite presents in the clinker. While the content of SO3 goes up to 0.9~1.4%, M1 alite is the main
phase in clinker. There are 8 characteristic windows for the identification of M1 and M3 type of alite (see
Figure 5), 5 of which are the same as the characters discussed by Courtial (Courtial, de Noirfontaine et al.
2003) and Taylor (Taylor 1997) and Maki (Maki and Kato 1982). To obtain the characteristics of the
identification of M1 and M3 alite, higher angle resolution is needed, and the Kα2 line of Cu radiation should
better be removed (Li, Xu et al. 2014, Wang, Li et al. 2014).
Based on the XRD patterns, the alite polymorphs were classified. A visual plot of the polymorph of alite
and MgO/SO3 content was then given in Figure 5. To get the MgO/SO3 value, the effective MgO was obtained
by deducting the periclase in the clinker from the overall MgO content.
 Characteristic ratio of MgO/SO3 for M3 and M1 alite was 2.682 and 1.115, respectively. The observed
values of MgO/SO3 is higher than those proposed by Maki (Maki and Goto 1982) which is 1 (as shown in
Figure 1).

Figure 4 Characteristic windows for M3 and M1 alite, W2 to W9 are feasible for the identification of alite polymorph.

Figure 5 Alite polymorph and MgO/SO3 relations(Li, Xu et al. 2014)hip for clinker from industrial trial.

3.4. Mechanical properties

Within the amount of SO3 dosed in this trial, there were no risks for the mechanical properties. The
obtained clinker showed similar mechanical properties compared to the normal produced clinker (as shown
in Table 2). All the related testing results were within the limits for the standard with some minor shift of
some specific values.
The compressive strength suffered a decrease at 1 and 3 days. For the later ages (28, 90 and 180 days),
all the clinkers performed similarly. The decreased amount of C3S for the clinkers was mainly attributed to
the drop of the early age strength of the cement.
 As the drop of the C3S content with the dosage of SO3, it was impossible to distinguish the relationship
of the alite polymorphs and the compressive strength even if the polymorphs of alite were identified.

Table 2 Mechanical properties of the clinker.

Date Milling time Specific area w/c Initial setting Final setting Soundness
2
min m /kg % min min
21 32.0 343.0 23.3 85.0 135.0 OK
22 32.5 341.0 23.5 83.0 113.0 OK
23 32.5 351.0 23.5 76.0 106.0 OK
24 33.0 349.0 23.3 90.0 136.0 OK
25 33.0 340.0 23.5 85.0 115.0 OK
26 34.0 343.0 23.5 90.0 130.0 OK
27 34.5 340.0 23.4 86.0 136.0 OK
28 35.5 351.7 23.3 85.0 130.0 OK
29 35.7 351.0 23.4 98.0 130.7 OK
30 35.5 351.3 23.4 88.3 133.3 OK
31 35.3 352.7 23.3 91.7 141.7 OK
Ave. 34.6 349.0 23.4 88.0 130.0 OK

80
1d 3d 28d 90d 180d
70
Compressive strength (MPa)

60

50

40

30

20

10

0
21 22 23 24 25 26 27 28 29 30 31
Date

Figure 6 Compressive strength of the clinker produced during the trial

4. Conclusion
The modification of the alite polymorph on industrial line was made by addition of desulfurized gypsum
into the raw meal. 1.15~1.39% of SO3 in the clinker could yield M1 alite for clinker with ~2.66% MgO.
Within the gypsum amount added, clinker can be produced, but more attention should be paid to maintain a
steady production of the clinker.
 Alite content decreased as the existence of extra SO3 in the clinker, which complicated the relationship
between the alite polymorph and the compressive strength. All the mechanical properties fall in the demand
of the standard.

Acknowledgement
Special acknowledgements are to Handan Jingyu Taihang Cement Corporation for the cooperation of
the industrial trial. The author gives thanks to the supports of the National Basic Research Program of China
(2009CB623100). A Project Funded by the Priority Academic Program Development of Jiangsu Higher
Education Institutions (PAPD) and Jiangsu Planned Projects for Postdoctoral Research Funds (1402059B)
should also be appreciated.

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