39

HIGH QUALITY SINTERED CALCIUM

5 ALUMINATE CEMENT PRODUCED IN
A ROTARY KILN

GUANGHUA LIU
China Building Materials Academy, Guanzhuang, Chaoyang District, Beijing,
P.R.C.

JINAN ZHOU and JIANTING WANG

Zhengzhou Dengfeng Smelting Materials Co. Ltd, Building 6-1-4,
Jinhe Residential District, No. 314, Longhai Eastroad, Zhengzhou P.R.C.

LUDO VAN NES

Caltra Nederland BV, Communicatieweg 27–3641 SG Mijdrecht,
The Netherlands

SUMMARY: Calcium aluminate cements produced in a rotary kiln are

called sintered calcium aluminate cements. They usually are more unstable,
have a shorter setting time, lower flowability and strength than fused
calcium aluminate cements. This article explains the way to attain high
quality calcium aluminate cement in a rotary kiln by selecting good quality
Calcium Aluminate Cements: Proceedings of the Centenary Conference, Avignon, 30 June–2 July 2008. Fentiman CH,
Mangabhai RJ and Scrivener KL. (Editors). IHS BRE Press, 2008, EP94. ISBN 978-1-84806-045-6. www.ihsbrepress.com.
40 Liu, Zhou, Wang and Van Nes

raw bauxite and a better preparation of the raw feed. Fineness of grinding,
better control of the kiln, control of the chemical composition, exact thermal
data in order to obtain a proper setting time, high early strength (30–40 MPa
at 6 hours) as well as a higher one day strength (60–80 MPa) and good
workability. These types of cement prove to be suitable in both the
refractory and the building chemistry industries.
Keywords: Calcium aluminate cement, rotary kilns, sintering process.

INTRODUCTION

China began to produce calcium aluminate cement by the sintering process in the early
1950s. Limited by the thermal characteristics of rotary kilns these calcium aluminate
cements were specified as follows; CaO 32–33.5%; Al2O3 50–55%; SiO2 <10%; Fe2O3
<2.5%; TiO2 2.5–3%, mineralogy after selection the CA/CA2 ratio is 1.5–2.0, saturation
coefficient is just 0.8–0.85.
Compared to fused calcium aluminate cement these types of cement have a lower
early strength but good refractoriness. Therefore they are widely used as a binder in
castables.
Most cement plants in China have little technical knowledge and poor production
facilities and hardly pre-homogenize their raw materials. With the development of
monolithic refractory castables, binders with higher early strength and a better final
strength, combined with a good and stable workability were required. Also in recent
years the “building chemistry industry” has increased the demand for calcium aluminate
cements with a stable speed of hydration and strength development. Traditional sintered
calcium aluminate cements cannot meet these requirements.
This article claims that high quality calcium aluminate cement can be produced
successfully in rotary kilns by selecting carefully the raw materials, controlling the fineness
of grinding, and keeping stable chemical composition through a steady well controlled
calcining process.
These calcium aluminate cements prove to be stable and far superior to the traditional
sintered CA cements and have proper setting times, high early strength (the 6-hour
compressive strength reaches 30–40 MPa), and high one-day strength of 60–80 MPa. This,
combined with good workability, means that these cements are increasingly being used in
both monolithic and in dry mixes.

TESTS

Three different types of bauxite were selected (dense, powder and loose), bauxite with
higher SiO2 as alumina source and a calcium carbonate with CaO 54.35% as limestone.
The bauxite and limestone were milled together in a 1.83 × 7 m (dia./length), three-
cabin ball mill and used as raw feed. A rotary kiln of 2.2 × 46 m (dia./length), with a
single cylinder cooler was used as calciner. Soft coal with VM 30% was used as fuel.
The chemical composition of the raw materials is listed in Table 1 and the analysis for
fuel in Table 2.
High quality sintered calcium aluminate cement produced in rotary kiln 41

Table 1. Chemical composition table for raw materials.

Chemical composition (%) Type of Type of
Serial No.
Loss **
SiO2 Al2O3 Fe2O3 CaO MgO TiO2 mineral bauxite
1 14.20 4.34 74.77 1.28 0.60 0.70 3.37 DK* Dense
2 14.12 4.10 74.38 1.85 0.68 1.04 3.38 DK* Powder
3 14.09 4.17 74.60 1.35 0.61 0.88 3.69 DK* Loose
4 14.20 9.20 70.21 1.32 0.61 0.70 3.12 DK* Dense
5 42.78 0.38 1.26 0.13 54.35 0.47 0.08 Limestone /
*DK type bauxite is diaspore and kaolinite.
**Loss = Loss on ignition (L.O.I)

Table 2. Soft coal analysis.

Ash (%) Volatile (%) Fixed carbon (%) Calorific capacity (kJ/kg)
12.48 31.20 55.32 28963

The setting time of cement and strength of mortar were measured in accordance with
Chinese Standard GB201-2000 (1).
• Cement : sand = 1 : 3; Water/cement ratio is to be determined as per standard
flowability, normally it is 0.4–0.45.
• Test method for acid insolubles: Specified as percentage of weight by residue of
calcium aluminate cement in a solution of 8% HCl .
• Measuring of flowability: cement : sand = 1 : 2, water/ cement ratio 0.6.
• Measure diameter of the mortar spread on the vibration table after 15 times
vibration.
• XRD test condition: Cu Ka λ=1.541A0 40 kV 40 mA 2.4 °/min
• Particle size analysis was done by laser size analyser
• The saturation coefficient used was:

CaO - [1.87 SiO2 + 0.7 (Fe2O3 + TiO2)] (1)

Am =
0.55 (Al2O3 - 1.7 SiO2 – 2.55 MgO)
When Am = 1 it means that SiO2 in the cement formed C2AS; Fe2O3 formed C2F; TiO2
formed CT, MgO formed MA, the rest of CaO and Al2O3 became CA.

TEST RESULTS AND DISCUSSION

Differences in types of bauxite have a great influence on the calcium aluminate clinker
after calcinations. The influence of its reacting activity is in the following order: powder
ore > loose ore > dense ore; test results are listed in Table 3.
From Table 3 we can learn that using a dense ore the reactivity is lower and
insolubles in the clinker reach 8.66%. The one-day compressive strength is just
48.8 MPa. While loose ore is more reactive than the dense ore, acid insolubles reduced
to 1.8% and one-day compressive strength increased drastically.
Powder ore has the best reactivity, acid insolubles reduced by another 1.85%
compared to loose ore, and the one-day compressive strength reached 79.5 MPa
(Bauxite No. 1 from Table 1 was used).
42 Liu, Zhou, Wang and Van Nes

Table 3. Influence of different types of bauxite on calcium aluminate cement.

Chemical composition of calcium aluminate cement (%) Acid 1 day
Bauxite compressive
insoluble
structure Loss SiO2 Al2O3 Fe2O3 CaO MgO TiO2 strength
%
(MPa)
Dense ore 0.24 5.14 54.20 1.89 34.45 0.87 2.55 8.66 48.80
Loose ore 0.45 5.10 53.28 2.00 34.86 0.93 2.86 6.86 64.80
Powder ore 0.28 4.89 55.13 1.43 34.21 0.70 2.64 5.01 79.50

Influence of SiO2 on strength development

When calcium aluminate cement is produced in a rotary kiln, the SiO2 will absorb CaO
and Al2O3 and form gehlenite, C2AS. This mineralogical phase is non-hydraulic. In
other words the higher the SiO2 content the less effective the cement will be as less CA
and CA2 phases in the cement are formed. The amount of C2AS must therefore be as
low as possible in producing sintered high quality calcium aluminate cement. Fig. 1
shows the influence on the strength development at different SiO2 contents.

Fig.1. Influence on the strength development at different SiO2 contents

Fig. 1 also tells us that not only is a higher 6-hour strength reached but also an
increased strength in 1 and 3 days is obtained. In other words, with an increased amount
of SiO2 the strength of the cement is reduced.

Influence of fineness of raw bauxite on the property of calcium aluminate clinker

Because limestone is more easily ground than bauxite and it will convert into CaO at
900–1000ºC: it is a highly reactive component. On the other hand the fineness of bauxite
is the main factor to restrict this reactivity. Table 4 shows the influence of reactivity from
different sizes of bauxite in a rotary kiln (illustrated by acid insolubles). It is apparent that
coarser bauxite reduces the reactivity and the acid insolubles are increased, which further
reduces the reactivity.

Table 4. Influence of particle size of raw bauxite to acid insoluble in clinker.

Particle size of bauxite D90um Acid insoluble in clinker
74.39 8.06
55.31 6.86
35.37 5.75
28.51 5.10
High quality sintered calcium aluminate cement produced in rotary kiln 43

Influence on the quality of clinker of stabilising the raw materials

We set CaO content in the ores at a range of ± 0.3% and evaluated the ratio of qualified
products by measuring the CaO content in the raw materials feed into the kiln every
hour.
Qualified ratio of CaO content in the powders could reach 90% min. by selecting
the raw materials, pre-blending them and having a tight control on the total process.
Steady operation of the kiln, the length and temperature in the burning zone is
stabilized so that calcium aluminate clinker with high CA content is calcined at a
0.9–0.96 saturation coefficient. As a result, the quality of the clinker changed significantly
and the CA content in the clinker increased sharply.
Table 5 shows the chemical composition of calcium aluminate cement produced by
the traditional method as well as after the improvements (No. 2 and No. 3).

Table 5. Changes of calcium aluminate clinker after improvements.

Chemical composition of calcium aluminate
Mineralogy Saturated Acid
clinker (%)
Serial No. coefficient insoluble
Loss SiO2 Al2O3 Fe2O3 CaO MgO TiO2 CA CA2 C2AS (Am) (%)

1# before
0.44 7.33 52.44 1.95 33.26 1.04 2.72 33.65 20.04 33.50 0.79 7.08
improving
2# after
0.27 4.40 55.49 1.53 34.31 0.70 2.64 57.31 11.79 20.11 0.90 5.01
improving
3# after
0.30 6.26 51.36 2.21 35.28 1.24 2.68 53.56 3.83 28.61 0.96 //
improving

Mineralogy (calculated) and content of acid insoluble and CA content by XRD

It is apparent that the CA content in the clinker increased after the improvements were
made (D value is 2.977 peak value). The acid insolubility reduced considerably. The
amount of sintering of the clinker changed clearly. Fig. 3 is the micrograph of clinker 1#
and 2#, It is noticed that there is a lot of porosity in clinker 1#, whose CA crystal
developed far smaller − less than 5 micron. Sample 2# shows a good sintering, less
porous, CA crystal developed well over 10 microns.
Counts /s

Fig. 2a. XRD diagram, Sample 1#

44 Liu, Zhou, Wang and Van Nes

Counts /s

Fig. 2b: XRD diagram, Sample 2#

Fig. 3. Micrographs of clinkers 1# and 2#.

The early strength of the cement obviously increased (at 6 hours), the strength after
one and 3 days increased significantly and the setting time was prolonged.
Table 6 shows changes of setting time and strength of calcium aluminate cement after
the improvements were made. The flowabilty of the cement is also improved (Fig. 4).
Table 6. Change of property of calcium aluminate cement after improvements.
Setting time Compression strength
Serial Blaine Flexural strength (MPa)
(h:m) (MPa)
No. (cm2/g)
Initial final 6h 1 day 3 day 6h 1 day 3 days
1# 3340 1:30 1:47 / 6.30 7.30 / 46.8 64.4
2# 4120 3:37 3:41 2.6 10.20 12.90 17.1 84.1 88.4
3# 4680 1:39 1:39 4.9 9.30 11.33 36.2 70.8 80.2
High quality sintered calcium aluminate cement produced in rotary kiln 45

Fig. 4. Flowability of three types of cement.

From Fig. 4 it can be seen that sample 1 has a reduced flowability after stirring for
15 minutes. After improvements were made, clearly sample 2 gives a good flowability
for 60 minutes and sample 3# after 30 minutes.
Summarizing the above test results; high CA cement content sintered calcium
aluminate can be produced in a rotary kiln by selecting raw bauxite with low SiO2, and
a good reactivity be obtained by tightening the production process control and
maintaining stable thermal conditions. It is well known that when CA hydrates it has a
longer induction interval.
Once started, the hydrates will form a rapid crystallisation, which sets and
hardens. In order to make clinker calcination saturate coefficient in a rotary kiln higher
than 0.90 or even 0.96, it is absolutely essential to form a stable burning zone in the
rotary kiln.
The temperature in the burning zone should not be too high so as to maintain a
liquid phase of the clinker of around 27% (at this time the size of ores are evenly between
5 to 20 mm and ores will be sticky when rotating along the walls of the kiln). The rotating
speed of the kiln should be adjusted at this time to let the ores stay longer in the burning
zone in order to obtain full chemical reaction and to prevent residue of C12A7 (leds to
variable setting times).
In order to achieve stable thermal parameters in the kiln, the first thing is to
guarantee even chemical composition of raw materials. When the quality of the raw
materials is more constant it is easier to avoid big changes on firing of the kiln.
Furthermore the use of a steady good quality of coal and a regular burning speed are
necessary to make a constant high quality clinker.
Test results have proved that high early strength calcium aluminate cement with a
high CA content can indeed be produced in a rotary kiln. The cement has a 70–80%
higher 6 hour strength than a traditional sintered calcium aluminate.
These type of calcium aluminate cements are consistent and have a proper even
setting time and high early strength with good workability. They are now increasingly
being used in the refractory- and dry-mix industry.
46 Liu, Zhou, Wang and Van Nes

CONCLUSION

Sintered high quality calcium aluminate cement with high CA content, high early
strength and increased long-term strength combined with good workability can certainly
be produced in a rotary kiln.
Low SiO2 content and both loose and in powder form bauxite are crucial.
Steady raw materials, good raw feed control, reduced particle size of bauxite,
stable calcining by a consistant speed of the kiln and the usage of good quality coal are
the key factors in producing this high quality calcium aluminate cement.
High quality sintered calcium aluminate cements produced in a rotary kiln are
being used successfully as a binder for refractory purposes (monolithics) and as an
accelerator and expansion agent in dry mixes by the “building chemistry industry”.

REFERENCES

[1] Gao Zhengxin and Li Guangping. Research on category of bauxite in China.

Journal of The Chinese Ceramic Society. Vol 1. No. 2, 1984.
[2] Zhou Jinan, Liu Guanghua, Wang Jian Ting. New development of high alumina
cement in China. The Third Forum of International Refractories, Beijing, China,
[3] Xie Guogang, Zhang Songmao. Practice and knowledge go upgrading quality of
high alumina cement. The Third Forum of International Refratories, Beijing,
China, November 1998.
[4] Liu Guanghua, Daio Guizhi, Zhou Jinan, Wang Jianting, Ludo van Nes. Testing
of sintered calcium aluminate cement and calcium sulpho aluminate.