Cement Science and Concrete Technology, No.

65, 2011

LOW TEMPERATURE BURNT PORTLAND CEMENT CLINKER

USING MINERALIZER

Makio YAMASHITA 1 and Hisanobu TANAKA 1

* *

*1 MITSUBISHI MATERIALS CORPORATION, Cement Research Institute（2270, Yokoze, Yokoze

machi, Chichibu gun, Saitama 368 8504, Japan）

ABSTRACT：Decreasing the burning temperature of cement clinkers leads to a rational reduction

of CO2 emitted from the cement industries. This study examines the use of CaF2 and CaSO4 as a
mineralizer or flux. It was possible to reduce the burning temperature 100 ℃ below that of the current
process（1450 ℃）by controlling the fluorine and sulfur trioxide in the clinker. The setting and hardening
properties of the low temperature cement equal those of ordinary Portland cement. It was also found
that the coating effect of additional mineralizer components on the preheater was insignificant.

KEY WORDS：Low temperature burning, Mineralizer, Flux, Fluorine, Sulfur trioxide, Clinker mineral,
Cement properties, Preheater coating

1. INTRODUCTION a percent order5）. However, few have addressed the

The cement industry consumes much energy and ac- problems mentioned above. Chloride input in a clinker
counts for six percent of the total carbon dioxide（CO2） production system is restricted not only by compliance
emissions from stationary sources1）. The reduction of with quality standards of cement, but also by the need
CO2 and the conservation of energy are social demands to avoid preheater kiln operational problems that result
for the cement industry. However, in the cement indus- from a high concentration of chloride in the preheater.
try, appreciable amounts of energy have been saved Also, increased heavy metals（e.g., lead）in cement
or conserved over time2）. At this point, cost effective may dissolve from concrete or mortar products. In this
ways of conserving energy are difficult to find. Lower- study, we used calcium fluoride（CaF2）and calcium
ing the burning temperature of clinker could be re- sulfate（CaSO4）as the mineralizer or flux for ordinary
garded as a pathway to reduce CO2 emissions. Portland cement clinker burning. We investigated the
Clinker burning requires high temperatures because conditions of the mineralizer, which enables a 100 ℃
the stabilization of alite requires a high tempera- reduction in clinker burning temperature. Also, clinker
ture, and alite forms more slowly than other clinker and cement properties obtained at low burning tem-
minerals. The rate of alite formation is controlled by perature were investigated. Fluoride volatility in the
the dissolution and the diffusion of CaO through the burning process was examined in order to determine
melt. Lower melting temperature and viscosity and its condensation in the area between the rotary kiln
increased liquid phase accelerate alite formation. A and the preheater, which may result in coating forma-
mineralized or flux agent changes the properties of the tion.
melt phase. In general, as the flux agent becomes more
electronegative, the melt becomes more viscous. 2. EXPERIMENTAL
Fluorinated salts accelerate the formation of clinker 2. 1 Fabrication of Clinkers
3, 4）
minerals because of their high electronegativity , In Each clinker was prepared in such a way that the
addition, sulfur, chloride, and heavy metal（e.g., lead） moduli were the same as those of ordinary Portland
behave as flux in clinker production. However, these cement clinker. Raw metal from a cement plant and
components may affect cement properties, stable plant commercially available reagents（e.g., calcium carbon-
operation, and the environment. ate, silicon oxide, aluminum oxide, iron oxide, calcium
Many studies have focused on reducing the burning sulfate, alkali carbonate, and calcium fluoride）were
temperature by adding salts containing fluoride, on used as starting materials to adjust the clinker moduli,

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Fig. 1 Relationship between F content and f.CaO content in clinker

along with sulfur oxide, alkali oxide, and fluorine in the The sample preparation, XRD measurement conditions,
clinker. A minimal amount of reagents（10 %）was used and Rietveld analysis method were the same as in the
to adjust the clinker s moduli and minor elements. The reference 6）. Tests for setting time and compressive
mixture of starting materials was calcined at 1000 ℃ strength of the cement were carried out in accordance
for 60min and then burned at 1450 ℃ for 90min in an with JIS R 5201：1997 Physical testing method for ce-
electric furnace, and quenched in air. ment.
JIS R 5204：2002 Chemical analysis method of ce-
ment by X ray fluorescence and Japan Cement As- 3. RESULTS AND DISCUSSION
sociation Standard（JCAS）I 01：1997 Determination 3. 1 Effect of the Mineralizer
method for free calcium oxide were used to determine Figure 1 illustrates the relationship between F
the chemical composition and the free lime（f.CaO） content and f.CaO content in clinker at burning tem-
amount of the clinker. Florine（F）content in clinker peratures of 1300 ℃ and 1350 ℃. The f.CaO content
was determined in accordance with spectrophotometry in clinker that is burned at the same temperature de-
in combination with steam distillation（JCAS I 51： creases with an increase in F. This result demonstrates
1981）. the effect of CaF2 as a mineralizer. Furthermore, SO3
2. 4 Fabrication of Cement content in clinker enhances burnability and strength-
The obtained clinker was crushed in a jaw crusher ens the effect of mineralization of CaF2. The improved
and roughly ground with a ball mill under constant burnability of a high F and high SO3 clinker can be ex-
conditions. Reagent gypsum was added to adjust the plained not only by reduced viscosity and surface ten-
total sulfur oxide（SO3）content in cement to 2.1 % sion of the oxide melt, but also by increased melt due
when the SO3 content in the clinker was less than 1.3 %. to eutectic formation of fluoride and sulfate mixtures,
When the SO3 content in the clinker was more than which enables alite to form at low temperatures7, 8）.
1.3 %, reagent gypsum addition was constant at 0.8 % In the present study, the degree of burnability was
SO3. The mixture was further ground with a ball mill evaluated by the f.CaO in clinker. When the mineral-
to a Blaine specific surface area（Blaine value）of 3250 ized clinker was burned at 1350 ℃, the F content in-
±50cm2/g. creased from 0.024 % to 0.067 %, and the SO3 content
2. 5 Physical Testing of Clinker and Cement increased from 0.6 % to 2.2 %, thus achieving the same
The bulk density of the clinker was determined by burnability as the normal clinker burned at 1450 ℃. In
filling a 400mL container and weighing the amount addition, in the clinker burned at 1300 ℃, as the F con-
of clinker with a particle size of 2 to 5mm to fill the tent was increased up to 0.27 % and the SO3 content
container. The number of revolutions of the finishing was increased up to 2.2 %, the burnability was equal to
mill required to obtain the intended Blaine value was that of the normal clinker burned at 1450 ℃.
used to evaluate the grindability of the clinker. Fewer Table 1 presents the chemical composition of miner-
revolutions indicated superior grindability. Bruker s alized clinkers burned at 1350 ℃ and 1300 ℃ in which
D8 ADVANCE and TOPAS Version 3 were used to mineralizer content was adjusted to same burnability
acquire an X ray diffraction（XRD）profile and used as normal clinker burned at 1450 ℃.
for the Rietveld calculation of the mineral composition. Although the Na2O and K2O contents in the raw

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Table 1（a） Chemical Compositions of the clinker（％）

Temperature SiO2 Al2O3 Fe2O3 CaO MgO SO3 Na2O K2O Na2Oeq F
1450 ℃ 22.15 5.71 3.03 66.11 1.19 0.55 0.29 0.37 0.53 0.024
1350 ℃ 21.78 5.62 2.97 64.72 1.19 2.28 0.30 0.50 0.63 0.067
1300 ℃ 21.61 5.62 2.97 64.44 1.19 2.37 0.31 0.53 0.66 0.270

Table 1（b） Clinker modules and Bogueʼs mineral composition（⊖, ％）

Temperature HM SM IM AI LSD C3S C2S C3A C4AF
1450 ℃ 2.14 2.53 1.88 3.88 0.916 56.1 21.2 10.0 9.2
1350 ℃ 2.13 2.54 1.89 3.88 0.894 49.6 25.0 9.9 9.0
1300 ℃ 2.13 2.52 1.89 3.85 0.894 49.1 25.0 9.9 9.0

Fig. 2 Characteristic alite peaks in XRD patterns

Fig. 3 Mineral composition by XRD/Rietveld method

mix of all clinkers were adjusted in the same way, the Figure 3 indicates the mineral composition of the
mineralized clinkers burned at low temperatures had mineralized clinkers burned at different temperatures,
somewhat higher alkali content, due to their reduced determined by the XRD/Rietveld method. The mineral-
volatility. ized clinker had higher belite and ferrite contents and
3. 2 Clinker minerals lower alite and aluminate contents than the normal
Conventional clinker minerals（e.g., alite, belite, alu- clinker, mostly due to the influence of higher F and SO 3
minate, and ferrite）were easily identified in all clinkers in clinker12, 13）.
by XRD. Other minerals containing F or SO 3 such as 3. 3 Physical Properties of Clinker and Cement
fluoroaluminates（C 11A 7・CaF 2）and calcium langbe- （1）Bulk density and grindability of clinker
inite（K2SO4・2CaSO4）were not identified with XRD The bulk density of the clinker was measured since
methods. However, the alite polymorphs differed in the there was a significant difference in shrinkage of the
samples studied here. In commercial clinker, alite ex- clinker after burning（Fig. 4）. The mineralized clinker
ists in two crystal systems（M1 and M3）, in which the burned at 1350 ℃ had higher bulk density than the
polymorphic state is reflected in the diffraction peak at normal clinker burned at 1450 ℃, primarily because
9, 10）
2θ＝51 52（CuKα radiation） . The M1 phase gives of increases of SO 3. However, the bulk density of the
a single peak, and M3 phase gives a double peak. Fig- mineralized clinker burned at 1300 ℃ was lower than
ure 2 presents their XRD profiles. Alite in mineralized that of other clinkers due to insufficient clinker sinter-
clinker burned at 1350 ℃ or 1300 ℃ resulted in M1, and ing. Decreasing f.CaO in clinker may not necessarily
alite in the normal clinker burned at 1450 ℃ resulted improve the clinker sintering characteristics.
in M3. The M1 phase of the alite in mineralized clinker Figure 5 presents the number of test mill revolutions
may be attributed to the high SO3 content, since it has required to achieve a specified Blaine surface area. The
been demonstrated that doping with SO3 stabilizes M1 grindability of clinker was primarily reflected in the
11）
polymorphs . bulk density.

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Fig. 4 The bulk density of clinker Fig. 5 The number of test mill revo- Fig. 6 Setting time of cement
lutions required to obtain the
target Blaine value

（2）Setting time
Cement was fabricated using mineralized clinkers
and gypsum. Figure 6 indicates the setting time of ce-
ment burned at different temperatures with or without
mineralizer. Setting time differed only slightly between
cement burned at 1450 ℃ and that burned at 1350 ℃.
However, the setting time of cement burned at 1300 ℃
was retarded to 50min. In the past study, the setting
time was retard to 60min with a 0.1 % increase of F12）.
（3）Compressive strength
Figure 7 illustrates the relationship between clin-
ker burning temperature and cement compressive
Fig. 7 Compressive strength of cement
strength. Compressive strength after three days was
not influenced by the clinker burning temperature or
the mineralizer in the clinker. However, the cement size of mineralised clinker was smaller than normal
burned at 1300 ℃ had lower compressive strength than one at the same Blaine value of the cement.
those burned at 1350 ℃ and 1450 ℃. 3. 4 Influence of Mineralizer on Preheater Coating
From the results of this study, we could not deter- （1）Influence of fluorine
mine a clear reason for the large strength gap between Chloride in the raw materials and fuels of the clinker
the two cements burned at 1300 ℃ and burned at burning process causes coating problems in preheater
1350 ℃. Several studies have focused on the effect of cyclones. The chloride that condenses on the kiln feed
F on cement compressive strength. Most report that or kiln gas reacts with sulfates, resulting in a low melt-
F in cement does not negatively affect the strength of ing point composition so that the materials become ad-
cement up to the order of 1 %12）. In this study, the F hesive and adhere to the preheater equipment. In this
content in the cement burned at 1300 ℃ was at most section, we discuss the chemical reactivity of fluorine
0.27 %. We assumed that the decreasing strength of with sulfate, as well as the volatility of fluorine com-
the mineralized cement at 28days was due to the rela- pared with that of chloride. The influence of mineraliz-
tively low burning temperature, which decreases active ers on preheater coating is then investigated.
alpha C2S in the high temperature phase. Figure 8 depicts the phase diagram for the CaSO4
Despite lower alite content in the mineralised clinker CaCl2 CaF2 system15）. Fluoride forms a eutectic system
burned at 1350 ℃, the compressive strength of the ce- with sulfate as well as chloride；eutectic liquid thus
ment is the almost same as the one burned at 1450 ℃. appears below the melting point of CaF2. The ternary
The reason for this seems to be lower gypsum addition eutectic temperature is 597 ℃. The amount of eutectic
to the mineralised clinker since the gypsum amount in liquid increases with fluoride, the same as chloride on a
the cement lower compressive strength14）, and particle molar basis. Therefore, increasing the fluoride content

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in raw material could lead to the emergence of coating

or build up in the upper preheater cyclone stage, as
well as chloride.
The F content in the clinker tended to increase
linearly with the addition of CaF2. Here, the burning
temperature and SO3 content in clinker affected the
F content in clinker, with the same CaF 2 addition.
Figure 9 indicates that the volatilization ratio of F
increased with temperature and decreased with SO3
content in clinker. The volatilization ratio increased
7 % per 100 ℃ as the temperature increased from 1300
to 1450 ℃. The decrease of F volatility with high SO3
content in clinker was due to the lower vapor pressure
of the fluoride salt in eutectic liquid with sulfate.
If F combines with alkalis to form alkali fluorides as Fig. 8 The system CaF2⊖CaCl2⊖CaSO415）
well as chloride in the preheater, significantly higher F
should be volatilized in the burning process. Figure 10
illustrates the relationship between the F content and
the alkali content in clinker. The alkali content did not
change with an increase in CaF2 addition. Therefore, F
exists in other compounds（e.g., CaF2）.
（2）Influence of sulfur
Increasing SO3 in clinker may seriously increase the
coating or build up in the preheater. In a general ce-
ment plant, SO3 in clinker is supplied by the fuel（e.g.,
high sulfur petroleum cokes）. However, cement plants
have already developed techniques to reduce SOx in
the preheater and in exhausted gas. Since we did not
examine the influence of SO3 on the coating or build Fig. 9 Relationship between burning temperature and
up, coating problems due to increased SO3 in the pro- volatilization of F
cess could be avoided by using existing technology.

4. CONCLUSION
We investigated the conditions of CaF2 and CaSO4
as a mineralizer or flux to lower the clinker burning
temperature. We also examined the properties of clin-
ker and cement fabricated used these components and
obtained the following results.
（1）Controlling the F content at 0.067 % and the SO3
content at 2.2 % achieved clinker burning at a
temperature 100 ℃ below that of the current pro-
cess（1450 ℃）.
（2）The setting and hardening properties of mineral-
ized cement burned at 1350 ℃ equal those of ordi- Fig. 10 Relationship between CaF2 addition and alkali
nary Portland cement burned at 1450 ℃. content in clinker
（3）Coating or build up on the preheater cyclone may
form due to the condensation of fluoride vapors, in did not significantly influence coating formation.
the same way as for chloride. However, lowering
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