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com
Kiln control using Continuous On-Stream XRD
By: Dr Peter Storer, Technical Manager, FCT-ACTech Pty Ltd and
Mr Con Manias, Managing Director, FCT-ACTech Pty Ltd
A Proven Technology
FCT-ACTechs Continuous On-Stream XRD Analyser (Figure 1) has proven to be a
reliable technology for analyzing the complete mineral content of a moving powder
stream in real time. It has proven performance in cement quality control applications,
operating successfully at cement mill installations in Australia and the USA
1,2,3
. In this
paper we discuss the benefits of using Continuous On-Stream XRD for monitoring
clinker mineralogy in real time as it is being produced.
Figure 1 FCT-ACTech continuous on-stream XRD analyser.
Clinker Production
The kiln pyro-processing is the heart of the cement manufacturing process, where the
greater part of the operating costs are incurred, and where subsequent cement quality is
largely determined. This part of the cement manufacturing process attracts more
attention that any other for many reasons, including:
The high cost of fuel, and the substantial savings possible from even a small reduction
in specific fuel consumption

1
Manias C, Retallack D and Madsen I, XRD for On-line Analysis and Control, World Cement, Feb 2000
2
Godek A, Crutchfield D, Blackham F, Storer P, Manias C and Madsen I, Proactive Not Reactive, World
Cement, Feb 2002
3
Manias C, Retallack D and Storer P, In Control, World Cement, Oct 2002
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The potential for improving clinker quality with improved heat flux profile, with
subsequent savings in grinding energy, and marketing advantages
The need to reduce gaseous emissions to meet compliance levels
Potential for other operating cost reductions (refractory use, kiln stability etc)
Mineralogical Composition
0
10
20
30
40
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1/07/02 0:00 1/07/02 8:00 1/07/02 16:00 2/07/02 0:00
Time
P
e
r
c
e
n
t
0
5
10
15
20
25
Alite
Belite-b
Belite-g
Ferrite
Aluminate-o
Aluminate-c
Fig 2 Continuous XRD Trend of clinker minerals in real time
Because of the large potential savings, cement plant operators have invested heavily in
improving kiln control, and over the decades very sophisticated expert systems have
evolved to this end. However, these control the equipment (fans, fuel, feed rates, etc)
without knowing what is happening to the material being processed in the kiln, except
through circumstantial evidence.
The continuous on-stream XRD is an invaluable tool for providing the missing
information continuously and in real time, on which kiln control can be based. This
provides the basis for a new level of kiln control, where the controlled parameter is the
clinker mineralogy, including percentages of alite, belite, ferrite, aluminate, free lime,
alkali sulfate, periclase or any other species of interest. Furthermore, by monitoring the
various forms of the clinker minerals (,,, ortho-rhombic, cubic etc) the kiln operation
could be adjusted (calciner operation, kiln speed, burner set up, cooler operation for
example) to ensure production at the optimum quality and cost position.
The On-Stream XRD Analysis Process
In cement product applications, the cement can be fed directly to the Continuous On-
Stream XRD without further treatment. For clinker analysis, the clinker must be ground
to approximately 50% passing 45 micron. This requires a continuous sample taken at the
cooler discharge, modified cooler grate or at the kiln nose ring, and further prepared for
presentation to the XRD. (It should be noted however that taking a representative
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sample at the kiln discharge or even along a cooler somewhere could be extremely
problematical because of the segregation that occurs there). A sample can also be taken
from a clinker transfer point, as shown in Figure 3.
A virtually continuous bulk sample is crushed and then sub-sampled to provide a smaller,
continuous, representative sample of about 300 - 600grams/minute which is milled to
provide a sample that is fed continuously through the XRD. The excess crushed clinker
sample and the ground, analyzed sample is continuously returned to the clinker transport
system.
The Continuous On-Stream XRD analyses a moving bed of ground clinker, using its
unique area detector to continuously collect the complete XRD pattern. In this way, the
analyser is able to produce real time trends of all clinker minerals including free lime
contained in the clinker. This trend displayed in the control room and laboratory is the
basis for control actions. No other XRD analyser on the market today produces a
complete mineralogical composition of a moving bed of material in real time. In addition
the moving bed of material provides the best opportunity to ensure that the analysis
returned is truly representative of the bulk stream. An automated laboratory based batch
analyser would take many days to analyze the amount of sample that moves through a
Continuous On-Stream XRD in one hour.
Clinker Mineralogy, Free Lime, NOx and Fuel Consumption
Clinker mineralogy is a function of the elements present in the kiln feed AND the
treatment they receive in the kiln. Bogue equations, historically used to calculate a
hypothetical mineral composition ignore the heat treatment in the kiln, and assume an
idealized equilibrium reaction. Consequently, as is now commonly known by cement
chemists, the Bogue equations rarely agree with the real composition of clinker and
cement, and can be very misleading.
A continuous on-stream XRD analyzing clinker will report exactly what is being
produced, and allow kiln adjustment to optimize the clinker composition. For example,
one plant site was found to have relatively high proportions of -C
2
S in the clinker,
pointing to a long slow cooling rate that could be addressed by cooler operation and
burner set up. Other plants experience large swings in clinker mineralogy as a result of
using alternative fuels, while others have large fluctuations in clinker reactivity and
cement behaviour without any warning or indication. None of these above are indicated
by the conventional XRF analysis that most plants still rely on.
Free lime has been used as an indication of clinker burning. The presence of free lime in
clinker may be due to a number of reasons. These include
4
:
inhomogeneous raw meal
raw meal too coarse
raw meal LSF too high
inadequate burning (such that the free lime is not combined with the other oxides)

4
D Knfel, in Labahn and Kohlhaas, Cement Engineers Handbook, Bauverlag, 1983
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Figure 3 Schematic for clinker sampling at a transfer point (1). A sampler cuts a
portion of the main clinker stream at the transfer point (2), and this is processed by
the crusher (3), reduced to a smaller sample by the rotary divider (4) and milled to a
powder (5). The powdered clinker is sent though the continuous XRD via a
feedscrew (6). Excess sample and analysed sample is returned to the process (7).
1
2
3
4
XRD
5
6
7
7
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By having a complete picture of variations in the free lime it should be possible to
correlate variations in the free lime with the correct cause, and thereby take appropriate
corrective action.
The laboratory test typically takes some hours to produce a result by conventional wet
methods, and almost as long with laboratory based XRD. The continuous on-stream
XRD produces a result in real time giving the kiln operator relevant and timely
information for kiln control. This free lime analysis together with other compositional
information can also be automatically read by an expert system controlling the kiln. It
should be noted here though that free lime on its own can be a dangerous measure if not
taken in context with the complete composition. There have been many cases of severe
damage done to kilns as a result of a kiln operator trying to achieve a free lime target that
was impossible to reach because of chemical composition.
Controlling free lime to a target though is normal for cement production. However, more
often than not, clinker free limes are much lower than the nominal target. The reasons
are that a hard burned kiln is more stable as it can cope with process variations better. It
may be that the chemical variation is high or feed rate or fuel rate variable and the kiln is
burned hard to prevent regular upsets. A continuous on-stream XRD would indicate all
of this and provide precise information for kiln control.
NOx Levels as a function of kiln burning
Hard burning is a very expensive way to operate, with the costs largely hidden. These
costs are in fuel consumption, production rate, clinker quality and NOx emissions. NOx
levels are primarily dependent on how hard a kiln is being burned, and figure 4 above is
from a recent investigation of a calciner kiln. Clearly, better kiln control can reduce NOx
emissions by 30 40%, and with the aid of a continuous on-stream XRD to achieve this,
such technology should be of interest to those plants striving to minimize NOx emissions.
Fuel Consumption as a function of kiln burning
It is well known that hard burning uses more fuel per kg of clinker. As a general rule,
increasing free lime in clinker from about 0.3% to an average of 1% will reduce specific
fuel consumption by around 5%, and will result in a 5% increase in production rate from
that kiln. This equates to a considerable economic advantage through better kiln control
possible now through the availability of continuous on-stream XRD.
Clinker Quality as a function of kiln burning
Clinker quality, or reactivity, is also largely affected by the kiln heat treatment. While
high free lime means that less alite and belite are formed, as well as introducing possible
soundness issues with concrete, low free lime is also detrimental. The hard burning of
clinker does form some of the less reactive phases leading to slow strength development.
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400
500
600
700
800
900
1000
0 0.2 0.4 0.6 0.8 1 1.2 1.4 1.6
Freelime, %
N
O
x

(
l
b
/
h
r
)
NOx
Figure 4 Correlation between free lime and NOx emissions.
So generally, as depicted in figure 5 below, there will be an optimum free lime for
optimal strength development in cement. Typically this lies in the 1.0% to 1.5% range.
Hard burning can reduce 28 day cement strengths by 5 10 MPa, compared to the
optimum potential strength of the cement.
Figure 5 also indicates the clinker grindability as a function of free lime, and as expected
harder burning leads to harder to grind clinker. Cement mill throughput can be affected
by up to 10% depending on how hard the clinker is burned.
The implications for this can be severe for a cement mill, especially where cement mill
capacity is limiting. Compare clinker at 1% free lime with clinker at 0.3% free lime as an
example. Firstly, a 10% drop in strength at 28 days will mean that finer grinding will be
required in an effort to regain some of that strength, while at the same time, the clinker
will be 6% harder to grind. The combined effect will be at least a 15% loss of cement
mill throughput.
Complete Analysis
In many plants a laboratory XRD is being used for free lime only. This is partly a legacy
of older XRD technology and analysis software. In older XRD analysers collecting a
iffraction pattern could be time consuming because the hardware required each angle to
be collected sequentially, by scanning the detector over the angular range of interest. For
this reason it became simpler to limit the data collection to the range of angles that were
relevant to free lime measurement. In addition the data analysis is likely to be based
simply on the count rate of one of the free lime peaks, which requires careful
standardization to maintain accuracy.
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Figure 5 Cement Strengths as a function of clinker free lime.
The FCT-ACTech Continuous On-Stream XRD analyser uses a patented full area
detector, which is able to measure the entire diffraction pattern simultaneously without
moving. This full area detector, combined with the latest fundamental parameter
Rietveld pattern analysis, is ideal for continuous measurement and provides a complete
picture of the cement mineralogy. Continuous On-Stream XRD analysis has the
advantage of providing a much more complete picture of what is actually happening.
Comparing laboratory XRD with continuous XRD is like comparing single photos to a
complete video of the mineralogy emerging from the kiln.
In the FCT-ACTech XRD analyser, the diffraction pattern analysis is performed using a
fundamental parameter Rietveld analysis, which gives a complete quantitative and
standardless analysis of the pattern. The accuracy of this method has been tested and
proven
2,5
. Rietveld analysis gives a complete breakdown of all of the minerals present in
the clinker stream. This is highly relevant to proper quality control. For example it is
possible to monitor the concentration of the gamma form of belite, which is an
undesirable consequence of operating the kiln with slow heating, and or inadequate
quenching of the hot clinker as it exits the kiln.

5
Scarlett N, Madsen I, Manias C and Retallack D, Powder Diffraction, June 2001.
45
0.5
50
55
2.0 1.5 1.0 3.0
110%
130%
150%
S
T
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G
T
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MPa
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A
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W.r.t.
300
2
/kg
% Free Lime
Schematic Optimum Free Lime vs. 28 Day Strength and Grindability
Strength1-2.ppt
G
rin
d
a
b
ility
( a
c
tu
a
l)
C
e
m
e
n
t S
tre
n
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th
(a
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Optimum %Free Lime
In
c
re
a
s
in
g
C
3 S
(th
e
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a
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th
)
O
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Mineral Shorthand, or composition
Alite C3S
Belite beta C2S-
Belite gamma C2S-
Aluminate cubic C3A-c
Aluminate orthorombic C3A-o
Ferrite alpha C4AF-
Ferrite beta C4AF-
Lime CaO
Periclase MgO
Arcanite K
2
SO
4
Quartz SiO
2
Table 1 Summary of some mineral phases measured (also trended with time)
FCT-ACTechs XRD Rietveld analysis includes the clinker minerals shown in Table 1.
From Table 1 it is clear that the analysis provided by a properly analysed XRD pattern is
indeed extensive, and other minerals can be included in the analysis if desired. It is
important to note that the values measured for the standard components (eg. C3S etc.) are
true measures of the cement mineralogy, and not the Bogue values that are calculated
from chemistry. As discussed earlier, there are usually large discrepancies between
Bogue calculated hypothetical composition and the true mineralogy as given by XRD.
XRD can also monitor any compound of interest in clinker such as the percentage of
Periclase (free MgO) in the clinker, which can be just as important for expansion as free
lime.
If the plant is producing more than one type of clinker then the Continuous On-Stream
XRD will give a clear indication of the type change, showing when to switch from one
storage point to another, since a change to a different type will be clearly distinguished in
a timely manner. This results in improved quality and an optimum usage of the higher
value clinker. This can be particularly useful with oil well clinker production, where
clinker quality and suitability for oil well cement can be difficult to establish.
Conclusion
Most modern plants now use sophisticated expert control systems to optimise their kiln
operation, but even the best control system cannot compensate for a lack of data. By
using a Continuous On-Stream XRD the control system has access to extremely valuable
information about the processes occurring in the kiln and clinker cooler. In particular the
XRD provides detailed information about the trends in mineralogy, and these trends can
be correlated with operating conditions. This information enables the control system and
operators to achieve the optimum operating conditions, with all of the associated benefits,
such as improved clinker quality, improved clinker grindability, reduced emissions and
reduced fuel consumption.