78 QUALITY CONTROL

Preventing build-ups and rings

The increased use of petcoke and alternative fuels has led to higher sulphur and chloride
inputs into cement production. Effective prediction and control requires a thorough
understanding of the development of such cycles.
n by Tom Lowes, OPECS, UK and Joana Bretz de Souza, Cinar, Brazil

W ith the need to use lower-cost fuels

such as petcoke and alternative fuels
(AFs), the sulphur (S) and chloride (Cl)
Figure 1: SO3- and Cl- data from an air-through calciner with 100 blasters

inputs into the cement production process

can increase to levels where the preheater
build-up and kiln rings become untenable
and their removal requires a plant
shutdown. At this point, several options
become available:
1. Cut back on the S and Cl inputs until a
trouble-free operation is possible.
2. Optimise process operation from a
fundamental knowledge of SO3- and
Cl- cycles, install up to 100 blasters and
carry out focussed shift cleaning of the
kiln.
3. Install a Cl by-pass for either the kiln
gases or the hot meal.
4. A combination of both process
optimisation and by-pass installation.
The conventional rule based on the
maximum input of Cl- in hot meal (HM)
being 300mg Cl/kg clinker is also tied to the
SO3- input by the equation:
Cl-max, HM = 2 - 0.4 • SO3-HM [Eq 1]
where two per cent ClHM equates to
400mg Cl/kg clinker.
This can be exceeded by optimising the
process operation (option 2), as shown in
Figure 1 for an air-through (AT) calciner
with 25 per cent tyre-derived fuel (TDF) fed
into the riser. The equation becomes:
Cl-max, HM = 4 - 0.4 • SO3-HM [Eq 2]
The fundamentals and control of
SO3- cycles and build-up
To understand the reasons for the build-
up on a plant it is necessary to look at the
fundamentals of SO3- cycles:
• Na2SO4 and K2SO4 are quite thermally
stable and need temperatures greater
than 1600˚C for complete volatilisation,
but when there is an excess of SO3- –
molar ratio (MR) >1 – over alkalis, less
thermally-stable SO3- compounds
form that are also more susceptible to
reduction and volatilisation.
• Hence the higher the alkalis, the
higher level of SO3- input a plant can
go to before major build-ups occur,
for the same level of Cl. While Na and
K sulphates produce soft build-ups,
compounds based on CaSO4 produce
hard build-ups and rings.
• The hot meal chemistry in terms of MR
or excess SO3- is an important first area
of focus. It is in the hot meal and not in
the clinker, where Cl takes the alkalis in
preference to SO3-, hence making way
for the less thermally stable species.
Key drivers
Two key compounds that form in the
calciner and after calcination zone drive
SO3- cycles:
• langbenite (KL) – K2SO4.2CaSO4 – is
thermally stable to 1520˚C in O2.
• calcium sulphate – CaSO4 – is
thermally unstable >1420˚C in O2 but
at 900˚C (end of calcination zone in
the kiln) under reducing conditions, C
+ CaSO4 = CaO + SO2 + CO. Due to more
SO3- cycling it produces hard
build-ups based on CaSO4.
• It should be noted that 0.2 per cent
carbon (C) (normal target: 0.1 per cent
C) volatilises 1.4 per cent SO3- and 0.2
per cent C is at 96 per cent burn-out of a
calciner fuel.
• For 0.5tph of tyres with 35 per cent
volatiles this is at 0.3 per cent C on the
feedshelf for 100tph clinker and will
drive the SO3- cycles for a calciner kiln.
• At the higher SO3- cycling rates,
2C2S•CaSO4 (ie sulpho-spurrite) is
formed, and is responsible for kiln rings.
• But without avoidance of reduction
in both the burner and the after-
calcination zone plus hard burning, high
SO3- inputs will produce bad build-ups
and/or rings.
• When there is an excess of SO3- over
alkalis in the clinker, then hard burning
or a combinability temperature (CT)
greater than 1450˚C breaks down the
CaSO4 and increases SO3- cycles. This
then increases the excess SO3- in the hot
meal and increasing build-up can often
lead to kiln rings.

©Copyright Tradeship Publications Ltd 2017

INTERNATIOINAL CEMENT REVIEW JULY 2017

Figure 2: combinability temperature of clinker as a function of LSF and +90µm AIR
Figure 3: coating behaviour
AR
Thick coating clinker ball
or sinter ring formation
(plenty of viscous melt phase)
1.9
Normal
1.6 coating
1.3
Thin coating
refractories attack
(plenty of fluid melt phase)
2.2 2.5
Excess SO3- in the hot meal
Excess SO3- in the hot meal is increased by:
• AF dropping through to the feedshelf
or unburnts in the hot meal
• tyres on the feedshelf
• unburnt matter from the calciner in
the hot meal (>0.1 per cent C)
Target excess SO3- to less than one per cent
in hot meal.
• The calculation of excess SO3- is:
SO3-exc = SO3-HM - 1.29 • (Na2OHM, eq - 0.9 •
Cl- HM)
• The excess SO3- to the KL as CaSO4 is:
2 • (K2O HM - 1.33 • Cl- HM) • 80/92
• SO3- in excess of this is CaSO4 on its
own and very susceptible to carbon
reduction greater than 900˚C.
Excess SO3- in the clinker
Excess SO3- in the clinker can be volatilised
by:
©Copyright Tradeship Publications Ltd 2017
Very thin coating
Dusty clinker
(little of viscous melt phase)
Thin coating
(little of fluid melt phase)
2.8 SR
• reducing conditions from the kiln
burner
• hard burning or a high CT. Figure 2
shows how the variation in clinker
lime saturation factor (LSF) and acid
insoluble residue (AIR) for the raw
material +90µm (quartz) can readily
drive the CT greater than 1520˚C.
• Even when the SO3- is not in excess
in the clinker, a low-momentum kiln
burner, low kiln back end (KBE) O2
and or a fuel (normally an AFR) being
allowed to drop into the burning zone
can drive SO3- to the hot meal. It then
becomes excess SO3- over alkalis and
gets driven into higher SO3- cycles and
build-up by the reducing conditions in
the hot meal or on the feedshelf.
Dusty clinker
Dusty clinker is produced when:
JULY 2017 INTERNATIONAL CEMENT REVIEW
QUALITY CONTROL 79
Figure 4: kiln ball formation
• there is insufficient liquid phase (LP),
which should be between 25-26 from:
LP [%] = 3.0 • Al2O3 + 2.25 • Fe2O3 + MgO
(max 2%) + Na2O+ K2O
• there is a MR in the clinker >1.5,
due to the excess SO3- going into the
LP (and not into the alkali sulphate
liquid phase). This reduces the LP’s
viscosity and surface tension and hence
produces less nodular clinker.
• when reducing conditions occur in the
burning zone. This does not allow the
SO3- to combine with alkalis and hence
more goes into the LP.
• the CT is high and hence the surface
tension and viscosity are less.
Resolving build-up and ring issues will
generally make the clinker less dusty.
Kiln balls
Kiln balls are the most difficult of build-up
issues to resolve. They have two causes.
Firstly, the clinker chemistry is such that it
is in the ball formation region (see Figure
3). Secondly, poor combustion in the kiln
and calciner are such that a circulation of
high amounts of alkalis and SO3- is building
up and breaking away so intensely that it
nodulises and produces balls.
As kiln balls are not often found
(see Figure 4), it is difficult to produce
general rules. However, based on limited
experience, it is possible to conclude the
following:
• A poor control of Fe2O3 can take an
average normal clinker composition to
the clinker ball region by decreasing its
silica ratio (SR).
• Unburnt matter in the hot meal and
low KBE O2 can produce internal cycles,
leading to kiln balls.
 80 QUALITY CONTROL

Figure 5: sticky factor values for different cement plants • K2O = 0.6
• Na2O = 0.2
• Cl- = 0.04 per cent
resulting in hot meal
values of:
• SO3- = 2
• K2O = 1.2 + 2.66
• Na2O = 0.3
• Cl- = 2 – (HM Cl- can be
predicted from: 50 • % Cl-
on clinker input without a
bypass)
This gives a SF of 8.16.
Generally, from experience
an SF of 8 is the maximum
a plant can run at without
severe disruption or
stoppages.
Figure 5 shows data
from a range of preheater
and calciner plants,
compared to predicted
values. This highlights
several plants to have
• A low burner momentum can set up Predict the required hot meal severe build-up issues with sticky factor
cycles that produce balls. SO3-, Na2O, K2O and Cl- values greater than they should be for a
The authors have resolved kiln ball The volatilisation factors (VF) are simply: well-managed and controlled operation.
issues by modifying the plant’s operation. • for SO3-: VF SO3 = SO3-HM / SO3-clk Table 1 shows a typical calculation
One cement plant received assistance to • for K2O: VF K2O = K2O HM / K2O clk where the green values represent the
eliminate each of the above issues. Initially • for Na2O: VF Na2O = Na2O HM / Na2O clk. predicted hot meal values from the clinker
the burner momentum was increased and For a well-operated calciner or data and Cl- input, the orange values
the AFR injection in the calciner modified, preheater kiln the target volatilisation are the plant hot meal data, and the red
which solved the presence of kiln balls. factors for its volatile compounds are: highlighting danger.
However, the issue returned six months • SO3- = 2
later and improved Fe2O3 control resulted • K2O = 1.8 Solving build-ups
in the required outcome. • Na2O = 1.5 To solve build-up issues, it is
In another cement plant, kiln balls • Cl- = 50. recommended that cement plant
developed when SO3 circulation became However, in the presence of Cl-, K2O is operators adhere to the following
too high, driven by a poor calciner fuel much more volatile and its volatilisation is methodology:
burn-out, as indicated by an increased increased by 1.33 • Cl- HM. • First check with the plant and its
SO2- (and picked up by the plant’s online All these added together is an indication of operators what the build-up or ring
SO2 measurement) and increased hot the sticky factor (SF) of the preheater. issue is and where it is occurring, so the
meal carbon. Balls were eliminated by the The plant in Figure 1, has values on problem to be solved is clear in one’s
operators increasing the KBE O2 until the clinker input of: mind.
SO2 levels came to < 3000ppm. • SO3- = 1 • Calculate the daily average VF SO3,

Table 1: sticky factor calculation

It is possible to calculate a good sticky factor from the Cl-HM and the clinker chemistry, plus HM KL and CaSO4

VF VF target Plant data Predicted from VFs Actual plant info and calculations

VF SO3- 2 Clk SO3- 0.72 HM SO3- 1.44 9.95

VF Na2O 1.5 Clk Na2O 0.35 HM Na2O 0.53 0.33
VF K2O 1.8 Clk K2O 0.91 HM K2O 1.64 2.97
VF K2O Cl -
Cl HM x 1.33
-
HM Cl -
0.90 HM K2O w Cl -
1.21
Clk MR 0.59 HM Cl- 0.90 0.90
Inputs HM SF 5.72 14.15
Calculations Na2O eq 2.40 2.29 As KL As CaSO4
Calculations of danger levels Excess SO3 -
-0.61 8.05 3.08 4.97

©Copyright Tradeship Publications Ltd 2017

ICR JULY 2017
 82 QUALITY CONTROL
Figure 6: SO3 in raw meal (RM – blue) and clinker (CLK – orange)
Figure 7: excess SO3- over soluble alkalis and potassium langbenite SO3- capture potential
which should be two with a maximum
of three. Plot the clinker SO3- measured
against the expected clinker SO3- from
the mass balance. This should match on
a daily average basis. Calculate SF and
compare to what it should be.
• Check the calciner combustion
performance from a plot of CO vs O2.
The CO should be <500ppm at two per
cent O2 with hot meal carbon (HMC)
below 0.1 per cent. A visual inspection
of the sample on a white paper can be
used in the absence of a Leco. It should
be noted that depending on the calciner
type, its fuel and residence time, as well
as the exit O2, the stratification in the
calciner may need to be overcome to
meet the target 0.1 per cent HMC.
• Check kiln burner momentum (N/
INTERNATIONAL CEMENT REVIEW JULY 2017
MW) against burning zone thermal
load (should be twice this level or O2
stratification will occur in the kiln back
end and not assist in burnout of hot
meal carbon).
• Look for reducing conditions in the
clinker. Keep in mind that often there
is reduction that cannot be detected
by visual inspection or FeO test.
Hence, checking XRD for orthorhombic
C3A, clinker for insoluble alkalis plus
microscopy may be necessary.
• The maximum insoluble alkalis for a
good flame is 0.01 • C2S if the SO3- is in
excess of the remaining alkalis, with the
maximum orthorhombic C3A being:
C3A OR, max = (Na2O eq - 0.01 • C3S - SO3-
/1.29) • 11.75 when the alkalis are in
excess.
©Copyright Tradeship Publications Ltd 2017
• Check KBE NOx and CO vs KBE O2. The
NOx peak should be at two per cent O2
and the CO should not begin to increase
before 1.5 per cent O2.
• Check the CT of the raw material. The
acid insoluble residue and clinker LSF
are the main drivers of high CT, first
target less than 1470˚C.
Following this methodology it should be
possible to ascertain if the problem is due
to: a. reducing conditions in the hot meal/
feedshelf, b. driven by the kiln burner and
its operation, or c. down to a combination
between raw material chemistry and its
combinability temperature.
Case studies
Below are three recent case studies where
the solution to build-up and rings have
been outside the problem-solving scope
of the plant or corporate resources and
the authors were asked to help resolve the
issue.
Case 1 – intermittent ring formation,
causing up to 10 shutdowns per year
Looking at the hot meal, raw meal and
clinker it was found that the VF SO3 was six
and the total SO3- in was not being seen in
the clinker as shown in Figure 6.
The plant was a preheater plant with no
combustion in the riser. The assessment
of the kiln burner showed the momentum
and the O2 to be adequate. However, it
was found that the input SO3 from the raw
materials was variable, which often meant
that the clinker MR was >1 and sufficiently
high to saturate the KL level and from
CaSO4 as shown in Figure 7.
This became an issue when it was
found that the clinker LSF had a standard
deviation (SD) of two per cent and the
+90µm AIR for the RM varied from three to
six per cent, meaning CTs well in excess of
1500˚C.
The solution was first to add alkalis to
the mix as needed to avoid excess SO3- as
required. Then longer-term action was
taken to improve the LSF control and
reduce the +90µm AIR to <2 per cent.
Case 2 – plant targets full thermal
substitution in riser but build-up
limits rate
The second case study shows a plant
that is seeking to achieve a thermal
substitution rate (TSR) of 100 per cent, but
as a result of build-up issues is unable to
reach beyond the 50 per cent mark.
Figure 8 shows the current plant’s
hot meal operation well above the

Figure 8: plant hot meal Cl- vs SO3-
established easy-to-operate region. The
plant has no by-pass and uses >50mm
TDF and nutshells in the calciner from the
same feed points and whole tyres on the
feedshelf.
Figure 9 shows the combustion of the
TDF and the nutshells. Only the ≤25mm
TDF fraction combusts in the calciner, the
>25mm fraction drops to the feedshelf.
The nutshells reach the exit and only
achieve a burn-out of 70 per cent. This
poor combustion, together with the whole
tyres on the feedshelf and the SO3- and Cl-
levels in the hot meal, lead to a difficult to
operate situation.
The AFR is inserted from only one inlet
above the splash boxes. This quenching
plus the mixing of the O2 results in
combustion issues. To achieve a 100 per
cent TSR the plant will need to:
• Install a venturi with approximately
2m length to promote gas velocities of
35m/s to stop the TDF dropping to the
feedshelf.
Figure 10: hot meal excess SO3-, potassium langbenite and CaSO4
©Copyright Tradeship Publications Ltd 2017
Figure 9: combustion of TDF and nutshells – (a) TDF <25mm, (b) TDF
>25mm, (c) nutshells
• Stop using
whole tyres or
install the fingers
system developed
by Blue Circle
Industries
• Relocate the AFR feed to below the
splash boxes and modify the splash
boxes to a two-step meal approach as
developed by PM-Technologies.
• Increase the momentum in the sleeves
of the calciner burners.
• Install a bypass to take out 300mg
Cl/kg clinker which is at three per
cent. This can be easily implemented
with a hot meal by-pass (80 per cent
less expensive than a gas bypass) as
developed and installed on several
plants by PM-Technologies.
Case 3 – plant with intermittent rings
and high free-lime flushes
Intermittent phenomena are the most
difficult to resolve. In this case, the clinker
JULY 2017 INTERNATIONAL CEMENT REVIEW
QUALITY CONTROL 83
data were checked to see whether the SD
of the LSF was at an acceptable level and
showed no trend with free lime. The hot
meal was checked and found to be OK and
below the Cl-HM = 2 - 0.4 • SO3- rule, with a
VFSO3 of 1.7 and SF of only 4.7.
However, on detailed checking of the
normal hot meal data it was found that the
excess SO3- in the form of CaSO4 was close
to the danger level of >1 per cent, as shown
in Figure 10.
The set-up at the plant is as follows:
• The burner has a low momentum. •
The calciner – similar to Case 2 – has the
coal just below the splash boxes on the
back wall.
• The tertiary air duct (TAD) setting and
operation can deprive the kiln burner
of O2.
• The coal, some of which is sourced
locally, can be difficult to grind to the
required fineness.
This combination of these factors can
result in the low burner momentum to give
a stratified KBE O2 at a low level depending
on TAD damper setting, which with a
difficult to burn coal will have a C HM of
>0.1 per cent. This will not burn out the
kiln, setting up bigger SO3- cycles that will
lead to flushes and rings.
Currently two measures are being
taken to resolve the issue. Firstly, a kiln
burn design has been selected to give a
non-stratified KBE O2, with a momentum
of 10N/MW. In addition, the coal injectors
have been moved to below the TAD’s
inclined down at 30˚ and a primary air (PA)
sleeve has been installed around the coal
injectors with seven per cent at 200m/s. n
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Housing start jitte
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THE NUMBER
OF housing starts
and Japan Contents

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significantly in and new planni
the first six month ng applications

n real estate service s of 2016, accord in central Londo

s and investment
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slowdown of 65
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Market Reports section
and declining 2
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recorded in four 34,300 in 1Q16 construction in
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good work of the charge and the s the end Cemex opens new
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mance is report Neil Chegwidden, New sand and
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Cement Plant Directory

US housing starts edly representativ director of researc
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