Fuel 99 (2012) 20–39

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Fuel
journal homepage: www.elsevier.com/locate/fuel

Alternative fuels in cement manufacturing: Modeling for process

optimization under direct and compound operation
Christos Aristeides Tsiliyannis ⇑
ANION Environmental Ltd., 26 Lykoudi Str., Athens GR 11141, Greece

a r t i c l e i n f o a b s t r a c t

Article history: Due to thermal, or exhaust air blower capacity limitations in cement manufacturing processes, the use of
Received 28 December 2010 alternative fuels may necessitate production volume reductions from the nominal value achieved by fos-
Received in revised form 13 March 2012 sil fuels, leading to considerable profit reductions. A novel linear algebraic model is presented herein,
Accepted 19 March 2012
which isolates combustion stoichiometry invariants from fuel feed flowrates (decision variables). It
Available online 10 April 2012
allows rigorous, though explicit modeling of the integrated kiln-soil mill-fuel mill system, based on fun-
damental mass and energy balances. It enables assessment of the impact of key operational parameters
Keywords:
and inner circuits on production level and kiln emissions, when alternative fuels (AFs) are used. Neces-
Alternative fuels
Cement manufacturing
sary conditions for balancing the integrated kiln – soil mill – fuel mill process are given in terms of a pri-
Waste recycling ori known physicochemical parameters and process operational data, both for compound and direct
Energy recovery operation. A five-step procedure for process balancing is proposed in order to reap the potential benefits
Clinker process modeling of AF use by selecting a non-inferior AF and conventional fuel mixture. It is shown and demonstrated by
an actual case-study, that the enthalpy balance is the clinker production level limiting factor (binding
constraint) while the kiln – soil mill offgas exhaust blower may be operated well below capacity.
Ó 2012 Elsevier Ltd. All rights reserved.

1. Introduction Due to process, economic and environmental constraints, e.g.

With 30–40% of the total costs attributed to energy costs (3.3 GJ
or 120 kg of coal per 1 ton of cement) [1], cement production is
benefiting worldwide by use of alternative fuels (AF). Economic,
as well as, environmental benefits result by substitution of fossil
fuels, mainly coal and petcoke. Specific types of AFs derived from
mixtures of wastes have been developed e.g. [1–8] such as animal
byproduct waste (ABW), agricultural plastic waste (APW), automo-
tive waste plastic (AWP), biological sludge (BIS), cutting oil emul-
sions (COI), cable plastic waste (CPW), demolition waste (DW),
industrial waste fuel (INBRE), refuse derived fuel (RDF or BRAM
or SRF), rice husk (RH), refinery sludge (RS), spent solvents (SS),
tyre derived fuel (TDF), waste oils (WO), etc. Biomass-based fuels,
including wastepaper and sewage sludge, are receiving increased
attention due to carbon emission credits. Suitability of AFs depends
on several properties, such as physical state (solid, liquid, gaseous)
lower heating value, composition and content of ash, toxicity (or-
ganic compounds, heavy metals), volatiles content [8], humidity
content, physical properties (scrap size, density, homogeneity)
content of circulating elements (Na, K, Cl, S), grinding properties
and storage/feeding capabilities.
⇑ Tel./fax: +30 210 2285650.
E-mail address: anion@otenet.gr
[9], the use of AFs may not be both ecologically and economically
justifiable while AF types and substitution must be carefully cho-
sen. Several criteria have to be met [9–15] towards this goal. The
critical issues involved are: (a) technological such as LHV and kiln
thermal rate or storage feeding modifications or process adjust-
ments (b) fate of pollutants present in the AFs and product quality
(c) legal issues relating to licensing and environmental compliance
and (d) economic issues related to the economic cost/benefit of the
AF within the technological, product quality and environmental
constraints. Adherence to pre-set quality specifications for AFs is
an important step towards control of atmospheric releases and
product quality.
Albeit such criteria are useful for screening of AFs, they are not
quantitative and they do not provide a method for selecting an
appropriate conventional fuel and AF mixture. In practice it is a
challenging task for kiln operators to define the real possibility of
substitution by evaluating the quality and thermal characteristics
of AF as the basic parameters, to define the compatibility at fixed
substitution ratios and to balance the kiln, let alone the issue of
selecting a non-inferior AF and conventional fuel mixture.
An important problem to be systematically addressed relates to
the economic and environmental trade-offs which have to be ob-
served. Higher flue gas volume related to calorific substitution of
conventional fuels by biogenic AFs, in conjunction with blower
capacity limitations may necessitate production cuts which must

0016-2361/$ - see front matter Ó 2012 Elsevier Ltd. All rights reserved.
http://dx.doi.org/10.1016/j.fuel.2012.03.036
 C.A. Tsiliyannis / Fuel 99 (2012) 20–39 21

Nomenclature

A be the inverse of the rxr diagonal matrix of atomic r pollutant emission mass rate vector (g/s)
weights A = {diag (AW)j}1, of the chemical elements Qfg kiln flue gas volumetric flowrate (Nm3/h)
in the conventional and alternative fuels C, H, O, S,Cl, Qfm kiln/fuel mill gas volumetric flowrate (Nm3/h)
N, P Qk sm kiln/soil mill gas volumetric flowrate (Nm3/h)
ABW alternative fuel, animal byproduct waste Qksmax maximum capacity of the kiln/soil mill APCS blower
APCS air pollution control system (Nm3/h)
APW alternative fuel, agricultural plastic waste Rmxm ¼ aqT þ hðI  aeT Þ ¼ hI þ M1 T
air awe M
AWP alternative fuel, automotive waste plastic R universal gas constant = 0.08206 (atm Lt)/(mol K)
a =vector giving the oxygen and nitrogen mass flows from RDF alternative fuel, refuse derived fuel
total air mass flow in the order of the flue gas vector RH alternative fuel, rice husk
constituents aT = (0, 0, 0,21, 0,79, 0,. . ..0) RS alternative fuel, refinery sludge
Bmxn matrix independent of the fuel vector B = :S A1 W + g Smxm stoichiometry matrix of fuel conversion to flue gas prod-
u1 (e1kT  rT) ucts
BIS alternative fuel: biological sludge SRF alternative fuel, solid refuse fuel
BRAM alternative fuel from solid waste (Brennstoff aus Mull) SS alternative fuel, spent solvents
COI alternative fuel: cutting oils, or COI emulsions T temperature, Tkiln: kiln, Ts: ambient, Tr: heat of reaction
CPW alternative fuel, cable plastic waste reference, Tp: preheater
c vector of pollutant concentrations TDF tire derived fuel
cp vector of heat capacities of the flue gases ui ith unit vector (0, 0, 0, . . ., 1, 0, 0)
ðcp1 ¼ cpCO2 ; cp2 ¼ cpH2 O; cp3 ¼ cpO2 ; cp4 ¼ cpN2 ; cp5 ¼ cpSO2 ; Wrxn rxn matrix of net fuel weight composition, without the
cp6 ¼ cpHCl2 ; cp7 ¼ cpP2 O5 in kca/kg K slag: the ith column of W is the % weight composition
cp clinker clinker heat capacity in kca/kg K of the ith fuel in the combustible elements, multiplied
cpf fuel heat capacity vecor, in kca/kg K by the net combustible content (1  ri) of the ith fuel,
cp rm raw meal heat capacity in kca/kg K Wj = (1  ri) (%C, %H, %O, %S, %Cl, %N, %P)T
DW alternative fuel, demolition waste WO alternative fuel, waste oils
ds sulphur detainment fraction by the clinker alkaline
matrix GREEK
dCl chlorine detainment factor asm air drawn in the soil mill, kg per kg clinker
e orthodiagonal vector eT = [1, 1, . . . , 1], afm air drawn in fuel mill, kg per kg clinker
f fuel feed mass flowrate vector (fi in t/y), in Case Study: b vector bT = (b1, b2, . . ., bn) of air drawn per kg of ith the
f1: coal, f2: petcoke, f3: trial AF, f3: TDF, f4: BIS, f5: RDF fuel in the fuel mill
h air moisture, molal fraction c =260 ton CO2 eq/ton N2O greenhouse gas equivalence
I identity matrix factor, N2O to CO2 eq
INBRE alternative fuel from industrial waste (Industrial Bren- DH =enthalpy with respect to a reference level
nstoff) d Difference between alternative fuel mixture and base-
k total clinker production level, (t/y) = e1 kTf line (conventional) fuel mixture, dLHV = LHV  LHVo.
km =(e1kT  rT)f = raw meal clinker production (t/y) (not e specific energy requirement per t of clinker (kcal/kg
including slag incorporation) clinker) or TJ/t clinker,
kCO formation reaction constant = 3  104 exp (67.000/RT) f f is the ww fraction of raw meal in CaO, typically f is be-
kN NOx reaction constant tween 0.4 and 0.5.
kN2 O N2O formation reaction N2 + 1/2 O2 ? NO, kN2 O ¼ 2:4 g g = f/56 (1  M1f/56)1, # kmols of CO2 produced via
exp (1027/RT) lime dissociation (reaction b) per t of clinker, km
kNO NO formation reaction 1/2 N2 + 1/2O2 ? NO kNO = 4.69 h fraction of flue gas cleaned in the kiln/soil mill
exp (21.600/RT) APCS
kNO2 NO2 formation reaction NO + 1/2 O2 ? NO2, kNO2 ¼2.5 jm annual clinker quantity originating from the raw meal
exp (13.720/RT) j, j0 scalars determined only in terms of baseline case data
LHV total heat rate from fuel combustion based on lower (Eqs. (21) and (24))
heating values = kTf j vector dependent on fuel type but independent of the
mfg vector of the mass of flue gases produced = mass flows fuel feed rate, Eq. (22)
of (CO2, H2O, O2, N2, SO2, HCl, P2O5). j0 vector dependent on fuel type but independent of the
mfg total mass of flue gases from reaction (a) fuel feed rate, Eq. (25) if the flue gas blower capacity
msm air total mass of soil mill air driven to the kiln/soil mill equals that of the baseline case
APCS k vector of lower heating values of the various fuels, 1, 2,
mfm air total mass of fuel mill air driven to the fuel mill APCS . . ., n, i.e. kT f is the total annual thermal rating of the kiln
mrm raw meal feed rate /preheater system
m fuel vector of mass feed rates q ¼ ðhI þ M1 air wMÞe that is component qi = [h + w (MWi/
Mmxm =diag {MW (CO2), MW (H2O), MW (O2), MW (N2), MW MWair)], e.g. q1 = h + w (MWCO2/MWair), etc.
(SO2), MW (HCl) MW (P2O5)} = diag {44, 18, 32, 28, 64, ri % ww of noncombustible solids (slag) contained in the it
36.5, 142) fuel,
Mair =MWair = molecular weight of air = 28.84 t specific molal flue gas volume underx P, T conditions
M1 molecular weight of CO2 = MW (CO2) = 44 = RT/P
NG natural gas w mass fraction of pseudo-air with respect to the kiln flue
P pressure gas (Pseudo-air is mixed with the flue gases after the
PC petcoke preheater)
22 C.A. Tsiliyannis / Fuel 99 (2012) 20–39
Subscripts
0 refers to the baseline case with conventional fossil fuels
1 refers to CO2
be balanced against revenues form CO2 emissions trading and low-
er AF cost. This renders the volume of flue gases one of the most
prominent technical/economical issues. Mixing the low heating va-
lue BIS with plastics or rubber (TDF) is a usual remedy. Substitu-
tion of pet coke (LHV = 34,000 kJ/kg) with a 17,000 kJ/kg RDF
leads to an increase of more than 15% in the produced flue gas [1].
Besides production cuts, which, in cases of economic expansion
and rising demand are hardly admissible, pollutant emissions are
affected by the AF use, not only with regard to the maximum stack
concentrations to which the plant must comply [9], but also, by the
off gas flowrate which determines pollutant emission rates. In
cases of higher offgas volumes, emissions rates are higher and con-
stitute the decisive factor for the resulting pollutant concentrations
in sensitive downwind receptors, where maximum concentration
limits must also be obeyed [16]. PCDD meaurements from actual
plant using BIS showed no substantial increase of receptor concen-
trations upon coal substitution by BIS [17–19]. In contrast, other
measurements showed that increasing amounts of sludge or tyres
directly fed to the kiln in an actual cement plant resulted in larger
flue gas volumes, as well as higher stack emissions of PAHs and
dioxins at high thermal substitution [20]. The average emission
factor for kilns burning halogenated hazardous waste was reported
about 90 times greater than for kilns burning nonhazardous waste
[21]. Pollutant emissions are affected not only by the concentration
in a specific AF, but from the fuel/air mixture, as well as, the pres-
ence of other AFs [8,22] and their content in various constituents:
for instance high oxygen concentration in the flue gases inhibits
PCDD/PCDFs albeit favors NOx formation. Chlorine bypass is also
an inhibiting factor for dioxine formation and for heavy metal re-
leases, but it results in considerable energy losses. NOx releases
may be reduced by slightly lowering excess air, or combustion
temperature – so as to not hamper alite formation [22] and product
quality. A benefit of 0.36 kg NOx/t of burned RDF is reported [14].
Lowering excess air may result in higher stack pollutant concentra-
tions. SOx are, in general, well retained by the alkaline micro-envi-
ronment and hence sulphur in the fuel is not traditionally
considered a pollutant precursor. In addition, coal sulphur may
reduce PCDD/PCDF emissions [23,24]. However, substitution of
petcoke with low sulphur AFs such as BIS, results in lower SOx
emissions.
The % ww of coal in the fuel mixture is also important since it
inhibits PCDD/PCDF emissions, albeit it may favor reactions with
different metals in raw meal and increase their release with the
flue gases [24]. Biogenic AFs containing sulphur (such as coal) pre-
vent the formation of alkaline and chlorine compounds on the fur-
naces [25,26]. AF chlorine, e.g. from biomass such as wheat straw
and rice husks, may also increase the volatility of heavy metals
[27,28] cause slagging and corrosion in the kiln and foster the for-
mation of dioxins.
Most heavy metals in the fuels or raw materials are effectively
incorporated into the clinker (almost 100% for As (mainly from
conventional coal), Sb, Ba, Be, Cr, Pb, Ni, V and Zn and at about
97% for Ni, 93% Cr, 72–96% for Pb [29]). The volatiles mercury
(Hg) and cadmium (Cd) are mainly found in the offgases, especially
in the presence of chlorine [30,31]. Some AFs, e.g. RDF, usually have
higher contents of Sb, Hg, Cd, As, Pb, Cu, Cr and Zn than petcoke.
Coal may also present Hg, Co, Cd and Tl. Clinker enrichment by
the slag contained in the various fuels affects the mass and energy
balance of the kiln, as well as product quality. Detained metal con-
centrations should not exceed 300–400 mg/kg (ppm) [29].
Superscript
T
transpose of a vector or a matrix
Insight into the impact of excess air upon use of AFs on the kiln
temperatures affecting alite – belite ratio and product quality was
gained by the modeling/simulation results presented in [22,32].
Investigation of the impact of using COI emulsion on NOx, CO,
VOC emissions via kinetic modelling, [33,34], showed that emis-
sion concentrations are likely to be lower by kiln injection, leading
to up to 50% reductions in NO levels, while injection of relatively
high nitrogen content COI in the precalciner may lead, under lean
conditions, to NO level increases. The possibility for PCDD/F forma-
tion is diminished by fine atomization and sufficiently long tertiary
air ducts, while case-specific composition analysis is a necessity for
metal species [35].
All the above are affected by process parameters set by the
operators, such as energy integration parameters and inner mass
circuits. For instance, a fraction (appropriately set by the operator)
of the kiln/precalciner/preheater flue gas is rendering inert and
heating up the fuel mill air, while during compound operation
(when the soil mill is on), another approrpiately set fraction is
heating up the raw meal. The latter is cleaned jointly in the kiln
APCS with the soil mill air and with an auxilliary air stream (pseu-
do air) regulated by the operator. During direct operation, the flue
gases are quenched and the pseudo air may be reduced. Since in
most cases, the fuel kiln/mill gases are separately treated from
the kiln/soil mill gases, the fuel mill may be operated well below
its design capacity when AFs are used, leading to lower volume
of gases to the respective APCS. It is clear that the interplay of
the operational parameters with the fuel mixture, prominently af-
fects production level, concentrations, rates of emissions and clin-
ker enrichment/quality, during the various phases of operation
(e.g. compound and direct) of a dry clinker process, thus being of
paramount importance. An efficient fuel inventory control on a
weekly or even day-to-day basis may be ante portas.
This accumulated practical and theoretical experience has not
yet been incorporated in a coherent modeling and quantitative
analysis tool, which would provide quantitative insight into the
above production capacity limits and product quality, as well as
economic and environmental repercussions of AF use. Such a tool
could provide valuable guidance for balancing the economic and
environmental trade-offs upon selection of an appropriate mixture
for partial substitution of coal or petcoke. Within this framework
the present research is addressing the following needs and ques-
tions: (1) the need for an explicit and integrated process model,
in terms of the fuel mixture, which would readily reveal the quan-
titative impact of various AFs and would allow comparison with
the baseline conventional fuel case (2) the need for easy to check
conditions for balancing the kiln and the integrated kiln-soil mill
– fuel mill system, (3) quantitative prediction of possible produc-
tion level cuts due to thermal or blower capacity limitations, (4)
impact of operational parameters such as excess air, fractions of
the flue gases circuited to the soil mill and the fuel mill, as well
as soil/mill air and pseudo air flows, (5) impact of raw material
characteristics and process parameters (e.g. raw meal CaO content
or fuel slag content, kiln temperature) under AF use (6) impact of
switching from compound to direct operation and the new param-
eter values balancing the kiln, (7) impact of AF use on greenhouse
gas emissions (8) a procedure for selecting an appropriate AF mix-
ture which results in low economic sacrifices while the process re-
main balanced. With regard to (8), the problem of selection
optimal fossil fuel mixtures for cement kiln was addressed in
[36], while in [37,38] alternative fuels were included; however
 C.A. Tsiliyannis / Fuel 99 (2012) 20–39
the enthalpy balance was not considered, while, in addition, the
internal mass and energy circuiting associated with compound
operation were not included in the mass balances.
The presentation is organized as follows. Section 2 describes the
process and presents the kiln stoichiomety in a systematic way
applicable to any mixture of alternative fuels with conventional
fuels. Section 3 presents the mass and energy balance model for
the integrated process, both for compound and direct operation,
in terms of the flowrates of the various fuels. Section 4 gives
necessary conditions for process balancing, taking into account
thermal capacity or exhaust air blower constraints. It also gives
the greenhouse gas emissions and proposes a five-step procedure
for balancing the integrated kiln-soil mill-fuel mill system in terms
of operator paramateres. Section 4.2 presents an actual case study.
2. Background: cement manufacturing process and flows
In a typical dry process plant, soil materials and combusted fuel
are transformed to clinker and off gases (Fig. 1) in temperatures
reaching 1500 °C (kiln). The clinker is subsequently air-cooled in
the clinker cooler, mixed with additives and ground to cement.
More precisely, the raw materials are ground to raw meal which
is then dried and heated by passing through a series of suspended
cyclone preheaters and (possibly) partially calcined in the precal-
ciner before being fed into the rotary kiln, where it is eventually
sintered into clinker. The heated cooler-air-stream from the clinker
cooler is fed both to the rotary kiln (secondary air) and to the pre-
calciner (tertiary air), recycling heat back into the process. Com-
bustion flue gas from the kiln is used to heat up the precalciner/
preheater process and part of this stream is heating up the air in
the soil mill. The cooled flue gas mixed with the soil mill air and
possibly an auxiliary air stream (pseudo air), is dedusted in the
kiln/soil mill APCS system. Another part of the hot kiln fluegas is
used to render inactive and to heat up the fuel mill air and is sep-
arately dedusted (Fig. 2).
In order to explicitly describe the above operation in terms of
the fuel types and quantities, a compact model of the system is
developed based on fundamental principles, i.e. stoichiometry
and mass/energy balance. The model is necessarily multivariable
and multiparameter, rendering the use of vector notation indis-
pensable for compact representation. The reactions taking place
in the rotary kiln preheater/precalciner are:
Cx1 Hx2 Ox3 Sx4 Clx5 Nx6 Px7 þ ð1 þ EÞ ðx1 þ u þ x4 þ 5=4 x7  0:5 x3 Þ O2 þ
hð1 þ EÞ ðx1 þ u þ x4 þ 5=4 x7  0:5 x3 Þ=0:21 H2 O þ ð1 þ EÞ 79=21 ðx1 þ u þ x4 þ 5=4 x7  0:5 x3 ÞN2
! x1 CO2 þ ð2u þ h ð1 þ EÞ ðx1 þ u þ x4 þ 5=4 x7  0:5 x3 Þ=0:21Þ H2 O
þE ðx1 þ u þ x4 þ 5=4 x7  0:5x3 Þ O2 þ ð0:5 x6 þ ð1 þ EÞ 79=21 ðx1 þ u þ x4 þ 5=4 x7  0:5 x3 ÞÞ N2 þ
X4 SO2 þ x5 HCl þ 1=2 x7 P2 O5
CaCO3 ! CaO þ CO2 ðbÞ
where
u = 1/4 (x2  x5) if x2 > x5
u = 0 if x2 6 x5
h = air humidity (molal fraction)
E = excess air.
23
3. Modelling of kiln reaction stoichiometry
3.1. Lime dissociation
Let i = 1, 2,. . ., n be the fuels of known ultimate analysis which
participate in the fuel mixture to be used. The first entries may
be reserved for conventional fuels, e.g. i = 1 for coal and i = 2 for
petcoke. Using matrix notation, with T denoting transpose let,
fT = (f1, f2, . . . , fn) denote the fuel mass feed rate vector in t/year,
r= the slag rate vector, ri is the % ww of noncombustible solids
(=slag) contained in the it fuel,
k be the vector of lower heating values of the various fuels, in
the same order 1, 2, . . ., n,
k denote the total clinker production level, t/y.
e = the specific energy requirement per tone of clinker (kcal/kg
clinker) produced, that is
e k ¼ kT f ð1Þ
T
i.e. k f is the total annual thermal rating of the kiln/preheater sys-
tem. If the raw meal CaO content, f, is known, e.g. f = 43% ww,
the raw meal feed rate and the carbon dioxide mass production rate
from raw meal dissociation (b) are given by (see Appendix A):
mCO2 ;lime ¼ M1 g ðe1 kT  rT Þf ð2Þ
1 T
ðraw mealÞ ¼ ð1 þ M 1 gÞ ðe k  r Þf T
ð3Þ
where M1 = MWCO2 = 44 and
g ¼ f=56ð1  M1 f=56Þ1 ð4Þ
Use of AFs affects clinker quantity via the incorporation of inerts.
The total mass of clinker produced/year is given by adding the in-
erts contained in the fuel and assuming the mass of non – combus-
tible volatiles to be negligible. Thus, if ri is the % ww of
noncombustible solids (slag) contained in the it fuel, and
rT = (r1, r2, . . . , rn), the total clinker term, k, in Eq. (1) includes the
respective slag contribution rTf.
3.2. Combustion stoichiometry
A fundamental problem encountered in kiln balancing when
partially substituting fossil fuels (usually coal/petcoke) by alterna-
tive fuels, is the introduction of a large number of variables and the
cumbersome task of calculations which do not reveal the marginal
ðaÞ
impact of substitution on flue gas volumes and species composi-
tion. The task becomes impossible when a non-inferior combina-
tion of fuels and feed rates is sought for economic and
environmental reasons. In the sequel a novel linear operator for-
mulation of combustion stoichiometry is presented, which allows
compact representation of the system relations and, in addition,
isolates the invariant kernel of the stoichiometric model under fuel
mixture modifications. Let MW and AW denote molecular and
24 C.A. Tsiliyannis / Fuel 99 (2012) 20–39

Fuel Air Soil

materials

Flue gas

Cleaned flue
Air Pollution gas (off gas)
Clinker Clinker Control
Cement
Production Systems
Production/
Packaging
Gypsum

Cement

Fig. 1. Cement manufacturing process.

Air
Fuel Mill
APCS

Coal Soil
Fuel Air materials
and
Petcoke 1-θ
Mill
Suspension Water Rotary
Preheater, Quen- Kiln/
θ
Precalciner, cher Calciner
Soil Mill Rotary Kiln /Preheater
and Soil
Mill APCS

Air

Flue gas flow Compound operation Direct operation

Fig. 2. Clinker manufacturing: flow diagram of dry process with main recycle and thermal integration circuits and flue gas pollution control.

atomic weight. Consider the stoichiometric combustion of the and M, A are augmented to 4  4 matrices to include oxygen and
hydrocarbon, CxHy, at a mass flowrate f, nitrogen, that is M33 = MWO2, M44 = MWN2, A33 = AWO2, A44 = AWN2,
W remains the same, while S becomes the 4  2 matrix:
Cx Hy þ ðx þ y=4Þ O2 ! x CO2 þ y=2 H2 O ðcÞ
0 1
The flue gas mass flowrates are given by mCO2 ¼MWCO2 (1/AWC) 1 0
B 0 1=2 C
(mass fration of C in the hydrocarbon molecule) or mCO2 ¼MWCO2 B C
S¼B C
1 (1/AWC) (12x/(12x + y)) f and mH2 O ¼MWH2 O (1/2) (1/AWH2) (mass @ E E=4 A
fration of H2 in the hydrocarbon molecule) f or mH2 O ¼ MWH2O (1/2) 79=21ð1 þ EÞ 79=21ð1 þ EÞ=4
(1/AWH2) y/(12x + y) f, e.g. for methane x = 1, y = 4. These expres-
sions may be written in vector notation as: in which the upper 2  2 part remains the same as before and the
flue gas flowrates are again given by mfg = MSA1Wf. Clearly, M
         
mCO2 MWCO2 0 1 0 1=AWC 0 12x=ð12x þ yÞ and A do not depend on the fuel. In addition, S is independent
¼ f
mH2 O 0 MWH2 O 0 1=2 0 1=AWH2 y=ð12x þ yÞ of the fuel, and in particular of its composition, i.e. of x and y.
M S A1 W Thus, in a mixture of two hydrocarbons, fed at mass rates f1
and f2, MSA1 remains the same, while W is augmented by a sec-
where M, S, A are 2  2 matrices and W is a 2  1 matrix (see be- ond column:
low). S is a key invariant matrix defined as follows: The number     
of rows of S equals the number of flue gas species. The number of f1 12x=ð12x þ yÞ 12x=ð12x þ yÞ f1
Wf ¼ W ¼
columns of S equals thenumber of elements in the fuel. The element f2 y=ð12x þ yÞ y=ð12x þ yÞ f2
S11 of the matrix S is the factor multiplying x in the stoichiometric
coefficient of the first product, CO2, in reaction (c) above (=1), S12 is (The columns of W are equal because both fuels are hydrocabons).
the factor multiplying y in the stoichiometric coefficient of the first Moreover, under any variation of the feed rates f1 and f2, of the
product, CO2, in reaction (c) above (=0), S21 is the factor multiplying two hydrocarbons, not only does the kernel MSA1 remain the same
x in the stoichiometric coefficient of product H2O in reaction (c) (=0) but the product MSA1 W will remain invariant, (i.e. W enters the
and S22 is the factor multiplying y in the stoichiometric coefficient kernel). If an alcohol Cx1 Hx2 Ox3 is added to the fuel mixture at a mass
of product H2O in reaction (c) (=1/2). If excess air is used then: flowrate, f3, then the flue gas species remain four, as before and the
clemical elements become 3. Thus M, A remain the same, while S is
Cx Hy þ ð1 þ EÞ ðx þ y=4Þ O2 þ ð1 þ EÞ ðx þ y=4Þ 79=21N2 augmented by a third column consisting of the factors of oxygen
! x CO2 þ y=2 H2 O þ Eðx þ y=4Þ O2 þ ðx þ y=4Þ 79=21 ð1 coefficient (x3) in the flue gas species according to reaction (a):
assuming air humidity, h, equal to zero for simplicity, the matrix
þ EÞ N2 ðdÞ S is given by the same exact procedure, as:
 C.A. Tsiliyannis / Fuel 99 (2012) 20–39
0 1
1 0 0 has nonzero first row equal to g (e1kT  rT), and all other rows
B 0 1=2 0 C
S¼B
@
C
A
E E=4 0:5E
79=21ð1 þ EÞ 79=21ð1 þ EÞ=4 ð0:5Þ79=21ð1 þ EÞ
e.g. in the last row S43 is the factor multiplying x3 in the stoichiom-
etric coefficient of the fourth fluegas product, N2, in reaction (a)
(=(0.5)79/21(1 + E), if h = 0). It is evident that the matrix S above
suits any fuel containing carbon, hydrogen and oxygen. In a fuel
mixture of n fuels a common matrix S for all fuels, may be utilized,
in which the dimensions correspond to the largest values of m
(number of flue gas species) and r dictated by the fuel with the
highest number of elements (r). Then S will remain the same mxr
matrix for all n combustion reactions (a). In addition, since the col-
umns of W are the ww elemental fuel compositions, if it corre-
sponds to the maximum number of fuels under investigation, it
applies to all candidate fuel mixtures arising by leaving out some
of the individual fuels (the respective feed rates, fi, are zero) and
the kernel MSA1W remains invariant under any variation of the
feed rates f1, f2, . . ., fn. In practical applcations and according to reac-
tion (a) the dimensions of S reach m = 7, r = 7. For instance, in a mix-
ture of 20 fuels represented by Cx1 Hx2 Ox3 Sx4 Clx5 Nx6 Px7 for differing
values of the xi, it follows that m = 7, r = 7, and MSA1W remains
invariant under any combination of f1, f2, . . ., f20; the fuel feed rate
vector f (decision variable) has been isolated from the combustion
stoichiometry kernel, MSA1W. Evidently, under variations in the
ultimate analysis of any fuel (say the jth fuel) only the respective
column of W changes (say the column Wj changes by dWj) and
the marginal change of the flue gas flowrates is equal to MSA1dWjf.
We proceed to the formal presentation. Let:
W be the rxn fuel composition matrix, i.e. the jth column of W is
the % weight combustibles’ composition of the jth fuel,
Wj = (1  rj) (%C, %H, %O, %S, %Cl, %N, %P)T
A1 be the inverse of the rxr diagonal matrix of atomic weights
Arxr = {diag (AW)j}1, in the order C, H, O, Cl, S, N, P.
e be the orthodiagonal vector eT = [1, 1, . . ., 1],
ui= the unit vector in the ith direction, e.g. uT1 ¼[1, 0, . . . , 0], etc.
Mmxm be the mxm products’ molecular weight diagonal matrix:
M ¼ diag fMWðCO2 Þ; MWðH2 OÞ; MWðO2 Þ; MWðN2 Þ; MWðSO2 Þ;
MWðHClÞ; MWðP2 O5 Þg:
Then the mass flowrate vector of fluegas produced in the kiln/pre-
calciner/preheater system, mTfg ¼ mfCO2 ; H2 O; O2 ; N2 ; SO2 ; HCl;
P2 O5 g resulting from reactions (a) and (b) is given by:
mfg ¼ M B f ð5Þ
where
B = SA1 W + u1g (e1kT  rT), a mxn matrix, invariant if the n
fuel types remain the same, Smxr is a mxr constant matrix indepen-
dent of the fuel (Appendix B). The element Sij is the factor multiply-
ing xj in the stoichiometric coefficient of fluegas species i. Under
constant excess air, E, and air humidity, h, the matrix S remains
constant independently of the fuel type or feedrates. Then, the
mxr matrix M S A1 is the combustion process stoichiometric
invariant and does not depend on the fuel, i.e. it is universal for
constant excess air. The jth column of the rxn matrix W consists
of the % ww elemental composition of the jth fuel. It is fixed once
the type of fuel mixture is chosen and does not depend on the rel-
ative feed rates of the fuel constituents, conventional or alterna-
tive. Similarly r remains the same once the types of fuels are
given. For instance, any mixture of (coal, petcoke, TDF BIS, RDF)
has the same W and r, while if APW is used instead of RDF, then
the 5th column of W corresponds to the % ww elemental compos-
tion of APW instead of RDF and the fifth element of r corresponds
to APW instead of RDF. In both cases MSA1 is the same. The mxn
matrix u1g(e1 kT  rT) is independent of the fuel rates as well; it
25
equal to zero; from Eq. (2) if multiplied by f it gives the annual mo-
lal rate of CO2 due to lime dissociation.
Proof. See Appendix A. h
Eq. (5) gives the individual flowrates of the total kiln/preheater/
precalciner fluegas constituents and allows all manipulations to be
performed in the fuel vector, f, on which the linear operator
M(SA1W + u1g (e1kT  rT)) (fuel and lime stoichiometry) acts
independently. As a direct consequence the m-vector of kiln flue
gas partial volumetric flowrates is given by Qfg = t M1B f or
Q fg ¼ t Bf ð6Þ
where RT/P = t is the specific molar volume (=22.4 L under normal
conditions). From Eqs. (5) and (6) the total mass and volumetric
flowrates are obtained by adding the individual components of
the vectors mfg and Qfg, or, as the inner product of mfg and Qfg with
the vector e,
mfg ¼ eT mfg ¼ eT M Bf ð7Þ
T T
Q fg ¼ e Q fg ¼ te Bf ð8Þ
3.3. Kiln and soil mill balance: inner/outer circuit & compound/direct
operation and bypasses
3.3.1. Compound operation
The vector formulation described above is employed in the se-
quel for representation of the actual cement process, featuring flue
gas cirquiting and heat integration. In the inner circuit, consisting
of kiln/cyclone/preheater, volatile compounds (e.g. Hg, Cd) are car-
ried with the gas flow from the kiln to the cyclone preheater,
where they condense and are transported by the raw meal to the
kiln. During normal compound operation the outer circuit kiln/cy-
clone/preheater/soil mill APCS is active and the dust containing
offgas from the cyclone preheater is used for drying and transport-
ing the raw meal from the soil mill. There is no quenching of the
flue gas and the dust from the kiln/soil mill APCS is passed onto
the raw meal silo, or the dust bypass leading to the cement mill.
Assuming, for the moment, no chlorine or sulphate bypass of the
fluegases directly to the APCS, the total flue gas flowrate is ob-
tained via a mass balance around the rotary kiln/cyclone/pre-
heater/soil mill system (Fig. 3).
Let mk sm denote the total mass rate of the gas mixture before
passed through the kiln APCS. It consists of part of the flue gases,
dusty air from the soil mill, and in addition, the pseudo air mass
inflowrate, which is set by the operator as a fraction, w, of the total
flue gas mass flowrate. The dusty air from the soil mill, msm air, is
proportional to raw material crushed in the soil mill, i.e. to the
raw meal as given by Eq. (3). Let the proportionality constant be
denoted by asm:
msm air ¼ ½asm ð1 þ M1 gÞ ðe1 kT  rT Þ f ð9Þ
The pseudo-air mass flow rate is proportional to the kiln mass flow-
rate of flue gases, mp = w mfg, or from Eq. (6)
mp ¼ w eT MB f ð10Þ
where the constants asm, w, are independent of the fuel mixture. If
the pseudo-air duct is closed, then w = 0. During direct operation
asm = 0. Let also (1  h) be the flue gas mass fraction which is fed
to the fuel mill in order to create an inert atmosphere and to heat
up the fuel, which will be dedusted in the fuel mill APCS. Then h
is the mass fraction of kiln flue gases which, without quenching,
is dedusted in the kiln/soil mill APCS and of which, a part (usually
close to 100%) is used to heat up the raw materials when the mill
26 C.A. Tsiliyannis / Fuel 99 (2012) 20–39

Fuel Mill stack

APCS

θ Kiln/Soil Mill
Water APCS stack
Quen-
cher

Coal and Pseudo

Petcoke Mill Air

Fuel Soil Raw materials

Mill
Air

1-θ
Air Raw meal

Milled
Fuel

Primary Air Fuel

Suspension Fuel
Preheater,
Precalciner, Air
Rotary Kiln
kiln

Clinker clinker
Tertiary air Secondary
Cooler
air

Flue gas flow

Direct operation
Compound operation

Fig. 3. Clinker manufacturing: dry process with main circuits.

is on (compound operation), that is, it is mixed with soil mill air, to asm = 0. During direct operation, albeit dust emissions in the kiln/
be jointly dedusted. Denoting the air molecular weight (=28.84) by cyclone/preheater/soil mill/APCS off gas may be lower, w may have
Ma and using the definition of the vector q (see notation) the flue to be increased in order to comply with limits of sulphur or tem-
gas mass and volumetric flowrate vectors become (see Appendix A): perature dependent emissions, e.g. volatile heavy metals, espe-
cially mercury, since the off-gas temperature is higher during
mk sm ¼ fR B þ M 1
air a asm ð1 þ M 1 gÞ ðe
1 T
k  rT Þg f ð11Þ direct operation. Alternatively, a different fuel mixture (e.g. con-
Qk sm ¼ t fR B þ M 1
air a asm ð1 þ M 1 gÞ ðe 1 T T
k  r Þg f ð12Þ taining lower RDF quantities) may be selected during direct oper-
ation. The collected dust is partly added to the raw meal, thus
where establishing inner loops of trace elements and partly to the cement
mill, the ratio regulating the accumulation of trace elements in the
Rmxm ¼ aqT þ h ðI  a eT Þ ¼ hI þ M 1 T
air a w e M ð13Þ
kiln/cyclone/preheater/soil mill/APCS circuit (Fig. 3). If a dust by-
is a constant matrix determined only in terms of the operational pass is present, the outer circuit is interrupted relieving the cycle
parameters h and w. The total gas volumetric flowrate is given by: from trace elements. The bypassed dust enters the cement as an
interground additive [31]. Eqs. (5)–(14) are valid in case of chlorine
Qk sm ¼ t fqT S A1 W þ ½q1 g þ M 1
air asm or sulphate bypass since the quantity of the flue gas to be treated
 ð1 þ M1 gÞ ðe1 kT  rT Þg f ð14Þ by the APCS is not changed. Similarly, to the same end, it may be
assumed that hot meal bypass (discharging part of the hot raw
where the first term t{qTS A1 W} f includes fluegas volumetric meal at the lowest cyclone), albeit with lower efficiency compared
flowrate from the kiln/precalciner/preheater process and the second to flue gas bypass, or dust bypass, does not affect flue gas flows.
1 T
term t [q1 g + (1 + M1 g) M1
a asm ] (e k  rT)} f includes CO2 from
lime dissociation, pseudo air and soil mill air (Fig. 4). 3.4. Fuel mill fluegas

3.3.2. Direct operation
During direct operation (Fig. 3) the raw meal is fed to the kiln
via the silo and the soil mill is off-line. The fraction h of the kiln/
precalciner/preheater flue gases is water quenched and then dedu-
sted. There is no soil mill air to be commonly dedusted with this
fraction of flue gases. Eqs. (9)–(14) may account for this by setting
The air mass drawn from the coal/petcoke mill and dedusted by
the air pollution control system of the fuel mill, denoted by mfm air,
is proportional to the quantity of the fuel crushed mfm air = bT f,
where the n-vector bT = (b1, b2, . . . , bn). For instance, if coal and pet-
coke are the fuels ground in the fuel mill, then mfm air = b1f1 + b2f2.
The constants bi represent the specific air mass drawn from the
 C.A. Tsiliyannis / Fuel 99 (2012) 20–39 27

4
11 18
12 23
15
7
Soil Mill Water
Rotary Kiln 22
5 6 6 Quen-
Coal and ching
/Soil Mill
19
Petcoke 17 APCS
Mill 10
Suspension
Preheater 4
14
3 Rotary Kiln
13
2
Precalciner
1
9

Fuel
Mill 20
APCS 8 Clinker Cooler
16
21

24

Flow of solids Fuel flow Air flow Raw Materials flow

Flue gas flow

Inflow streams 1, 11, 12, 15, 16, 17, 23

Outflow streams 21, 22, 24

Fig. 4. Clinker manufacturing: dry process flowdiagram. 1: Primary air. 8: Secondary air. 20: Tertiary air. 17: Pseudo air. Direct operation: Flow of stream 5 = 0. Compound
operation: Flow of stream 5 > 0.

fuel mill per unit fuel mass and are independent of the quantities
of the conventional or alternative fuels, which will partially
substitute coal or petcoke, i.e. they are independent of f. In case
an alternative fuel is not ground then the corresponding bi is zero.
Therefore, the total gas flow dedusted in the fuel mill APCS is
given by the sum of the kiln preheater/precalciner fluegas directed
to the fuel mill and the fuel mill air, i.e.
mf m ¼ M fð1  hÞ B þ M1 T
air a b g f
Q f m ¼ t fð1  hÞ B þ M 1 T
air a b g f
Q f m ¼ tfð1  hÞ eT S A1 W þ ð1  hÞ gðe1 kT  rT Þ þ M1 T
air b g f
Eqs. (2)–(17) give the main gas flows which are affected by the use
of AFs, explicitly in terms of the fuel vector f. Note that eTS A1 is the
row vector resulting from adding the columns of S A1 (given in
Appendix B) while W remains invariant once the mixture of fuels
is chosen, independently of the relative composition of the fuel
mixture.
3.5. Energy balance and clinker production
Due to changes in the energy balance the specific energy con-
sumption, e, is affected by the use of AFs. The impact may be taken
into account by an overall enthalpy balance: DHtotal = DHreactants +
DHflue gas + DHclinker + Heat Loss. With the kiln temperature and
thermal conduction characteristics being the same as in the base-
line case, it follows that the heat loss is the same. It is noted that,
upon partial substitution, DHreactants will not be much different and
is at least one order of magnitude less than the other terms. Intu-
itively this implies that if, upon use of AFs, the sensible heat leav-
ing with the flue gases is larger, then the clinker sensible heat must
ð15Þ
decrease so that the enthalpy balance be satisfied. This will be
ð16Þ established rigorously in the sequel. From the overall balance,
ð17Þ the additional energy needs, d(LHV), supplied by the heat of reac-
tion (a) with respect to the baseline case (use of conventional
fuels), is equal to the sum of (i) the difference in the heat required
to raise the reactants to the reaction temperature (=the
temperature at which the LHV values correspond, i.e. 150°C) (ii)
the difference in the heat required to raise the temperature of
the flue gases to the preheater exit conditions and (iii) the
difference in the heat transferred to the clinker which includes
slag incorporation and accounts for production variations, i.e. equal
to dDHtotal = d{mreactants cpreactants ðT r  T s Þ þ mTfg cp (Tkiln  Tp) +
cp clinker (k  k0) (Tkiln  Tr)}. The resulting expression (see
Appendix A) is:

e k ¼ e0 k0 þ ðcTpf f  cTpf0 f 0 ÞðT r  T s Þ þ cp rm ½ð1 þ M1 gÞ ðk  rT f Þ  ð1 þ M1 gÞ ðk0  rT0 f 0 Þ ðT r  T s Þ

þcp air ½eT ðM S A1 W  IÞ f þ rT f  eT ðM S A1 W0  IÞf 0  rT0 f 0  ðT r  T s Þþ
h  i ð18Þ
cTp M S A1 ðWf  W0 f 0 Þ þ ðk  k0 Þ ðcp CO2 M CO2 gÞ þ cp1 M1 g rT0 f 0  rT f ðT p  T r Þþ
ðk  k0 Þ cp clinker ðT kiln  T r Þ
28 C.A. Tsiliyannis / Fuel 99 (2012) 20–39
The heat capacities of the flue gasses, cp, of the raw meal, cp
the fuels, cpf, and of clinker, cp clinker, are known in advance. Given
any fuel mass feed rate vector, f, the vector Wf the total heat rate, e
k(=kT f) and the total slag difference rT0 f0  rT f may be determined
and since MSA1 is known, the scalar linear Eq. (18) may be readily
solved for k. Note that the simplified version of Eq. (18) obtained
by taking Tr = Ts introduces insiginificant error (<1% on the k value).
Thermal substitution means that kT f is within the maximum heat
rate of the kiln and possibly equal to the total baseline heat rate va-
lue, e0 k0 (in which case thermally equivalent substitution is neces-
sary). If, in the baseline case, the kiln is operated well below its
thermal capacity, then e k can be greater than e0 k0. If the heat rate,
e k, equals to the baseline heat rate, e0 k0, and the initial heating
terms are neglected, then Eq. (18), simplifies to:
k ¼ k0  ½cp1 M1 g
h i
þ cp clinker 1 cTp MS A1 W  cp1 M 1 g rT ðf  f 0 Þ
from which, k may be readily obtained. Eq. (19) is particularly use-
ful since it reveals directly that under isothermal subsitution and
within 1% error, the marginal impact ok/of of the jth fuel flowrate
on clinker production loss is the jth component of the row vector
h i
[cp1 M1 g + cp clinker]1 cTp MS A1 W  cp1 M 1 g rT which is the
gradient of k with respect to f. Eqs. (5)–(18) provide the principal
flowrates affected by the use of alternative fuels in a state of the
art dry cement manufacturing process in closed form, explicit, lin-
ear expressions in terms of the fuel mixture feeding rates f. It be-
comes evident that the impact of process design on how the use
of AFs affects production level, clinker quality and emissions is
dominant, due to internal circuiting of fluegases, to kiln process
characteristics, reaction conditions, excess air and to the nature of
raw materials. In the model at hand, these impacts are conspicu-
ously represented by the parameters E, h, asm, b, w, g. Moreover,
Eq. (18) may be put in the form (see Appendix A):
k ¼ j þ jT f
where j and j do not depend on the operating parameters asm, b, w,
h, or on the fuel feed rate vector, f, and may be determined only
from baseline and physicochemical data:
j ¼ fcp1 M1 g ðT p  T r Þ þ cp clinker ðT kiln  T r Þ þ cp rm ð1 þ M1 gÞ ðT r
 T s Þg1 fe0 k0 þ cp1 M1 g k0 ðT p  T r Þ þ cp clinker k0 ðT p  T r Þ
 
þ cTp M S A1 W0  cp1 M1 g rT0 ðT p  T r Þ f 0
   
1
þ cTpf0 f 0  cp rm ð1 þ M 1 gÞ rT0 f 0  k0 þ cp air ½eT ðM S A W0  IÞ f 0
þ rT0 f 0  ðT r  T s Þg
jT ¼ fcp1 M1 g ðT p  T r Þ þ cp clinker ðT kiln  T r Þ þ cp rm ð1 þ M1 gÞ ðT r
 
 T s Þg1 fkT  cTp M S A1 W  cp1 M 1 grT ðT p  T r Þ
þ ½cp þ M 1 gÞ rT  cTpf  cp air ðeT ðM S A1 W  IÞ
rm ð1
þ rT Þ ðT r  T s Þg
(The simplified versions of Eqs. (20)–(22) via Tr = Ts introduce less
than 1% error in k). Eq. (20) gives the clinker production level corre-
sponding to a fuel feed rate vector f. It states that with higher flue
gas volumes, i.e. higher flue gas enthalpy outflow, the enthalpy out-
flow associated with the clinker must be lower, necessitating a low-
er clinker production level (see also Section 4 and case study).
Therefore, using lower heating value AFs, such as biological sludge,
the clinker produced per kiln fluegas volume is lower than using
rich AFs, such as TDF. In addition, @k/oQfg < @k/oQk sm < 0 and the
rm, of difference @k/ oQk sm  @k oQfg becomes smaller as richer AFs are
used. Product quality will vary by the incorpopration of slag: the
slag fraction in the clinker is now equal to rT f/k, where k is given
by Eq. (20), compared to the baseline slag fraction, rT0 f 0 =k0 .
4. Impacts of alternative fuels on production and emissions
4.1. Kiln/soil mill fluegas blower capacity and clinker production
Production level may also be given by (see Appendix A):
k ¼ j0 þ j0T f ð23Þ
where
j0 ¼ Q k sm =½t ðq1 g þ ð1 þ M1 gÞ asm =Mair Þ ð24Þ
j0T ¼ rT  ½qT S A1 W=½ðq1 g þ ð1 þ M1 gÞ M1 air asm Þ ð25Þ
ð19Þ Exhaust blower limitations dictate that Qk sm 6 Qk sm max, and from
Eqs. (23) and (24), a lower value of k resulting from the enthalpy
balance, corresponds to a lower value of Qk sm. By combining the
blower capacity limitation with Eqs. (23) and (24) it follows that
Qk sm in Eq. (24), may be ascribed the maximum possible value
Qk smax, with the value of k given by Eq. (20) only by varying the
parameters q or asm. Recalling (see notation) the definitions of
q1 = h + w (MWCO2/Mair), and q, it is seen that j0 and j0 T are indepen-
dent of the fuel flowrates, f, but depend on the operational circuit-
ing parameters asm, h and w, which determine the inner thermal
integration circuit flue gas and air flows. Since asm, h and w do
not enter the kiln enthalpy balance, Eqs. (20)–(22), they may be
manipulated to adjust Qk sm. The following cases are possible:
I. The value of k obtained by Eq. (20) equals the upper limit of
k dictated by kiln and soil-mill blower capacity given by Eqs.
(23)–(25) with Qk smax in place of Qk sm. Then, the enthalpy
balance determines production level k and the kiln-soil-mill
fluegas blower operates at capacity.
II. The value of k obtained by Eq. (20) is lower than the upper
ð20Þ
limit of k given by Eqs. (23)–(25) with Qk smax. Then produc-
tion level, k, is given by Eq. (20) and the blower is operated
well below capacicty, i.e. Qk sm < Qk sm 0. This implies that in
practice, asm, h and w can be adjusted towards blower capac-
ity i.e. to increase Qk sm to Qk sm 0.
III. The value of k obtained by Eq. (20) is larger than the upper
limit of k dictated by kiln and soil-mill blower capacity given
by Eqs. (23)–(25). Then, either the blower fan must be
revamped to higher capacity so as to obtain case I, or the
operator must decrease the kiln/soil-mill flue gas volumetric
flowrate, Qk sm to Qk sm 0, by manipulating anyone of the
parameters asm, h and w, in order to attain case I. Evidently,
ð21Þ this brings about a stringent trade–off between environmen-
tal compliance and production level (profits).
Alternatively, excess air, E, may be varied to rebalance the sys-
tem. In such a case the stoichiometry matrix, S and consequently,
the matrices B and R will be modified and conditions 20–25 are
redetermined.
ð22Þ
4.2. Necessary process balance conditions independent of the fuel feed
rates
Eqs. (20) and (23) give the necessary condition:
ðj  jÞT f ¼ ðj  j0 Þ
0
ð26Þ
Eq. (26), together with Eq. (20) constitute the necessary and suffi-
cient conditions for balancing the integrated process. Models
1–25 and condition 26 are the fundamental results of the present
 C.A. Tsiliyannis / Fuel 99 (2012) 20–39 29

work and pave the way for balancing the kiln by the proper settings
of the parameters, E, asm h, w and for selection of an appropriate AF
rate vector f, for compound or direct operation. A five -step proce-
dure is proposed to this purpose (see Section 4.4). The following
proposition is the cornerstone of the procedure.
Proposition 1.
(a). The kiln/soil mill fluegas volumetric flowrate Qk sm, is a strictly
increasing function of the parameters asm, h and w. In other
words, in case II above, Qk sm can be increased to the baseline
value Qk sm 0, by increasing the value of anyone of the param-
eters asm, h and w. In the (unlikely) case III the operator must
lower the value of at least one of the parameters asm, h and
w, in order not to exceed blower capacity and consequently,
pollutant concentrations will rise.
(b). In practical applications, substitution of conventional fuels with
AFs featuring lower heating value, corresponds to case II: The
production level dictated by the enthalpy balance is lower than
the production level determined by blower capacity, i.e. the
enthalpy balance determines kiln production level as an active
constraint (equality) and its consideration in any attempt
towards non-inferior AF selection is a sine-qua-non. Poor AFs,
such as biological sludge, imply greater production cuts due to
this restriction.
Proof. See Appendix A. h
Proposition 1 unveils two important and novel features of the
present work not previously revealed: (a) Consideration of the
fluegas circuiting through the soil mill, of the kiln/fuel mill energy
integration and of the use of pseudo air, significantly modifies the
plant mass and energy balances and introduces new manipulating
parameters which the operator may use advantageously and (b)
since AFs are usually poorer fuels than fossil fuels, the enthalpy
balance dictates production losses as a binding constraint. More
specifically: if the types of fuels in the fuel mixture are given but
the feed rates are yet to be determined, then upon variation of f,
the parameters asm, h and w remain constant, j, j0 , j, j0 , remain
constant, independently of the specifc feed rates, i.e. of the vector
f, the projector (j0  j) and the projection (j  j0 ) of f remain con-
stant. Assuming the blower costs/kg clinker to be much lower than
profits/kg clinker, it follows that Qk sm in Eq. (23) may be ascribed
the maximum possible value Qk smax, given the fuel mixture, with
the value of k given by Eq. (20). Thus the plant operator has merely
to adjust the feed rates (for instance, by increasing f3 and decreas-
ing f4, f5) in order to maximize production level for the given fuel
types, as dictated by the enthalpy balance, Eq. (20), while satisfying
Eq. (26).
If the fuel feed rates are finalized, a fine tuning may follow via
the circuiting parameters, asm, h and the pseudo-air flow fraction,
w, which can be manipulated by the operator in order to finely
tune Eq. (26) and to satisfy environmental constraints: In view of
Proposition 1a, since production level is uniquely determined by
the enthalpy balance (Eq. (20)), this tuning is achieved by the plant
operator by increasing asm, h and/or w, up to the point where
Qk sm = Qk sm 0. Hence, the decrease in production level due to high-
er flue gas enthalpy outflow, allows lower mass of fluegases to the
fuel mill, or higher soil mill specific air, or higher volumes of pseu-
do air, which may be desirable manipulations for emission compli-
ance and improved environmental performance.
For instance if, in the baseline scenario (conventional fossil
fuels), operation was at blower capacity, then upon use of AFs,
since the kiln fluegas volumetric rate increases, i.e. the associated
enthalpy increases, production level, k from Eq. (20) decreases, so
that clinker enthalpy outflow decrease and the enthalpy balance
remain satisfied. This new clinker production level corresponds
to a lower value of kiln-soil mill fluegas volumetric flowrate (de-
spite the higher kiln fluegas volume rate), allowing the plant oper-
ator to increase the volume of pseudo air, or to reduce the fraction
of flue gas directed to the fuel mill, or to increase the specific air in
the soil mill, asm, up to the limit where Qk sm = Qk sm 0. Note that
since the parameters j, j0 are obtained in terms only of baseline
data and the vectors j, j0 , are independent of the various AF feed
rates, both j, j0 and the values of the individual components of
the vectors j, j0 remain constant under any fuel feed rates. The val-
ues of j0 and j0 will change however, if the operator modifies the
settings of the circuiting parameters asm, h and w: if for instance,
RDF participates in any fuel mixture, the respective component
of the vector j, is the same. In mathematical terms the components
keep the same value because they form the gradient of k with re-
spect to 1 t of the AF in Eq. (20), which is linear in f. By the same
token, if an AF participates in any fuel combination, under constant
asm, h and w, the components of j0 in Eq. (23) are the same, since
they constitute the gradient of k with respect to 1 t of the AF,

Table 1
Actual plant characteristics and fuel properties.

e 5.338 TJ/y clinker Case study plant data k1 (kcal/kg) 6685 [43], Case study plant data
f 0.43 Case study plant data k2 (kcal/kg) 8342 [43], Case study plant data
g (kmol/kg) 0.0116 Case study plant data k3 (kcal/kg) 6800 [43], Case study plant data
q1 1.079 Case study plant data k4 (kcal/kg) 3000 [18,19], Case study plant data
Tkiln (K) 1700 Case study plant data k5 (kcal/kg) 4300 Case study plant data
Tp (K) 1273 Case study plant data cp1 (kcal/kg °C) 0.2807 [44]
Tr (K) 423 Case study plant data cp2 (kcal/kg °C) 0.5214 [44]
Ts (K) 298 Case study plant data cp3 (kcal/kg °C) 0.2503 [44]
E 20% Case study plant data cp4 (kcal/kg °C) 0.2712 [44]
h 65% Case study plant data cp5 (kcal/kg °C) 0.1974 [44]
b1 0.15 Case study plant data cp6 (kcal/kg °C) 0.2034 [44]
b2 0.059 Case study plant data cp7 (kcal/kg °C) 0.2000 [44]
b3 0 Case study plant data cp clinker (kcal/kg °C) 0.1860 [44]
b4 0 Case study plant data cp air (kcal/kg °C) 0.2663 [44]
b5 0 Case study plant data cp (coal) (kcal/kg °C) 0.370 [44]
r1 (% ww) 0.0980 [40] cp (petcoke) (kcal/kg °C) 0.403 [44]
r2 (% ww) 0.0058 [40] cp (TDF) (kcal/kg °C) 0.415 [44]
r3 (% ww) 0.0000 [40] cp (BIS) (kcal/kg °C) 0.374 [45]
r4 (% ww) 0.1790 [40] cp (RDF) (kcal/kg °C) 0.326 [45]
r5 (% ww) 0.0000 [40] cp (CaCO3) (kcal/kg °C) 0.219 [44]

Heat capacities, cp, were determined as a function of temperature (see Appendix A) with the constants taken from [42,44]. The corresponding temperature range is according
to Eqs. (20)–(22), e.g. for the fluegases the temperature range is from Tr to Tp.
 30
Table 2
Parameter values: case study.

Scenario Fuel feed: mass flowrate vector f (tn/y) asm (kg air/kg clinker) h w j (tn/y) j0 (tn/y) j1 j2 j3 j4 j5 j01 j02 j03 j04 j05
Direct operation, no pseudo air f1 = 57 218 0 1 0 72 093 20 233 854 7.66 10.60 0.0000 0.0000 0.0000 38.1339 43.1293 0.0000 0.0000 0.0000
f2 = 106 989
1 f1 = 57 218
Baseline f2 = 106 989 1.75 0.85 0.15 72 093 2 252 885 7.66 10.60 0.0000 0.0000 0.0000 4.1789 4.8277 0.0000 0.0000 0.0000
2 f1 = 190 726 1.75 0.85 0.15 72 093 2 252 885 7.66 0.0000 0.0000 0.0000 0.0000 4.1789 0.0000 0.0000 0.0000 0.0000
Coal 100% 1.75 0.8 0.2 72 093 2 246 311 7.66 0.0000 0.0000 0.0000 0.0000 4.1733 0.0000 0.0000 0.0000 0.0000
1.75 0.8 0.25 72 093 2 227 447 7.66 0.0000 0.0000 0.0000 0.0000 4.3546 0.0000 0.0000 0.0000 0.0000
1.75 0.8 0.38 72 093 2 179 853 7.66 0.0000 0.0000 0.0000 0.0000 4.8121 0.0000 0.0000 0.0000 0.0000
3 f2 = 152 841 1.75 0.85 0.15 72 093 2 252 885 0.0000 10.60 0.0000 0.0000 0.0000 0.0000 4.8277 0.0000 0.0000 0.0000

C.A. Tsiliyannis / Fuel 99 (2012) 20–39

Petcoke 100% 1.75 0.85 0.1 72 093 2 272 183 0.0000 10.60 0.0000 0.0000 0.0000 0.0000 4.6166 0.0000 0.0000 0.0000
1.75 0.9 0.02 72 093 2 290 718 0.0000 10.60 0.0000 0.0000 0.0000 0.0000 4.4911 0.0000 0.0000 0.0000
4 f1 = 57 218 1.75 0.85 0.15 72 093 2 252 885 7.66 10.60 5.86 0.0000 0.0000 4.1789 4.8277 5.1088 0.0000 0.0000
Petcoke 10% f2 = 91 705 1.75 0.9 0.18 72 093 2 229 115 7.66 10.60 5.86 0.0000 0.0000 4.4748 5.1630 5.4735 0.0000 0.0000
(HV) TDF f3 = 18 750 1.75 0.85 0.2 72 093 2 233 911 7.66 10.60 5.86 0.0000 0.0000 4.3607 5.0353 5.3310 0.0000 0.0000
1.75 0.85 0.22 72 093 2 222 679 7.66 10.60 5.86 0.0000 0.0000 4.4326 5.1174 5.4188 0.0000 0.0000
5 f1 = 57 218 1.75 0.85 0.15 72 093 2 252 885 7.66 10.60 0.0000 1.85 0.0000 4.1789 4.8277 0.0000 2.6348 0.0000
Petcoke 10% f2 = 91 705 1.75 0.9 0.27 72 093 2 195 898 7.66 10.60 0.0000 1.85 0.0000 4.7921 5.5253 0.0000 3.0024 0.0000
(HV) BIS f4 = 42 500 1.75 0.85 0.3 72 093 2 196 906 7.66 10.60 0.0000 1.85 0.0000 4.1789 4.8277 0.0000 2.6348 0.0000
1.75 0.85 0.31 72 093 2 193 273 7.66 10.60 0.0000 1.85 0.0000 4.7501 5.4799 0.0000 2.9722 0.0000
6 f1 = 57 218 1.75 0.85 0.15 72 093 2 252 885 7.66 10.60 0.0000 0.0000 2.77 4.1789 4.8277 0.0000 0.0000 3.7439
Petcoke 10% f2 = 91 705 1.75 0.9 0.23 72 093 2 210 538 7.66 10.60 0.0000 0.0000 2.77 4.6522 5.3656 0.0000 0.0000 4.1576
(HV) RDF f5 = 29 651 1.75 0.85 0.3 72 093 2 196 906 7.66 10.60 0.0000 0.0000 2.77 4.7153 5.4402 0.0000 0.0000 4.2122
1.75 0.85 0.28 72 093 2 204 209 7.66 10.60 0.0000 0.0000 2.77 4.6453 5.3603 0.0000 0.0000 4.1511
7 f1 = 57 218 1.75 0.85 0.15 72 093 2 252 885 7.66 10.60 5.86 1.85 2.77 4.1789 4.8277 5.1088 2.6348 3.7439
Petcoke 10% f2 = 61 136 1.75 0.85 0.28 72 093 2 204 209 7.66 10.60 5.86 1.85 2.77 4.6453 5.3603 5.6788 2.9103 4.1511
(HV) TDF, 10% (HV) BIS, 10% (HV) RDF f3 = 18 750 1.75 0.85 0.31 72 093 2 193 273 7.66 10.60 5.86 1.85 2.77 4.7501 5.4799 5.8069 2.9722 4.2426
f4 = 42 500 1.75 0.85 0.52 72 093 2 119 660 7.66 10.60 5.86 1.85 2.77 5.4554 6.2853 6.6690 3.3888 4.8583
f5 = 29 651 7.66 10.60 5.86 1.85 2.77

Notation: Petcoke 10% (HV) TDF means that 10% of the total energy required was supplied by TDF substituting for petcoke, that is 533.8 TJ/year were contributed by TDF.
Table 3
Process balance upon AF use: case study.

Scenario Fuel feed: mass flowrate asm (kg air/kg h w k (tn/ Qk sm (N Qfg (N @k/@ DH (tn/ mCO2eq dmCO2eq @mCO2eq/@k mCO2eqa @mCO2eq/ @mCO2eq/@ DH⁄ (tnCO2eq/
vector f (tn/y) clinker) y) m3/h) m3/h) 100 Gcal) (tn/y) (tn/y) (tn/tn) (tn/y) @ka (tn/tn) substituted TJ)

Direct Operation, f1 = 57.218 0 1 0 1 500 246 000 246 0,00E + 00 1 274 0 0 1 274 053 0
no pseudo air 000 012 053
f2 = 106.989 1 500
000
1 f1 = 57.218 1.75 0.85 0.15 1 500 600 730 246 0.00E + 00 1 274 0 0 1 274 053 0 0.0
000 012 053
Baseline f2 = 106.989 1 500
000
2 f1 = 190.726 1.75 0.85 0.15 1 388 547 027 255 8.7 1 218 55 174 0.3537 1 218 879 0.3537 0.0
820 977 879
Coal 100% 1.75 0.80 0.20 1 388 548 338 255
820 977
1.75 0.80 0.25 1 388 562 297 255
820 977
1.75 0.80 0.38 1 388 598 590 255
820 977
3 f2 = 152.841 1.75 0.85 0.15 1 547 623 745 241 3.7 1 298 24 077 0.3783 1 298 131 0.3783 0.0
639 766 131

C.A. Tsiliyannis / Fuel 99 (2012) 20–39

Petcoke 100% 1.75 0.85 0.10 1 547 609 926 241
639 766
1.75 0.90 0.02 1 547 599 967 241
639 766
4 f1 = 57.218 1.75 0.85 0.15 1 447 577 700 250 4.1 1 245 28 180 0.3923 1 245 874 0.3923 0.0
816 739 874
Petcoke 10% (HV) f2 = 91.705 1.75 0.90 0.18 1 447 598 534 250
TDF 816 739
f3 = 18.750 1.75 0.85 0.20 1 447 591 633 250
816 739
1.75 0.85 0.22 1 447 599 992 250
816 739
5 f1 = 57.218 1.75 0.85 0.15 1 416 555 075 253 6.5 1 233 40 101 0.3321 1 103 968 1.9093 243.5
794 183 953
Petcoke 10% (HV) f2 = 91.705 1.75 0.90 0.27 1 416 600 814 253
BIS 794 183
f4 = 42.500 1.75 0.85 0.30 1 416 596 616 253
794 183
1.75 0.85 0.31 1 416 599 385 253
794 183
6 f1 = 57.218 1.75 0.85 0.15 1 420 564 417 252 6.3 1 230 43 121 0.3921 1 156 330 1.3369 139.7
301 891 933
Petcoke 10% (HV) f2 = 91.705 1.75 0.90 0.23 1 420 599 298 252
RDF 301 891
f5 = 29.651 1.75 0.85 0.30 1 420 606 310 252
301 891
1.75 0.85 0.28 1 420 600 725 252
301 891
(continued on next page)

31
32 C.A. Tsiliyannis / Fuel 99 (2012) 20–39

provided the off-gas volumetric flowrate by the kiln/soil mill

blower is constant.

(tnCO2eq/substituted
Similar necessary conditions may be obtained using the fuel
@mCO2eq/@ DH⁄ mill volumetric flowrate Qfm, by substituting k = e1 kT in Eq. (17)
from which k = j00 + j00 T f results, where now j00 and j00 depend
upon h, and b, which are the manipulated parameters (increasing
119.1
bi will increase Qfm but the fuel mill atmosphere becomes less in-
TJ)

ert). Exhaust fuelmill APCS blower capacity limitations may also

be used, e.g. Qf m 6 Qf m 0, but in practice, fuel mill requirements
@ka (tn/tn)
@mCO2eq/

are lower upon use of AFs and such a condition is usually not nec-
1.2949

essary (not binding).

4.3. Greenhouse gas emissions

mCO2eqa

971 286
(tn/y)

The principal greenhouse gas is CO2, which is produced at a rate

of uT1 mfg : ¼ uT1 M B f . If nitrous oxide, N2O, is considered as well,
then, with kN2 O denoting the rate constant of the reaction N2 + 1/
@k (tn/tn)
@mCO2eq/

2 O2 M N2O at the kiln flue gas conditions and with c denoting

0.3790

the greenhouse equivalency between kg (N2O) and kg (CO2),

(c = 260, [39]), the total greenhouse gas emissions’ rate is given
by the relation (see Appendix A):
dmCO2eq
(tn/y)

112

 1=2
001

rCO2 eq ¼ uT1 M B f þ t1 c kN2 O MN2 O Q 1=2

fg uT4 Q fg uT3 Q fg ð27Þ
mCO2eq

where Qfg is given by Eq. (8). AF logistics and CO2 emissions (around
1 162
(tn/y)

052

100 kg CO2/dry t) of collecting and transporting biomass residues,

should be included in such a balance [40]. If the second term (cor-
@k/@ DH (tn/

responds to CO2eq from N2O) is ignored (around 1% of the first) then

100 Gcal)

CO2eq emissions are reduced by by r CO2 eq  r CO2 eq 0 ¼ uT1 M B ðf  f 0 Þ

16.8

and the marginal gain with respect to the jth fuel is the jth element
of the row vector uT1 M B. Upon fossil fuel substitution by AFs, Eq.
(27) gives (see Case Study below, Table 5) CO2eq emission reduc-
Qfg (N
m3/h)

264
754
264
754
264
754
264
754

tions of the order of 243.5 t CO2eq/substituted petcoke TJ by BIS,

of 139.7 t CO2eq/substituted petcoke TJ by RDF, and 119.1 t CO2eq/
Qk sm (N

495 733

532 189

599 494
540 602

substituted petcoke TJ by an isothermal mixture of TDF, BIS and

m3/h)

RDF, figures which agree with reported values, e.g. 14.159 t CO2eq/
@mCO2eq/@ DH = reduction in CO2eq emissions due to the use of AF (t CO2eq per substituted petcoke TJ).

87 coal TJ by RH, [41] (=162.7 t CO2eq/coal TJ by RH).

1 286

1 286

1 286

1 286
k (tn/

312

312

312

312

4.4. A five-step procedure for process balancing

y)

Refers to CO2eq emissions non-including the renewable biogenic fraction contribution.

0.15

0.28

0.31

0.52

1. Obtain xi, E, h, and determine S, MSA1 (Appendix B).

w

2. Obtain physicochemical data, cp clinker, cp rm, cpf, Tkiln, Tr, Ts, cp

0.85

0.85

0.85

0.85

and baseline data including f, g, total heat rate, e0 k0, f0, W0,
h

r0. Determine the scalar parameter j from Eq. (21). Obtain

asm (kg air/

baseline parameters, asm, w, h, and determine the scalar param-

kg clinker)

eter j0 from Eq. (24).

1.75

1.75

1.75

1.75

3. Select the types of AFs to be assessed. Select f by substituting

annual quanitites of conventional fuel (e.g. petcoke) with ther-
flowrate vector f (tn/y)

mally appropriate quantities of AFs and obtain the respective k

and r. Obtain W and determine j and j0 from Eqs. (22) and (25)
Fuel feed: mass

respectively. Obtain the clinker level, k, form the enthalpy bal-

ance, Eq. (20). If the total heat rate is equal to the heat rate of
f1 = 57.218

f2 = 61.136

f5 = 29.651
f3 = 18.750

f4 = 42.500

the baseline case, then determine k from Eq. (19).

4. To avoid excessive production cuts, check by use of Eq. (6), that
the new kiln, volumetric fluegas flowrate, Qfg, will not be much
larger than in the baseline case. Due to the docile nonlinearities,
10% (HV) RDF, 10%

guidance is provided by the marginal volumetric flowrates cor-

(HV) BIS, 10% (HV) TDF

responding to each sublstitution (oQfg/@ DH, in Nm3/h per 100

Gcal/year) or, directly, by the marginal production level ( ok/
@ DH, in tn/year per 100 Gcal/year). If necessary, select a new f
Table 3 (continued)

by lowering the feed rate of AFs which produce large volumes

⁄

of gases (e.g. coal, biomass, NG, BIS, RH, ABW) and by increasing
Scenario

Petcoke

the feed rate of thermally equivalent low gas producing AFs, e.g.
TDF, APW, RDF, plastic wastes. Obtain the clinker production
7

level from the enthalpy balance, Eqs. (20)–(22).

 C.A. Tsiliyannis / Fuel 99 (2012) 20–39 33

700.000
Qk sm Nm3/h
Qfg Nm3/h

Volumetric flowrates, (Nm /h)

600.000

3
500.000

400.000

300.000

200.000

100.000

0
scenario 1 scenario 2 scenario 3 scenario 4 scenario 5 scenario 6 scenario 7
Kiln fluegas volumetric flowrate, Q fg (Nm /h)

270 000
3

265 000

260 000

255 000

250 000

245 000

240 000

235 000

230 000
scenario 1 scenario 2 scenario 3 scenario 4 scenario 5 scenario 6 scenario 7

Fig. 5. Kiln fluegas, Qfg, and kiln/soil mill flue gas, Qk sm, volumetric flow rates, under calorific (HV) substitution of petcoke with respect to the baseline case, as dictated by the
enthalpy balance (Eq. (18)). (Baseline: petcoke 70%, coal 30% HV contribution.)

1 600 000

1 500 000
clinker production, k (t/y)

1 400 000

1 300 000

1 200 000

1 100 000

1 000 000

900 000

800 000
scenario 1 scenario 2 scenario 3 scenario 4 scenario 5 scenario 6 scenario 7

Fig. 6. Clinker production level associated with use of AFs.

5. Obtain the kiln/soil mill fluegas volumetric flowrate Qk sm using modified). If, by decreasing the parameters, asm, w, h, off-gas
Eq. (14) and check that it is below the respective blower capac- pollutant concentrations exceed the maximum limits, then go
ity as expected by Proposition 1. If yes, then increase anyone of back to step 3 with a new f. With the finally selected f, deter-
the parameters, asm, w, h, so that Eq. (26) be satisfied; if no, any- mine e from Eq. (1), i.e. e = k1 kT f, the matrix B and the mass
one of the parameters asm, h and w, may be decreased in order and gas flowrates from Eqs. (5)–(17).
to satisfy Eq. (26). If condition 26 is satisfied, obtain b, and check
other blower (e.g. fuel mill) capacity requirements. If not satis- The procedure should be followed for both compound and di-
fied by manipulating b, or even asm, w, h, go to step 3 (r and k rect operation (asm = 0), since the respective values of the parame-
remain the same if the types of the various fuels in the AF mix- ters h, w, may have to be different in order to satisfy all process
ture are the same and only the relative mass feeding rates are requirements. It is evident that the environmental compliance
34
1.8000
mCO2eq / k * (t CO2 eq / t clinker)
1.6000
1.4000
1.2000
1.0000
0.8000
0.6000
0.4000
0.2000
0.0000
scenario
1 2
Fig. 7. Marginal reduction of greenhouse gas emissions associated with use of AFs per ton of product lost due to necessary reduction in the level of clinker production.
action included in step 5 is rudimental and the overall optimiza-
tion including satisfaction of environmental constraints by fine
tuning may be further elaborated – a task beyond the scope of
the present work. For instance, not all N in the rotary kiln is trans-
formed to N2; a part of it is transformed to NOx depending on the
kiln temperature, excess air, N content in the fuel and type of fuel,
as well as on the conditions along the circuiting of the flue gases.
The resulting NOx, together with dust emissions, usually constitute
the most stringent to comply with. Investigation using the present
formulation is under way.
5. Case study
An actual dry process plant producing 1.500.000 t per year clin-
ker at a specific thermal rate of 850 kcal/kg includes 2 rotary kiln/
preheater lines with a baseline fuel corresponding thermally 70%
to petcoke and 30% to coal at blower capacity. Kiln fluegas thermal
circuits to both the soil mill and the fuel mill are active, while more
than 90% of operation is under compound mode. The plant has
been running at capacity during 2000–2008, driven by excessive
building development in Greece. Table 1 presents baseline opera-
tional data and fuel propoerties. In view of the falling demand
and anticipated production cuts, an appropriate AF or/and coal/
petcoke fuel mixture is sought which could balance off some of
the profit losses. Candidate AFs include tire derived fuel, (TDF)
(EC code 16 01 03), dried biosludge from wastewater treatment
plants BIS (EC code 200306) and RDF (EC code 19 12 10). Due to
the high price of petcoke relaitively to coal, interest is focusing in
petcoke substitution by the above AFs.
From Proposition 1, since the heating values of the candidate
AFs are lower than the HV of the conventional fuel to be substi-
tuted (petcoke) the enthalpy balance is expected to be the produc-
tion limiting constraint.
Steps 1 and 2 of the procedure in Section 4.4 give the data pre-
sented in Table 2. Seven scenaria are investigated: Scenaria 2 and 3
correspond to 100% coal, 100% petcoke respectively. Scenaria 4, 5, 6
correspond to 10% thermal substitution of petcoke by each one of
the above AFs in the respective order. From step 3 of the 5-step
procedure j, j, are obtained. It is corroborated that j and the com-
ponents of the vector j are independent of the inner circuiting
parameters, asm, h and w and that they are also independent of
the fuel mixture: the components of j are all included in the full
mixture scenario (scenario 7). If a fuel is absent from the mixture
then fi is equal to zero and the full vector j may be used in Eq.
(20). Similarly the values of j0 and the vector j0 are obtained;
C.A. Tsiliyannis / Fuel 99 (2012) 20–39
scenario scenario scenario scenario scenario scenario
3 4 5 6 7
under the same values of the inner circuiting parameters, asm, h
and w, they are the same; the values are given in the full mixture
scenario 7. Then the clinker level is obtained from Eq. (20) (Table 3)
and the blower constraint is checked. As expected from Proposition
1 in all scenaria (except scenario 3, 100% petcoke) production is
lower: fluegas volumetric flowrates given in Fig. 5 corroborate
the high kiln fluegas volumes of poor fuels which result in produc-
tion cuts – see clinker production level determined via Eq. (20) in
Fig. 6. Petcoke, being the richest fuel, corresponds to the highest
production level (1.56  106 t/y), while dried BIS (the poorest AF)
necessitates production cuts of the order of 107,000 t/y. Table 3
also presents step five of the procedure: tuning of the parameters
asm h, w, achieving equal kiln/soil mill volumetric flowrate,
Qk sm, with the baseline scenario (exhaust blower at capacity
600.000 m3/h).
The marginal production levels (@k/@ DH, in t/y per 100 Gcal/y)
with respect to the baseline case, which are used in step 4 of the 5-
step procedure to obtain a non-inferior fuel feed rate vector f, are
determined for the six additional scenaria (Table 3). Petcoke sub-
stitution by coal or TDF corresponds to a marginal production more
than twice lower than subistution by BIS or RDF. Concerning CO2 eq
emissions the relative contribution of N2O is about 1% of the CO2
contribution, while biogenic AF transportation contributes about
0.5% of CO2. BIS presents the highest marginal benefits with respect
to CO2eq emissions (Table 3, Fig. 7): that is, four times the mass of
CO2eq per t of clinker lost due to production cuts, than for TDF and
30% higher than for RDF. In addition, BIS may bring the highest tip-
ping fee income, followed by RDF. The marginal clinker production
loss levels with respect to enthalpy (@k/@ DH) in t clinker/100 Gcal
are 5.2 for TDF, 8.4 for BIS and 8.0 for RDF. These findings favor BIS
as an AF for petcoke, if demand falls. For instance, if environmental
constraints are not taken into account, and demand is projected to
drop from the baseline level of 1.5 million t/y to 1.39–1.40 million
t/y, then both RDF and BIS are appropriate (Table 5 gives clinker
levels 1.393 million t/y and 1.398 million t/y respectively). If they
present the same tipping fee, BIS is more beneficial due to lower
CO2 eq emissions (Table 5, last column) and scenario 5 is selected
which gives 40% more income from greenhouse gas emissions.
Otherwise they may suggest an AF balanced fuel mixture with
approximately equally distributed petcoke substitution by TDF,
BIS and RDF: scenario 7 presents such a case with 30% HV petcoke
substitution (10% by TDF, 10% by BIS and 10% by RDF) leading to a
considerable (275,000 t/y  18%) reduction in clinker production.
The pseudo-air flow parameter w, may be increased from the base-
line value (0.15) up to the value 0.52, where the exhaust blower
operates at capacity, in order to compensate for any pollutant
 C.A. Tsiliyannis / Fuel 99 (2012) 20–39
emissions increase due to BIS or RDF. The results may be particu-
larly valuable today: the current economic crisis is taking a severe
toll on the local cement plants, with more than 70% profit down-
turn in 2010 and a 55% reduction in demand in the first quarter
of 2011.
6. Conclusions
Use of alternative fuels in cement manufacturing processes is
attractive due to environmental and potential economic benefits.
The results presented here provide a systematic way for determin-
ing the flows of the main process fluegas streams when alternative
fuels are used and for quantifying the effect of critical operational
parameters, such as thermal integration by inner circuiting of kiln
fluegas to the soil mill and to fuel mill, or varying pseudo-air flow.
During periods of economic expansion, with high building activity
and product demand, when cement plants are running at capacity,
use of alternative fuels results in higher fluegas volumes, necessi-
tating production cuts and consequent profit losses. In contrast
to common belief, that such losses are due to the fact that the flue-
gas volumes are beyond the operating range of installed process
equipment (e.g. blowers), it was shown, based on a rigorous, yet
compact model for the integrated process developed herein, that
production cuts and associated losses originate from the funda-
mental kiln enthalpy balance, while the kiln/soil mill fluegas blow-
ers are forced to operate well below capacity, despite the higher
kiln fluegas volumes. Significant margins are therefore provided
to the plant operator towards environmental compliance. Eco-
nomic contraction, on the other side and weak demand for cement,
renders production cuts necessary and therefore, use of alternative
fuels may be both environmentally and economically attractive.
The results may serve for mass and heat balancing the integrated
process at acceptable production levels, both during compound
and direct operation and for selection of AF mixtures which profit-
ably compensate economic sacrifices from production cuts, with
greenhouse gas emission cost reduction and higher AF tipping
fee income or lower fuel mixture costs.
Appendix A
A.1. Proof of Eq. (3)
From the reaction CaCO3 ? CaO + CO2, with mass stoichiometry
(100 ? 56 + 44) it follows that if the raw meal content in calcium
oxide, CaO, is known (a typical value is 43% ww) then
mCO2 ;lime ¼ v ðraw mealÞ MBCO2 =MBCaO or
mCO2 ;lime ¼ ðraw mealÞ M1 v=56 ðA1Þ
If km is the clinker mass rate from raw meal, then
ðraw mealÞ ¼ km þ mCO2 ;lime ðA2Þ
Substituting (A2) in (A1) and soloving for mCO2 ;lime gives
mCO2 ;lime ¼ M 1 v=56ð1  M 1 v=56Þ1 km or, since g = v/56 (1  M1v/
56)1
mk sm ¼ h M B f þ M a M 1 T 1
air w e M B f þ Ma M air asm ð1 þ M 1 gÞ ðe
1 T
k  rT Þ f ()
mk sm ¼ Mfh B þ aM 1 T 1
air w e M B þ a M air asm ð1 þ M 1 gÞ ðe
1 T
k  rT Þg f or
mk sm ¼ M fðh I þ M1 T 1
air a w e MÞB þ M air a ð1 þ M 1 gÞ asm ðe
1 T
k  rT Þg f
35
mCO2 ;lime ¼ M1 g km ðA3Þ
T T
But k = km + r f or km = k  r f or, using Eq. (1)
km ¼ ðe1 kT  rT Þ f ðA4Þ
Substituting Eq. (A4) in Eq. (A3) gives
mCO2 ;lime ¼ M1 g ðe1 kT  rT Þ f ð2Þ
From Eqs. (A3) and (A2) it follows that:
ðraw mealÞ ¼ km þ M1 gkm or
ðraw mealÞ ¼ ð1 þ M 1 gÞ km ¼ ð1 þ M1 gÞ ðe1 kT  rT Þ f ð3Þ
A.2. Proof of Eq. (5)
The fuel combustion producess a flue gas mass rate vector
equal to MSA1 W f where S is corresponds to reaction (a). Then
the total flue gas mass rate vector mfg = flue gas mass flowrate
vector from (a) + CO2 from (b) =M S A1 Wf + M1g (e1 kT  rT)
f = M S A1 W f + M u1g k = M S A1 W f + M u1g (e1 kT  rT)
f = M B f, where B = S A1 W + g u1(e1 kT  rT), a mxn matrix.
The mxn matrix u1g (e1 kT  rT) has nonzero first row equal
to g (e1kT  rT) and all other rows equal to zero; from Eq. (2)
if multiplied by f it gives the molar rate production of CO2 due
to lime dissociation.
A.3. Proof of Eqs. (6)–(27)
Qfg = (RT/P) M1 mfg = t (S A1 W + g(e1 kT  rT)) f () Qfg = t
B f which is Eq. (6).
Eq. (7) results from mfg = eTmfg and noting that eTu1 = 1. For Eq.
(8) the total volume, if t = RT/P is the gas molar volume at T, P and
ni is number of moles of the ith flue gas then, Qfg = t
(n1 + n2 +    + nm) or Qfg = t eT M1 mfg or Qfg = eT tM1mfg or
Qfg = eT Qfg or Qfg = t eT B f.
The soil mill air mass drawn, is proportional to raw material
crushed in the soil mill. i.e., to the raw meal: from Eq. (2): soil
mill air = msm = asm (1 + M1 g) (e1kT  rT) f, where asm is con-
stant. The total air flow, which will be mixed with the flue gas
contains in addition the pseudo air mass inflow, set by the oper-
ator as a fraction, w, of the total flue gas mass flowrate. Thus the
total air mass inflow rate is msm p = asm (1 + M1 g)
(e1kT  rT) + mp, where mp = w mfg. Substitution of mfg from Eq.
(7) gives Eq. (10).
Define the m vector aT = [0, 0, (21/100), (79/100), 0, 0 . . . , 0]
which serves to transform air mass flowrate drawn by the soil mill
fan, to individual oxygen and nitrogen mass rates, in the appropri-
ate order, i.e. as they appear in the flue gas vector, mfg. Then the
oxygen and nitrogen mass rate contributions of a an air mass rate
to the respective flue gas vector components results by multiplica-
tion of the air mass rate by the vector Ma Mair1.
For Eq. (11): mk sm ¼ h mfg þ M a M 1 1
air w mfg þ M a M air msm and
using Eqs. (6), (9) and (10):
ðA5Þ
36 C.A. Tsiliyannis / Fuel 99 (2012) 20–39

T
From the definition of q follows that qT ¼ eT ðh I þ M 1 air w MÞ A.4. For the enthalpy balance
T T 1
or a q = ae ðh I þ M air w MÞ. Adding h I to both sides gives
h I þ a qT ¼ h I þ aeT ðh I þ M 1 1 T
air w MÞ () h I þ M air w ae M ¼ Ts = 25 °C corresponds to the ambient temperature, Tr(=150 °C)
T T 1 T T
h I þ a q  ae h I () h I þ M air w ae M ¼ a q þ h ðI  aeT Þ is the reference temperature for the lower heating value
and upon substitution in Eq. (A5) mk sm ¼ M f½a qT þ h ðI  aeT ÞB (DHreaction), Tp = 1000 °C is the preheater temperature, Tkiln =
þM1 air a ð1 þ M 1 gÞ asm (e1 kT  rT)} f ¼ M fR B þ M 1 air a 1415 °C is the kiln tempertature. Then the enthalpy balance is:
ð1 þ M1 gÞ asm (e k  r )} f which is Eq. (11) with R = a qT + h
1 T T

(I  aeT) = h I + Mair1 a w eT M. Note that R depends only on the Products at Tkiln Clinker at Tkiln
system parameters, h, w. (Clinker at Tkiln +
Eq. (12) results from Eq. (9) via right multiplication by t M1, Fluegas at Tkiln)

where t = RT/P is the gas molar volume at T, P.

For the total gas volumetric flowrate Eq. (14): As before in Eq. Fluegas at Tp
Product Heating
(8), Qk sm is the inner product of Qk sm with eT, i.e. Qk sm = eT Qk sm.
Using Eq. (A5) and noting that eT a = 1 and that eT M a M 1 air ¼ 1 it
Reactants at Tr Products at Tr
follows that
Kiln reactions

Qk sm ¼ eT Q k sm () Q k sm Initial
Heating
T
¼ t fe h B þ M 1
air
T
w e M Bþ M1
air asm ð1 þ M1 gÞ
Reactants at Ts
 ðe1 kT  r Þg f () Q k
T
sm

¼ t feT ðh I þ M1 1
air w MÞB þ M air asm ð1 þ M 1 gÞ

 ðe1 kT  rT Þg f LHVT r ¼ DHreactants T s !T r þ DHproducts T r !T kiln  DHfluegas T p !T kiln

þ Heat Loss ðA8Þ

Subsituting for B = S A1 W + g u1(e1 kT  rT) it follows
that Q k sm ¼ t feT h ðS A1 W þ u1 g ðe1 kT  rT ÞÞ þ M 1 T
air w e ae M
T
1 1 T T T 1
ðS A W þ u1 g ðe k  r ÞÞ þ e a M air asm ð1 þ M1 gÞ ðe k  1 T LHVT r ¼ DHreactants T s !T r þ DHflue gas T r !T p þ DHclinker T r !T kiln

rT Þ}f () Qk sm = t {eT h S A1 W + eT h u1g(e1 kT  rT Þþ þ Heat Loss ðA9Þ

1
M1 T
air w e M S A W þ M 1 T
air w e M u1 g (e1 kT  rT Þ þ M 1air asm
ð1 þ M 1 gÞ ðe k  r Þg f . But e ðhI þ M1
1 T T T T
air w MÞ ¼ q , h þ M air
1 If (A9) is written for the AF and the baseline cases and the two
M CO2 w ¼ q1 and also eT M u1 ¼ M1 ¼ MCO2 ð¼ 44Þ. Thus are subtracted, the result is:
dðLHVÞ ¼ ðcTpf f  cTpf0 f 0 Þ ðT r  T s Þ þ cp rm ðmr m
Qk sm ¼ t fqT SA1 W þ ½q1 g þ ð1 þ M 1 gÞ M 1
air asm 
 mr m0 Þ ðT r  T s Þ þ mair cp air ðT r  T s Þ
 ðe1 kT  rT Þg f
 mair 0 cp air 0 ðT r  T s Þ þ cTp ðmfg
which is Eq. (14).  mfg 0 Þ ðT p  T r Þ þ cp clinker ðk  k0 Þ ðT kiln  T r Þ ðA10Þ
A first estimate of the new kiln/soil mill flowrate may obtained
where mr m stands for raw meal mass flowrate and the expression
by assuming that the raw meal clinker km = (e1 kT  rT)} f will be
for sensible enthalpy change rate DH = m cp DT was used with the
the same as in the baseline case. Then
appropriate (median) cp value: for the initial heating (or cooling)
Qk ¼ Qk þ t ðqT S A1 W f  qT0 S A1 W0 f 0 Þ ðA6Þ stage (from Tr ? Ts): the heat capacity of the solids (fuel and raw
sm sm 0
meal) may be considered constant from 25 °C to 150 °C and for
which, if the operational parameters h, w are the same as in the the product heating stage (from Tr ? Tkiln for the clinker and from
baseline case, i.e. q = q0, simplifies to Tr ? Tp for the fluegas) or for the fluegas: DH ¼ m
n    o
aðT p  T r Þ þ b=2 T 2p  T 2r  c T 1 1
p  Tr or, since the third
Qk sm ¼ Qk sm 0 þ t qT0 S A1 ðW f  W0 f 0 Þ ðA7Þ
term for the cement kiln products is six orders of magnitude smaller
 
For the fuel mill mass and gas volumetric flowrate vectors: than the other terms, DH=m ¼ a ðT p  T r Þ þ b=2 T 2p  T 2r ¼
a ðT p  T r Þ þ b=2 ðT p  T r Þ ðT p þ T r Þ ¼ fa þ b=2 ðT p þ T r ÞgðT p  T r Þ
mf m ¼ ð1  hÞ M B f þ M a M 1 T
air b f () mf m
or DH = cp (mass flowrate) (Tp  Tr) where cp = a + b/2 (Tp + Tr).
¼ M fð1  hÞ B þ a M 1 T
air b g f The constants a, b are known for the fluegases and the clinker. From
Eq. (3), mr m = (1 + M1 g) (e1 kT  rT) f and (A10) becomes:
which is Eq. (15).
Eq. (15) results from Eq. (13) via right multiplication by t M1 dðLHVÞ ¼ ðcTpf f  cTpf0 f 0 Þ ðT r  T s Þ þ cp rm ðð1 þ M 1 gÞ ðk
T T
where t = RT/P is the gas molar volume at T, P:  r f Þ  ð1 þ M 1 gÞ ðk0  r f 0 ÞÞ ðT r  T s Þ 0

Qf m ¼ t fð1  hÞ B þ M1
air
T
a b g f () Q f m þ cp air mair ðT r  T s Þ  cp air mair 0 ðT r  T s Þ

¼ t fð1  hÞ SA 1
W þ u1 ð1  hÞ g ðe 1 T T
k r Þ þ cTp ðmfg  mfg 0 Þ ðT p  T r Þ þ cp clinker ðk

þ M 1 T  k0 Þ ðT kiln  T r Þ ðA11Þ
air a b g f

which is Eq. (16). From the law of Lavoisier for reaction (a), total fuel
Eq. (17) results from Eq. (15) by right multiplication by eT and mass + mair = mcombustion flue gas + slag or mair = mcombustion flue gas +
noting that eT a = 1 and eT u1 = 1. slag  total fuel mass or mair = eT mfg + rT f  eT f or using Eq. (5),

Qf m ¼ t fð1  hÞ eT S A1 W þ ð1  hÞ g ðe1 kT  rT Þ mair ¼ eT M S A1 Wf þ rT f  eT f or

T 1 T
þ M 1 bT g f mair ¼ e ðM S A W  IÞf þ r f
air
 C.A. Tsiliyannis / Fuel 99 (2012) 20–39 37

and the air heating term becomes þ k0 cp clinker ðT kiln  T r Þ

cp air mair ðT r  T s Þ  cp air mair 0 ðT r  T s Þ ¼ cp air ½eT ðM S A1 W  IÞ ¼ k ½cp rm ð1 þ M 1 gÞ ðT r  T s Þ
f þ rT f  eT ðM S A1 W0  IÞf 0  rT0 f 0  ðT r  T s Þ: þ cp CO2 MCO2 g ðT p  T r Þ þ cp clinker ðT kiln  T r Þ ðA13Þ

Using Eq. (5) for the flue gas mass flowrate vectors, mfg, (A11) is
(or by grouping the f–terms) ()
written in terms of the fuel mass rate vectors, f and f0 and by using
Eq. (1), i.e. k = e1 kT f, Eq. (A11) becomes: kfcp1 M 1 g ðT p  T r Þ þ cp clinker ðT kiln  T r Þ þ cp rm ð1 þ M 1 gÞ ðT r  T s Þg
¼ e0 k0 þ cp1 M 1 g k0 ðT p  T r Þ þ cp clinker k0 ðT kiln  T r Þ
dðLHVÞ ¼ ðcTpf f  cTpf0 f 0 Þ ðT r  T s Þ þ cp rm ðð1 þ M1 gÞ ðk  rT f Þ h i  
þ cp air eT ðM S A1 W0  IÞ f 0 þ rT0 f 0 ðT r  T s Þ þ cTp M S A1 W0  cp1 M1 g rT0
 ð1 þ M 1 gÞ ðk0  rT0 f 0 ÞÞ ðT r  T s Þ  
 ðT p  T r Þ f 0 þ ½cTpf0 f 0  cp rm ð1 þ M 1 gÞ rT0 f 0  k0 ðT r  T s Þ
þ cp air ½eT ðM S A1 W  IÞ f þ rT f n    
þ kT  cTp M S A1 W  cp1 M 1 grT ðT p  T r Þ þ cp rm ð1 þ M1 gÞ rT  cTpf ðT r  T s Þ
 eT ðM S A1 W0  IÞ f 0  rT0 f 0  ðT r  T s Þ o
cp air ½eT ðM S A1 W  IÞ þ rT  ðT r  T s Þ f () k ¼ j þ jT f ð20Þ
þ cTp MðBf  B0 f 0 ÞðT p  T r Þ þ cp clinker ðk  k0 Þ ðT kiln  T r Þ
() dðLHVÞ ¼ ðcTpf f  cTpf0 f 0 Þ ðT r  T s Þ þ cp rm ½ð1 þ M1 gÞ j ¼ fcp1 M1 gðT p  T r Þ þ cp clinker ðT kiln  T r Þ þ cp rm ð1 þ M1 gÞ

 ðk  rT f Þ  ð1 þ M 1 gÞ ðk0  rT0 f 0 Þ ðT r  T s Þ  ðT r  T s Þg1 e0 k0 þ cp1 M1 gk0 ðT p  T r Þ þ cp clinker k0
 
þ cp air ½eT ðM S A1 W  IÞ f þ rT f  ðT kiln  T r Þ þ cTp M S A1 W0  cp1 M 1 g rT0 ðT p  T r Þ f 0
 eT ðM S A1 W0  IÞ f 0  rT0 f 0  ðT r  T s Þ h  
þ cTpf0 f 0  cp rm ð1 þ M 1 gÞ rT0 f 0  k0
þ cTp M ðS A1 W f þ u1 g k  u1 g rT f  S A1 W0 f 0 i o
 u1 g k0 þ u1 g rT0 f 0 Þ ðT p  T r Þ þ cp clinker ðk  k0 Þ ðT kiln  T r Þ þ cp air ðeT ðM S A1 W0  IÞ f 0 þ rT0 f 0 Þ ðT r  T s Þ ð21Þ

or, since d(LHV) = (LHV)  (LHV)0 = ek  e0 k0 and e k = kTf jT ¼ fcp1 M1 g ðT p  T r Þ þ cp clinker ðT kiln  T r Þ þ cp rm ð1 þ M1 gÞ
T n  
k f  e0 k0 ¼ ðcTpf f  cTpf0 f 0 Þ ðT r  T s Þ  ðT r  T s Þg1 kT  cTp M S A1 W  cp1 M 1 grT ðT p  T r Þ
h
þ cp ð1 þ M 1 gÞ ðk  rT f Þ h i
rm
 i þ cp rm ð1 þ M 1 gÞ rT  cTpf  cp air ðeT ðM S A1 W  IÞ þ rT Þ
ð1 þ M1 gÞ k0  rT0 f 0 ðT r  T s Þ  ðT r  T s Þg ð22Þ
þ cp air ½eT ðM S A1 W  IÞ f þ rT f The initial heating terms (all terms multiplying (Tr  Ts)) are rel-
 eT ðM S A1 W0  IÞ f 0  rT0 f 0  ðT r  T s Þ atively small and Eqs. (21) and (22) may be simplified by setting
h Tr = Ts; then cp rm, cpf, cp f0, cp air data are not necessary.
þ cTp M ðS A1 W  u1 g rT Þ f þ u1 gk
  i
A.5. For the level of production
 S A1 W0  u1 g rT0 f 0  u1 gk0 ðT p  T r Þ
þ cp clinker ðk  k0 Þ ðT kiln  T r Þ ðA12Þ Use of the relation, e1 kT f = k, in Eq. (14) gives:
n h i o
Noting that cTp M u1 ¼ cp1 M 1 , Eq. (A12) gives Eq. (18): Q k sm ¼ t qT S A1 W þ q1 g þ ð1 þ M1 gÞ M1
air asm ðe
1 T
k  rT Þ f
  h i
kT f ¼ e0 k0 þ cTpf f  cTpf0 f 0 ðT r  T s Þ () Q k sm ¼ t fqT S A1 Wg f þ t q1 g þ ð1 þ M 1 gÞ M 1
air asm k
h  i h i
1 T
 q1 g þ ð1 þ M 1 gÞ M air asm t r f () Q k sm
þ cp rm ð1 þ M 1 gÞ ðk  rT f Þ  ð1 þ M 1 gÞ k0  rT0 f 0 n h i o
h ¼ t qT SA1 W  q1 g þ ð1 þ M 1 gÞ M 1 T
air asm r f
 ðT r  T s Þ þ cp air eT ðM S A1 W  IÞ f þ rT f  eT h i
i 1
þ t q1 g þ ð1 þ M 1 gÞ M air asm k () k
ðM S A1 W0  IÞ f 0  rT0 f 0 ðT r  T s Þ n h io1
h ¼ t q1 g þ ð1 þ M 1 gÞ M 1
air asm Q k sm
þ cTp M S A1 ðW f  W0 f 0 Þ þ ðk  k0 Þ ðcp CO2 M CO2 gÞ h i1
 i  q1 g þ ð1 þ M 1 gÞ M 1
air asm qT SA1 W þ rT g f
þ cp1 M 1 g rT0 f 0  rT f ðT p  T r Þ
which is Eq. (23) with j0 and j0 given by Eqs. (24) and (25).
þ ðk  k0 Þ cp clinker ðT kiln  T r Þ ð18Þ h i
1
Q k sm 6 Q k smax () t fqT SA Wg f þ t q1 g þ ð1 þ M1 gÞ M1air asm k
(Eq. (19) results upon isothermal substitution, kT f = e0 k0, by h i
neglecting the reactant heating terms, Tr = Ts). Keeping the k-terms  q1 g þ ð1 þ M1 gÞ M1 air asm t r f
T

in the same side (right hand side), Eq. (18) becomes: n h i o

1
  h 6 Q k smax () t qT SA W  q1 g þ ð1 þ M1 gÞ M1 air asm r
T
f
kT f  e0 k0  cTpf f  cTpf0 f 0 ðT r  T s Þ  cp rm ð1 þ M1 gÞ ðrT f Þ h i
  i þ t q1 g þ ð1 þ M1 gÞ M1 air asm k

 1 þ M 1 gÞ k0  rT0 f 0 ðT r  T s Þ 6 Q k smax () k
h n h io1
 cp air eT ðM S A1 W  IÞ f þ rT f  eT 6 t q1 g þ ð1 þ M 1 gÞM 1
air asm Q k smax
 i
nh io1
 M S A1 W0  IÞ f 0  rT0 f 0 ðT r  T s Þ  q1 g þ ð1 þ M 1 gÞ M 1 qT SA1 W þ rT g f
air asm
h
 cTp M S A1 ðW f  W0 f 0 Þ  k0 cp CO2 MCO2 g
which, if baseline blower capacity is the operating constraint,
 i
 cp1 M 1 g rT0 f 0  rT f ðT p  T r Þ Qk sm = Qk sm 0, then, given Qk sm 0, it may be solved for the clinker
production level, k corresponding to blower capacity:
38 C.A. Tsiliyannis / Fuel 99 (2012) 20–39
k ¼ j0 þ j0T f
h  i
j ¼ Q k sm; 0 = t ðq1 g þ 1 þ M1 gÞ M1
0
air asm
h i
j0T ¼ rT  ½qT S A1 W= q1 g þ ð1 þ M1 gÞ M1
air asm
Necessary condition (26) results directly by equating k from
Eqs. (20) and (23). It is a scalar binding constraint between n + 2
variables, the components of f and h, w. Sufficient, but excessively
restrictive conditions for Eq. (26) to be satisfied are: j = j0 and
(j  j0 )Tf = 0, or (j  j0 ) and f be vectors perpendicular to each
other.
A.6. Proof of Proposition 1
(a) It follows directly from the definitions of q, q1 and from Eq.
(14) which determines Qk sm.
(b) Uon equivalent partial thermal substitution of a conven-
tional fuel by an AF with lower heating value, k, it is shown
via Eqs. (20)–(24) that the following is valid:
(j  j0 ) < (j0  j)T f, or j + jT f < j0 + j0 T f which gives the
result. For an AF mixture with n components featuring lower
heating values ki, i = 1, 2, . . . , n, the same is shown by induc-
tion on n.
A.7. For Greenhouse gas emissions
kN2 O ¼ ðQ N2 O =Q fg Þ=ðQ N2 =Q fg Þ ðQ O2 =Q fg Þ1=2 () kN2 O
 
1=2 1=2 1=2 1=2
¼ Q N2 O Q fg = Q N2 Q O2 () Q N2 O ¼ kN2 O Q N2 Q O2 =Q fg
() r N2 O ¼ MN2 O t1 kN2 O Q N2 Q 1=2 1=2
O2 =Q fg () r N2 O
1=2  1=2
¼ t1 kN2 O M N2 O Q fg uT4 Q fg uT3 Q fg
 from which Eq: ð27Þ is obtained : r CO2 eq
1=2  1=2
¼ uT1 M B f þ c t1 kN2 O MN2 O Q fg uT4 Q fg uT3 Q fg
Appendix B
The matrices S, A1 (excess air E = 20%, air humidity h = 65%,
number of chemical elements in the reactants, r = 7, number of flue
gas chemical species, m = 7). Note that the upper 4x3 part of S is
the same as in Section 3.2 (the difference in the H2O row is due
to h > 0 as dictated by reaction (a)).
0 1
CO2 1:0000 0:0000 0:0000 0:0000 0:0000 0:0000 0:0000
B 0:0806 0:6007 0:0403 0:5000 0:0806 0:0000 0:0000 C
H2 O B C
B C
O2 B 0:2000 0:0500 0:1000 0:0500 0:2000 0:0000 0:2500 C
B C
B C
N2 S ¼ B 4:5143 1:1286 2:2571 1:1286 4:5143 0:5000 5:6429 C
B C
SO2 B 0:0000 0:0000 0:0000 0:0000 1:0000 0:0000 0:0000 C
B C
B C
HCl @ 0:0000 0:0000 0:0000 1:0000 0:0000 0:0000 0:0000 A
P2 O 5 0:0000 0:0000 0:0000 0:0000 0:0000 0:0000 0:5000
0 1
C 0:0833 0:0000 0:0000 0:0000 0:0000 0:0000 0:0000
H B 0:0000 1:0000 0:0000 0:0000 0:0000 0:0000 0:0000 C
B C
B C
O B 0:0000 0:0000 0:0625 0:0000 0:0000 0:0000 0:0000 C
B C
1 B C Council for Sustainable Development;; 2005. p. 38.
S A ¼ B 0:0000 0:0000 0:0000 0:0313 0:0000 0:0000 0:0000 C
B C
N B 0:0000 0:0000 0:0000 0:0000 0:0714 0:0000 0:0000 C
B C
B C
Cl @ 0:0000 0:0000 0:0000 0:0000 0:0000 0:0286 0:0000 A
P 0:0000 0:0000 0:0000 0:0000 0:0000 0:0000 0:0323
The matrices W and MSA1W for any composition of the AF
mixture fT = mass feed rates of (petcoke, coal, TDF, sewage sludge,
RDF).
ð23Þ B.1. Ultimate analysis of conventional and alternative fuels
ð24Þ
Case study data.
(Fuel ultimate analysis, matrix W for the various fuel mixtures.)
ð25Þ
In the various scenaria considered in the Case Study, only the
columns of W corresponding to the AFs included in the fuel mix-
ture are used: e.g. in scenario 2 (coal 100%) W is the column vector
(0.7527, 0.047, 0.0793, 0.0028, 0, 0, 0.0984); in the baseline sce-
nario, W is the 7  2 matrix formed by the first two columns of
W above corresponding to coal and petcoke; in scenario 4, W con-
sists of the first three columns of W above, etc.
0 1
CO2 2:7599 3:2340 2:9957 1:4850 1:9433
H2 O B 0:5968 0:5009 0:9415 0:7916 0:8114 C
B C
B C
O2 B 0:4697 0:5374 0:5791 0:2665 0:4017 C
B C
B C
N2 MSA1 W ¼ B 9:2764 10:6133 11:4363 5:2674 7:9339 C
B C
SO2 B 0:0905 0:1083 0:0261 0:0384 0:0005 C
B C
B C
HCl @ 0:0032 0:0488 0:0204 0:0014 0:0000 A
P2 O5 0:0000 0:0000 0:1617 0:0000 0:4349
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