Fuel 79 (2000) 1195–1207

www.elsevier.com/locate/fuel

Impact of incinerator internal hydrodynamics on hazardous organic

waste destruction efficiency
Estelle Desroches*, Gérard Antonini
Université de Technologie de Compiègne UPRES A 6067, Centre de Recherche de Royallieu, BP 325–60205, Compiègne Cédex, France
Accepted 19 November 1999

Abstract
The results of a study concerning the influence of internal hydrodynamics of incinerators on the principal organic hazardous constituents
(POHCs) destruction efficiency are presented in this paper. A model of two tanks-in-series is used to describe internal hydrodynamics of
incinerators via residence time distributions (RTD). Two cases corresponding, respectively, to the presence of a short-circuit and a deadwater
zone within the internal flow are examined in detail. The results indicate that the incinerability ranking, based on plug-flow laboratory
experiments for thermal stability determination, is disrupted. Temperatures required to obtain a conversion rate of 99.99% in a perturbed flow
are higher. Simple relationships allow calculation of the temperature requirement deviation from the plug-flow case knowing the kinetic
parameters of the waste combustion and the characteristics of the reactor hydrodynamics.
This study shows that the selection of compounds to be spiked in the waste feed of an incinerator during a trial burn should be coupled to a
direct determination of the residence time distribution of the incinerator itself for a proper selection of the compound that is more difficult to
burn than any other organic expected in the actual waste.
Methane, chlorobenzene and methyl chloride, which are characterized by a high stability whatever the species residence time distribution
in the incinerator, are good candidates for trial burns. q 2000 Elsevier Science Ltd. All rights reserved.
Keywords: Incinerability ranking; Hazardous wastes; Destruction and removal efficiency; Residence time distribution; Hydrodynamic ills

1. Introduction plug-flow reactor [4,5]. This approach has been extended to

The combustion efficiency or thermal destruction capa-
cities of a thermal treatment system are generally evaluated
on the basis of the “three Ts” rule, based on temperature,
mixing turbulence and residence time of the system, in rela-
tion to failure modes potentially existing within the system
(poor atomization, quenching, pyrolytic zones…) [1,2].
The ability of a thermal treatment system to destroy
organics can be evaluated via trial burns based on spiking
the waste feed with selected principal organic hazardous
constituents (POHCs) [3]. The selection of POHCs is made
by assuming that these components are ideally more difficult
to burn than any organic expected to be in the actual waste.
This has imposed a ranking of various candidates based
on incinerability indices of POHCs like heat of combustion,
auto-ignition temperature and T99.99(2) index, corresponding
to the temperature required to obtain a four nine destruction
and removal efficiency (DRE) of the molecule with a resi-
dence time of 2 s. This hierarchy of incinerability of POHCs
has been obtained from kinetic data obtained in laboratory
* Corresponding author. Tel.: 133-3-44-23-44-23; fax: 133-3-44-23-19-80.
E-mail address: Estelle.Desroches@edf.fr (E. Desroches).
0016-2361/00/$ - see front matter q 2000 Elsevier Science Ltd. All rights reserved.
PII: S0016-236 1(99)00266-5
a thermal stability index under an oxygen deficient environ-
ment (Ts, low O2), based on compounds that are thermally
stable at low or deficient oxygen conditions.
The results of a comparison of 10 field studies with ther-
mal stability scales indicate that no ranking based on pure
compound properties can provide an appropriate scale of
incinerability [6,7].
It is the purpose of the present paper to show that the
scales of incinerability of POHCs are deeply affected by
the real conditions of internal hydrodynamics within an
incinerator, that is to say by its convective failure modes
(deadwater zone, short circuit…). This paper shows the
impact of these hydrodynamic ills of operating conditions
on the destruction and removal efficiency of incinerators.
2. Theoretical considerations
For large excess air combustion, gaseous species destruc-
tion reactions can be described with a first order kinetic law:
 
dc 2EA
ˆ 2kc with k ˆ k0 exp ) c…t† ˆ c0 e2kt
dt RT
1196 E. Desroches, G. Antonini / Fuel 79 (2000) 1195–1207

Nomenclature
c(t) Concentration of gaseous industrial waste in the reactor (mol m 23)
E(t) Residence time distribution function
EA Activation energy
f Volumetric fraction of the main flow that is perturbed
k Combustion rate constant (m s 21)
k0 Pre-exponential factor of the Arrhenius expression of the kinetic constant (m s 21)
m Number of reactors in the secondary branch of the tank-in-series model
n Number of reactors in the main branch of the tank-in-series model
Q Volumetric flow rate of gaseous industrial waste (m 3 s 21)
T Reactor temperature (8C)
T99.99 dw(2) Temperature required for a destruction rate of 99.99% in the plug flow reactor perturbed by a deadwater zone
with a mean residence time of 2 s (8C)
T99.99 pf(2) Temperature required for a destruction rate of 99.99% in the plug flow reactor with a mean residence time of
2 s (8C)
T99.99 sc(2) Temperature required for a destruction rate of 99.99% in the plug flow reactor perturbed by a short-circuit with
a mean residence time of 2 s (8C)
td Ignition delay (s)
V Reactor volume (m 3)
v Perturbed-zone volume (m 3)
Xdw Conversion rate in the deadwater zone perturbed reactor
Xpf Conversion rate in the plug-flow reactor
Xsc Conversion rate in the short-circuit perturbed reactor
a Ratio of the residence times in the two branches of the tank-in-series model
t Total residence time in the reactor (s)
t2 Residence time in the secondary branch of the tank-in-series model
t2 Residence time in the main branch of the tank-in-series model

where c is the molar concentration of the gaseous reactant, R the following relation:
the ideal gas constant, EA its activation energy (kJ mol 21 or  Z∞ 
kcal mol 21) and k0 its pre-exponential factor (s 21). These cin 2 cout
DRE ˆ × 100 ˆ 100 × 1 2 e2kt E…t†dt
constants have been experimentally determined and are cin 0

available for most POHCs [8].

where E(t) is the residence time distribution function of the
This leads to the determination of combustion
equipment and k the kinetic constant of the molecule to be
temperatures necessary to destroy the species with a
burnt out.
destruction removal efficiency of 99.99% for a given
Thus, the thermal destruction efficiency of an incinerator
residence time (generally 2 s); these combustion temp-
for POHCs can be directly linked with its time residence
eratures being calculated on the assumption of a plug-
distribution function and it can be seen that all the internal
flow ideal reactor.
hydrodynamic pathologies, contained in the function E(t),
In fact, internal flow through equipment practically
directly influence the furnace performances in terms of
always results in a certain residence time distribution that
DRE.
means elements fed simultaneously will generally leave the
system at different times. This distribution of residence time
can be described by the function E(t) which is the residence 2.1. Residence time distribution (RTD)
time distribution (RTD) of the system, characteristic of the
The residence time distribution in ideal reactors is well
reactor used for combustion.
defined. A plug-flow reactor behaves as a pure delay and its
The variations of the internal residence time of molecules
RTD can be described with a Dirac function, which leads to
within the equipment will give various conversion rates for
the following expression for the DRE:
the same species, and the DRE of a given species will not
only depend on its kinetic constants but also on the RTD …DRE†pf Z∞
within the equipment for a given mean residence time ˆ12 e2kt d…t 2 t†dt ˆ 1 2 e2kt
100 0
imposed by the waste and air feed.
Then, the DRE of a given species should be calculated by where t is the gas residence time in the reactor defined as
 E. Desroches, G. Antonini / Fuel 79 (2000) 1195–1207 1197

V/Q where V is the volume of the reactor and Q is the where t 1, t 2 are the residence time in each of the two
volumetric flow rate, depending on feed conditions. branches,
For a perfectly mixed reactor, this expression becomes:
v
Z∞   t1 ˆ
…DRE†pf 1 2t=t kt fQ
ˆ12 e2kt e dt ˆ
100 0 t 1 1 kt
and
The RTD in a non-ideal reactor is generally considered as
intermediate between the plug-flow and the perfectly-mixed V 2v
t2 ˆ
reactor. This real case can easily be described with a cascade …1 2 f †Q
of n series perfectly-mixed equivalent reactors (the extreme
cases n ˆ 1 and n ˆ / corresponding, respectively, to the The total mean residence time in the reactor can be
perfectly mixed and the plug-flow reactor). obtained according to the relation:
Z∞
tˆ tE…t†dt ˆ f t1 1 …1 2 f †t2
0

Then, the introduction of a parameter a equal to the ratio t 2/

The RTD of a real reactor can then be described through t 1 of the residences times in each branch, allows to quantify
the relation: the ratio between the secondary zone volume v and the
tn21 t furnace total volume V:
En …t† ˆ  n e2n t
t
…n 2 1†! v f
n ˆ
V f 1 …1 2 f †a
Moreover, internal flows in a reactor can be disturbed: by-
pass and/or deadwater zones can exist and have an impor- It can also be noticed that, for a given value of f, cases with
tant impact on the reactor performances. The impact of a . 1 correspond to the existence of a deadwater region,
these hydrodynamic defects on the RTD can be illustrated whereas the condition a , 1 induces the presence of a by-
considering that the reactor is equivalent to the following pass. The non-disturbed case is described by the model with
system [9,10]: f ˆ 0 and a ˆ 1.

The gaseous flow rate Q is divided into a secondary Consequently, the DRE for a non-ideal reactor can be
flow—corresponding to a fraction f of the total flow expressed as follows:
rate—and a main modified flow equal to (1 2 f )Q. If m 2
and n are, respectively, the number of reactors in the 1st
Z∞ 6
and 2nd branch (m and n account for the difference of each DRE 6 tm21 t
branch compared with ideality), each branch of volume V ˆ12 e2kt 6
6f !n e2m t1
100 0 4 t1
and v, respectively, can be considered as a succession of …m 2 1†!
m
perfectly mixed reactors of volume v/m and (V 2 v)/n.
The RTD for the whole system can be written as 3
follows: 7
tn21 2n t 7
t
1…1 2 f † ! ne
7dt
2
7
tm21 t t2 5
E…t† ˆ f  n e2m t1 …n 2 1†!
t n
…m 2 1†! 1
m

tn21 t
1…1 2 f †  n e2n t2 DRE
ˆ12f 
1
 1 …1 2 f † 
1

t 100 t1 m t2 n
…n 2 1†! 2 11 k 11 k
n m n
1198 E. Desroches, G. Antonini / Fuel 79 (2000) 1195–1207

Table 1
Expression of the DRE for different types of reactors in the case of a delayed reaction

DRE
Plug flow reactor t , td ) ˆ0
100
DRE
t . td ) ˆ 1 2 e2k…t2td †
100
 
DRE td kt
Perfectly mixed reactor ˆ e2 t
100 1 1 kt

0 0 11
 i  i
DRE B t
2m d BmX
21
1 mtd 1 mX
21
1 m CC
Real reactor ˆ 1 2 fB
@1 2 e t1 B
@ 2  × 1 k tdi CC
AA
100 i! t1 kt m i! t1
iˆ0 11 1 iˆ0
m
0 0 11
 i  i
B t
2n d BnX
21
1 ntd 1 nX
21
1 n CC
2 …1 2 f †B
@1 2 e t2 B
@ 2  × 1 k tdi C
AA
C
i! t2 kt n i! t2
iˆ0 11 2 iˆ0
n

Fig. 1. Evolution of T99.99(2) in a plug-flow reactor as a function of kinetic parameters (EA/ln(k0)).

 E. Desroches, G. Antonini / Fuel 79 (2000) 1195–1207 1199

Fig. 2. Residence time distribution in a plug-flow reactor disturbed by a short-circuit. Influence of the parameter a .

2.2. Delayed reactions The parameters k0, EA, X1, X2 have been experimentally
measured by several authors [5,8].
For a lot of organic components, the kinetic destruction For delayed reactions, the DRE expression is modified in
law includes an ignition delay [6]. For large excess air the following way:
combustion, the reaction rate can then be described with a Ztd 
first order kinetic law modified by a temperature specific lag DRE Z∞
ˆ12 E…t†dt 1 e2k…t2td † E…t†dt
time: 100 0 td

c…t† ˆ c0 for t , td Table 1 gives the analytical expressions of the DRE for
the different types of reactors.
c…t† ˆ c0 e2k…t2td † for t . td

where k is the kinetic constant and td the ignition delay that 3. Results and discussion
linearly depends on the temperature:
To illustrate the influence of hydrodynamic perturbations
t d ˆ X1 2 X2 T
on the DRE, the temperature required for a destruction level
of 99.99% at a 2 s residence time was calculated for two
EA
k ˆ k0 e2 RT types of reactor:
• a plug flow reactor disturbed by a short circuit
where X1 and X2 are constants characteristic of the
(n ˆ m ˆ 50, a , 1)
component.
• a plug flow reactor disturbed by a deadwater region
(n ˆ m ˆ 50, a . 1).
We supposed that the organic wastes flow is nearly a
plug-flow in the two branches (high values for n and m).
The results obtained for benzene, ethyl-mercaptan and
methane destruction were then compared with the temp-
erature calculated considering the furnace as a plug flow
reactor.

3.1. The usual case: the plug-flow reactor

Fig. 3. Impact of the parameter a on the difference T99.99sc(2) 2 T99.99pf(2) In a plug-flow reactor, for non-delayed reactions, the
(n ˆ m ˆ 50, f ˆ 0.1). value of the temperature required for a destruction level of
1200 E. Desroches, G. Antonini / Fuel 79 (2000) 1195–1207

Fig. 4. Illustration of the linear relation between parameter ln(a ) and the difference 1/T99.99pf(2) 2 1/T99.99sc(2) … f ˆ 0:1; n ˆ m ˆ 50†.

99.99% is given by the expression:
EA
T99:99 ˆ  
k0 t
Rln
ln…104 †
This shows that, for a given residence time, T99.99 only
depends on kinetic parameters of the considered species.
Fig. 1 shows the evolution of T99.99 as a function of the
kinetic data given by Lee and al. [5,8] for 15 organic wastes.
It can be seen that the destruction temperature varies line-
arly with the ratio EA/ln(k0). The departure from linearity,
which can be observed for methane, propylene, allyl alco-
hol… reflects the fact that the ignition delay of these wastes
is not negligible, even at high temperatures. In the range of
combustion temperatures, ignition delay is, most of the
time, very short compared with the residence time.
It can be deduced that ethyl mercaptan, which is
characterized by a very low activation energy, is destroyed
at very low temperatures (about 3738C), whereas methane
with its moderate pre-exponential factor and its high activa-
tion energy can only be burnt at a high temperature
(882.58C).
3.2. The plug flow reactor disturbed by a short-circuit
The first case of perturbed flow that we studied corre-
sponds to channeling of fluid in the reactor that is also called
“short-circuit”. This creates a secondary flow considered as
a plug flow but characterized by a shorter residence time
than the main gaseous flow.
If the flow in the reactor is expected to approximate to
plug flow, then the RTD curve is centered on the mean
residence time and has not a very large spread (as can be
seen in Fig. 2). The short-circuit provokes the appearance of

Fig. 5. Illustration of the linear variation between ln(1 2 f) and the difference 1/T99.99pf(2) 2 1/T99.99sc(2) (n ˆ m ˆ 50, case of benzene).
 E. Desroches, G. Antonini / Fuel 79 (2000) 1195–1207
Fig. 6. Influence of the parameter f on the difference T99.99sc(2) 2 T99.99pf(2)
(n ˆ m ˆ 50, case of benzene).
a small first peak for short residence times and a moderate
enlargement of the RTD later (see Fig. 2).
The relative importance of the first peak and its appearance
time are directly related to the variables a and f. We under-
stand that these parameters have a high influence on the calcu-
lations of the temperature required to obtain a conversion of
99.99%. Indeed, at the same temperature, the species
contained in the secondary flow have a shorter residence
time and are consequently less converted. To obtain the
same conversion level as in a plug-flow reactor, the combus-
tion temperature has to be higher. In fact, it can be observed
from Fig. 3 that when a molecule is burnt for the same global
residence time of 2 s in a reactor, the destruction efficiency
directly depends on the RTD, which is the signature of the
internal hydrodynamics of the furnace used. There is usually
Fig. 7. Residence time distribution in a plug-flow reactor disturbed by a short-circuit. Influence of the secondary flow proportion.
1201
a reduction of the effective DRE compared with the reference
case of the norm (plug-flow reactor). For example, to obtain
the same destruction efficiency for ethyl mercaptan, the
temperature level must be between 40 and 1208C higher in a
perturbed-flow reactor than in a plug-flow reactor.
Fig. 3 also shows the impact of a —the ratio between the
residence times in the two branches—on the difference
between the temperatures required for a destruction rate of
99.99% in a plug-flow and in a short-circuit perturbed reac-
tor (T99.99sc(2) 2 T99.99pf (2)). We can notice a deep decrease
of T99.99(2) when a grows.
As can be seen in Fig. 2, the decrease of the parameter a
essentially induces a transfer of the first peak towards the
shorter residence times. The second peak is nearly simulta-
neous to the RTD of a plug-flow reactor and we can consider
that the fraction of molecules, which composes the main flow
(90% in that case), is converted in the same way. This signifies
that the difference observed is directly caused by the conver-
sion efficiency of the 10% of molecules which go to the short-
circuit. In a plug-flow reactor, the residence time of these 10%
of molecules is t ˆ 2 s although in the short- circuit, it is equal
to a /(0.1a 1 0.9) × t (for f ˆ 0.1). In other words, the conver-
sion in the short-circuit must be compared with the conversion
which is obtained in a plug-flow (in that case a ˆ 1).
If we consider the secondary flow as an ideal plug-flow,
then we have:
 
EA af
2k0 :exp 2
RT99:99sc …2† af 1…12f † t
1 2 Xsc e
ˆ   ˆ1
1 2 Xpf E f
2k0 :exp 2 RT A …2† f 1…12f † t
e 99:99pf
where Xsc and Xpf are the conversion rates, respectively,
in the short-circuit perturbed reactor and the plug-flow
reactor.
1202 E. Desroches, G. Antonini / Fuel 79 (2000) 1195–1207

Fig. 8. Variation of T99.99sc(2) 2 T99.99pf(2) with the parameter EA/(lnk0) 2 (f ˆ 0.1, n ˆ m ˆ 50).

Consequently, the difference between the temperatures It can also be noticed that, for a given reactor, the
required for a destruction rate of 99.99% in a plug-flow difference between T99.99sc(2) and T99.99pf(2) depends on the
and in a short-circuit perturbed reactor corresponds to: value of the kinetic parameters:
  T99:99sc …2† 2 T99:99pf …2†
1 1 R 1
2 ˆ2 ln
T99:99pf …2† T99:99sc …2† EA …1 2 f †=a 1 f T99:99pf …2†
ˆ
EA
Fig. 4 shows the linearity of the difference between the 11  
1
inverse of the respective temperatures with the logarithm Rln T …2†
…1 2 f †=a 1 f 99:99pf
of the parameter a for a constant value of f, that confirms
the assumptions that the weak conversion in the by-pass is Including the expression of T99.99(2) in a plug-flow reactor
responsible for the variations of T99.99(2). defined earlier, we find that:
Considering this relation, we can also see that for a  
EA a
constant value of a and a given waste, this difference is T99:99sc …2† 2 T99:99pf …2† ˆ ln
R…lnk0 †2 12f
nearly proportional to the quantity ln(1 2 f ). Indeed for
a , 0.5, and 0.05 , f , 0.4, we have (1 2 f )/a . 5f ). This relation shows that the variation increases with the
Fig. 5 confirms the linearity relation. That signifies that ratio EA/ln(k0) 2 (as illustrated in Fig. 8).
T99.99sc(2) grows when f decreases (as can be seen in Fig. 6. For two components, which are characterized by the
When the volumetric fraction of the secondary flow same pre-exponential factor, the difference increases when
increases, a higher proportion of molecules exit after a the activation energy grows. This is logical because, for a
short residence time. Simultaneously, the residence time weak activation energy, the conversion is faster and the
in the short-circuit increases (see Fig. 7) inducing a higher molecules of the short-circuit which have a short residence
conversion of these molecules. It seems that this second time are nevertheless well converted and the difference for
phenomenon is preponderant, while a lower temperature is the plug-flow reactor decreases.
necessary to obtain 99.99% of conversion in the case of very For a constant activation energy, the best converted
perturbed flows. molecules are characterized by a high pre-exponential factor

Table 2
Impact of the kinetic parameters on the destruction temperature variation caused by a short-circuit (a ˆ 0.2, f ˆ 0.1, n ˆ m ˆ 50)

Waste k0 (s 21) EA (kcal mol 21) EA/ln(k0) 2 T99.99pf(2) (8C) T99.99sc(2) 2 T99.99pf(2)

Benzene 7.43 × 10 221 95900 37.81 718 34

Ethyl mercaptan 5.2 × 10 25 14700 84.85 373 75.5
Methane 1.68 × 10 211 52100 77.98 809 61.5
 E. Desroches, G. Antonini / Fuel 79 (2000) 1195–1207
Fig. 9. Comparison of the incinerability ranking in an ideal plug-flow and in a plug-flow reactor perturbed by a short-circuit (a ˆ 0.2, f ˆ 0.1, n ˆ m ˆ 50).
k0. Consequently the difference between the temperatures
required for a complete waste conversion in a plug-flow
and in a short-circuit perturbed reactor increases for the
weaker values of k0.
This causes different behaviour for the various wastes
burnt in the reactor. Table 2 shows the values of kinetic
parameters and destruction efficiencies for benzene, ethyl
mercaptan and methane.
It can be noticed that ethyl mercaptan is more sensitive
than benzene to the perturbation, especially because of its
low pre-exponential factor. In the case of the three compo-
nents under consideration, the classification is not modified
by the hydrodynamic ill. Considering the waste stability, the
ranking remains ethyl mercaptan , benzene , methane.
However, for wastes which have a close T99.99pf, such as
propane and acrylonitrile—indeed, T99:99pf …propane† ˆ
706 . T99:99pf …acrylonitrile† ˆ 704:5—an inversion in the
classification can be observed. The ratio EA/(lnk0) 2 is higher
1203
for acrylonitrile (64.6 against 41.3 for propane). This
corresponds to increases of the temperature—compared
with the destruction temperature in a plug-flow reactor—
of, respectively, 18 and 108C, that reverses the hierarchy.
Fig. 9 shows an example comparison between the inciner-
ability ranking in a plug-flow and in a short-circuit
perturbed reactor (a ˆ 0.2, f ˆ 0.1, n ˆ m ˆ 50). Several
inversions can be observed, however it can also be noticed
that the hierarchy for species like methane, chlorobenzene
and methyl chloride, which are characterized by a high
stability in a plug flow reactor and which are very sensitive
to hydrodynamic ills (because of a high value of their
parameter EA/(lnk0) 2), is not disturbed.
3.3. The plug flow reactor disturbed by a deadwater region
The term deadwater accounts for a portion of fluid that is
relatively slow moving compared with the main flow. In this
1204 E. Desroches, G. Antonini / Fuel 79 (2000) 1195–1207

Fig. 10. Residence time distribution in a plug-flow reactor disturbed by a deadwater zone. Influence of the parameter a .

case, the main peak appears for a shorter time than in difference between the temperatures required for a destruc-
the non-disturbed case and is followed by a trail of the tion rate of 99.99% in a plug-flow and in a stagnant region
RTD for longer times (see Fig. 10). Once again, it perturbed reactor (T99.99dw(2) 2 T99.99pf(2)). A moderate
appears that the important factor is the proportion repre- increase of T99.99(2) is observed when a grows.
sented by the first peak and its appearance time, which If we consider that the difference observed is directly
are linked with the variables a and f. Indeed, the mole- caused by a lower conversion of 90% of the molecules
cules are conveyed to the deadwater zone, stay a long which compose the main flow, we can write:
time in the reactor and are well converted. The conse-  
E 1
quence of the presence of stagnant zones is essentially
1 2 Xdw e
2k0 :exp 2 RT A …2†
99:99dw af 1…12f † t
to reduce the residence time in the main part of the ˆ   ˆ1
reactor. A higher combustion temperature is conse- 1 2 Xpf E
2k0 :exp 2 RT A …2† t
e 99:99pf
quently necessary to obtain a given conversion rate. In
the case of methane for example, the temperature level where Xdw and Xpf are the conversion rates, respectively, in
must be between 10 and 508C higher in a reactor the deadwater zone perturbed reactor and in the plug-flow
perturbed by a deadwater zone than in a plug-flow reactor.
reactor. Consequently, the difference between the temperatures
Fig. 11 shows the impact of the parameter a on the required for a destruction rate of 99.99% in a plug-flow

Fig. 11. Influence of a on the difference T99.99dw(2) 2 T99.99pf(2) for a plug-flow reactor perturbed by a deadwater zone (f ˆ 0.1, n ˆ m ˆ 50).
 E. Desroches, G. Antonini / Fuel 79 (2000) 1195–1207 1205

Fig. 12. Illustration of the linear relation between parameter ln(a ) and the difference 1/T99.99pf(2) 2 1/T99.99dw(2) (f ˆ 0.1, n ˆ m ˆ 50).

Fig. 13. Illustration of the linear variation between ln(a f 1 (1 2 f)) and the difference 1/T99.99pf(2) 2 1/T99.99dw(2) (n ˆ m ˆ 50, case of methane).

and a dead water zone perturbed reactor corresponds to: of the inverse of the respective temperatures and the
  logarithm of the parameter a for a constant value of f
1 1 R 1
2 ˆ2 ln (see Fig. 12).
T99:99dw …2† T99:99sc …2† EA …1 2 f † 1 af
Fig. 13 confirms the proportionality relation of this differ-
Indeed we found a linear relation between the difference ence with the quantity ln(1/(1 2 f ) 1 a f ) for a constant

Table 3
Impact of the kinetic parameter on the destruction temperature variation caused by a deadwater zone (a ˆ 5, f ˆ 0.1, n ˆ m ˆ 50)

Waste k0 (s 21) EA (kcal mol 21) EA/ln(k0) 2 T99.99pf T99.99dw 2 T99.99pf

221
Benzene 7.43 × 10 95900 37.81 718 10
Ethyl mercaptan 5.2 × 10 25 14700 84.85 373 26.5
Methane 1.68 × 10 211 52100 77.98 809 20
1206 E. Desroches, G. Antonini / Fuel 79 (2000) 1195–1207

Fig. 14. Variation of T99.99dw(2) 2 T99.99pf(2) with the parameter EA/(lnk0) 2 (f ˆ 0.1, n ˆ m ˆ 50).

value of a and a given waste and shows that T99.99dw(2) 4. Conclusion

grows when f decreases.
As in a case of the short-circuit, the temperature variation, The results of this study on the influence of hydro-
compared with the plug-flow combustion temperature, dynamic pathologies on the waste destruction efficiency of
differs from one molecule to another. The difference incinerators show the difficulty of obtaining a reproducible
between T99.99dw and T99.99pf can be expressed as follows: hierarchy of incinerability.
We observed that the temperature required for a destruc-
T99:99dw …2† 2 T99:99pf …2† tion rate of 99.99% strongly depends on the flow pattern in
the reactor. Two cases were examined: perturbation of the
T99:99pf …2† main plug-flow reactor by a short-circuit or a deadwater
ˆ zone.
EA
11  
1 The results obtained showed that waste sensitivity to
Rln T …2†
…1 2 f † 1 f a 99:99pf hydrodynamic perturbations varies a lot, as a function of
their destruction kinetic parameters. For a given waste, the
temperature variation depends on two parameters that can
If we include the expression of T99.99(2) in a plug-flow
be easily estimated: the volumetric fraction represented by
reactor:
the secondary flow and v/V, the ratio between the secondary
  zone volume and the furnace total volume.
EA 1
T99:99sc …2† 2 T99:99pf …2† ˆ ln According to the magnitude of the perturbation, this can
R…lnk0 †2 …1 2 f † 1 f a give rise to inversions in the ranking given by the method
based on laboratory-determined thermal stability. For exam-
It can be seen once again that the variation increases with ple, propylene is easier to burn than propane in a plug-flow
the waste kinetic parameters, exactly the ratio EA/ln(k0) 2 (as reactor but more stable in a plug-flow reactor perturbed by a
illustrated in Fig. 14). short-circuit.
Table 3 shows the relation between the kinetic parameters In order to be certain that the trial burn ensures that all
for benzene, ethyl mercaptan and methane and their sensi- compounds that may be fed into the incinerator are effi-
tivity to deadwater zone perturbation. ciently incinerated, we must use selected compounds
Fig. 15 shows an example of a comparison between the which are, indeed, more difficult to incinerate than the
incinerability ranking in a plug-flow and a deadwater zone other wastes but also very sensitive to hydrodynamic ills.
perturbed reactor (a ˆ 5, f ˆ 0.1, n ˆ m ˆ 50). The hierar- This work shows that the best candidates are methane,
chy is disrupted to a lesser extent than a short-circuit chlorobenzene and methyl chloride, which are characterized
perturbed furnace. Once again, methane, chlorobenzene by a high stability whatever the species residence time
and methyl chloride show a high stability for their inciner- distribution in the incinerator.
ability ranking. On the contrary, simultaneous determination of the RTD
 E. Desroches, G. Antonini / Fuel 79 (2000) 1195–1207
Fig. 15. Comparison of the incinerability ranking in an ideal plug-flow and in a plug-flow reactor perturbed by a deadwater zone (a ˆ 5, f ˆ 0.1, n ˆ m ˆ 50).
corresponding to given POHC spiking and DRE measure-
ments could lead to more successful trial burns that could
account for modifications of the thermal stability scale for a
given incinerator.
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