Combustion, Explosion, and Shock Waves, Vol. 38, No. 4, pp.

401408, 2002
Investigation of Heterogeneous Combustion
and Gasication of Carbon and Solid Fuel (Review)
UDC 662.61; 662.87 E. S. Golovina
1
Translated from Fizika Goreniya i Vzryva, Vol. 38, No. 4, pp. 2534, JulyAugust, 2002.
Original article submitted May 15, 2001.
A review of literature data is presented on experimental and theoretical investigations
of carbon and solid-fuel gasication in various gas media at high temperatures (up
to 1373 K). Methods of experimental and theoretical investigations are described.
A theoretical formulation of the problem of nonstationary gasication of carbon is
presented. The value of the real kinetic constant of carbon gasication by carbon
dioxide is given.
Key words: carbon, carbon dioxide, active areas, nonstationary gasication, kinetic
constant.
Some new approaches to studying the mechanism
and laws of heterogeneous reactions of combustion and
gasication of carbon and solid fuel have been devel-
oped.
Within the framework of the diusion-kinetic the-
ory of heterogeneous combustion and gasication of car-
bon and fuel, the laws of the process were deduced from
the behavior of the gas phase only [14], whereas the be-
havior of the solid phase, in addition to the gas phase,
is taken into account in the current studies. For this
purpose, the notion of active surface areas (ASA) or a
more extended notion of reactive-active surface areas
(RSA) is introduced, which describes the active sur-
face entering the reaction. The reactive-active surface
area is determined by the concentration of active carbon
atoms on which a carbonoxygen complex is formed; de-
composition of this complex yields a gaseous product.
Boundaries of the basis plane and defects of the struc-
ture inside this plane are referred to active areas (active
surface).
The reactive surface is determined by methods
of chemisorption and desorption, more exactly, the
method of instantaneous nonstationary kinetics and the
method of temperature-programmed desorption.
The consumption of the substance per unit time
normalized to the reactive-active surface or, otherwise,
to the number of reactive-active atoms, determines the
true reaction rate.
The notion of an active surface was introduced by
Leine et al. [5] in the 1960s, but this notion has been in
1
Krzhizhanovskii Energy Institute, Moscow GSP-1, 117927.
active use only since early 1980s. The papers [57] are
of the greatest interest from this new point of view.
1. The experiments of [5] were performed with
gasied soot by means of oxidizer chemisorption at
low temperatures and pressures. The specimens were
preliminary prepared to determine further the overall
active surface area (ASA) and the total surface area
(TSA). The specimens made in the form of a layer of
gasied soot interacted with oxygen under kinetic con-
ditions at a temperature of 625

C to dierent degrees of
conversion (from 0 to 35%). As a result, specimens with
dierent numbers of active surface areas were obtained.
These specimens were heated in vacuum to 950

C dur-
ing three hours to remove the oxide formed.
The total surface of the specimens obtained was
determined by the BrunauerEmmetTeller (BET)
method. Chemisorption of a CO molecule was per-
formed later on this surface. The overall active surface
area of such specimens was determined from the amount
of oxides on the surface, which were formed during 24 h
under chemisorption at a temperature of 300

C and a
pressure of 500 m Hg. At this temperature, gaseous
oxides are not formed, and only surface complexes are
formed. The resultant complex was converted back to
the form of CO and CO
2
at T = 950

C and recalcu-
lated per atom of carbon. It was admitted that the
complex exists on one carbon atom located in the plane
(100). This means that the carbon atom occupies an
area of 8.3

A. The gas analysis was performed using a
mass-spectrometer.
0010-5082/02/3804-0401 $27.00 c 2002 Plenum Publishing Corporation 401
402 Golovina
TABLE 1
Degree of entrainment
K

i
, 10
6
sec
1
m
2
(BET) K
i
, 10
3
sec
1
m
2
(unoccupied ASA)
K

O
2
K

CO
2
K

CO
K

C
K
O
2
K
CO
2
K
CO
K
C
0 5.2 2.4 2.7 5.1 9.8 4.8 5.4 10.2
3.3 11.0 3.2 9.0 12.2 5.1 1.4 4.3 5.7
6.4 16.3 3.7 20.1 23.8 4.5 1.1 5.7 6.8
8.5 21.3 4.5 26.5 31.0 5.0 1.0 6.0 7.0
14.4 27.4 6.0 33.1 39.1 4.5 1.0 5.9 6.9
20.8 34.4 7.1 38.0 45.1 4.9 0.9 5.4 6.3
25.8 39.8 9.2 48.8 58.0 4.8 0.9 5.9 6.8
34.9 40.7 11.0 59.1 70.1 4.9 1.0 5.8 6.8
Then, experiments were performed to determine
the reactivity of these specimens at T = 575, 625, and
675

C and a partial pressure of oxygen equal to 39 m

Hg. The experiments were short-time, and the entrain-
ment rate was 0.1%. Therefore, the total surface area
measured by the BET technique and the overall active
surface area increased insignicantly.
After determining the reactivity of the specimen at
the temperatures mentioned above, the specimen was
heated in vacuum up to 950

C to desorb stable oxygen

complexes. Based on the material balance of desorbed
products, the number of oxygen complexes was found.
Based on these data and results obtained for the
total reactive surface, it was possible to determine the
number of free places on the surface and, thus, the reac-
tive surface area RSA and the unoccupied surface, i.e.,
RSA=TSA (total surface) ASA (occupied surface).
The results obtained show that the initial total sur-
face area (TSA) measured by the BET technique was
76 m
2
/g, whereas the active surface area (ASA) of the
initial specimen was only 0.29% of TSA. After the re-
action with T = 625

C and 35% degree of conversion,

TSA was 128 m
2
/g, and ASA was 4 m
2
/g. This means
that ASA increases by a factor of 18, whereas TSA is
only doubled.
Based on these data, the constant K
O2
of the rate
of consumption of O
2
and formation of CO and CO
2
was calculated:
using the equation

dP
O2
dt
= K

(P
O2
)TSA (1)
for the case of ASA determined by the BET technique;
using the equation

dP
dt
= K(P)ASA(1 ) (2)
if the reactive-active surface RSA was chosen. Here is
the degree of surface covering, i.e., ASA(1 ) = RSA.
The rst-order reaction was chosen. The gaseous
products (CO and CO
2
) are formed from an unstable
oxide; the rate of their formation is decelerated by a
stable oxygen complex on the active surface of carbon.
The rate constants for reactions of graphitized soot
and O
2
for T = 625

C and dierent degrees of conver-

sion, which are normalized to TSA determined by the
BET technique and to the unoccupied surface are listed
in Table 1.
The rate constants obtained using Eq. (1) increase
monotonically with increasing degree of conversion of
graphite. Vice versa, the rate constants determined
by Eq. (2) are unchanged for degrees of conversion of
3.334.9%.
2. The paper of Lizzo et al. [6] became famous be-
cause of the RSA investigation technique and the results
obtained. The authors posed the problem of determin-
ing the reaction rate with a varied degree of conversion.
The main expression for the kinetics of gasication
of char carbon in O
2
, CO
2
, or H
2
O were taken in the
form
r
A
=

s
aR
sp
M
C
= K

C
AS
, (3)
where
s
is the density of carbon, a is the stoichiometric
coecient, R
sp
[h
1
] is the specic rate of gasication
measured, M
C
is the molecular mass of carbon, and
C
AS
is the concentration of the gaseous reagent on the
reactive surface.
The specic rate of gasication was found by the
formula
R
sp
=
1
1 X
C
dX
C
dt
[h
1
],
where X
C
is the degree of carbon conversion:
X
C
=
(m
CO
m
C
)
m
CO
(m
C
is the dry mass without ash). Then, we have
Heterogeneous Combustion and Gasication of Carbon and Solid Fuel 403
dX
C
dt
= R
sp
(1 X
C
) = K

C
AS
M
C

s
a
(1 X
C
)
= K

C
AS
(1 X
C
).
If the process is controlled by desorption (zeroth
order of the reaction) or the partial pressure of the gas
is constant (excess of the oxidizer), the concentration
of the gaseous reagent on the reactive surface is deter-
mined by the chemisorption isotherm
C
AS
= KC
ES
,
where C
ES
is the concentration of active carbon on the
reactive surface [mole of reactive carbon/total number
of carbon moles]. Then, we have
dX
C
dt
= KC
ES
(1 X
C
)
or
dX
C
dt
1
1 X
C
= KC
ES
= R
sp
.
Hence, the constant K = R
sp
/C
ES
[h
1
] should be a
function of temperature only and should not depend on
the type of carbon, temperature processing (pyrolysis),
and degree of conversion. Only in this case can the time
necessary for total or partial gasication be obtained by
integrating the expression, i.e.,
t =
1
K
1
_
0
dX
C
C
ES
(1 X
C
)
.
For integration, one has to know the relation between
the reactive surface of carbon determined via C
ES
and
the degree of its conversion: C
ES
=RSA [m
2
/g or
(mg C)/(g C)].
Thus, to determine K, one has to know C
ES

RSA.
For this purpose, we posed the problem of direct ex-
perimental determination of the reactive-active surface
RSA. Two methods were recommended: the method of
instantaneous nonstationary kinetics and the method of
temperature-programmed desorption.
Let us discuss the rst technique. A xed layer with
an initial mass of 2070 mg and a particle size smaller
than 75 m was gasied. A quartz ow reactor 20 mm
in diameter was used. The test gas was carbon diox-
ide. Char of bituminous coal, Saransk coal, and lignite
was chosen for the experiments. Prior to the experi-
ment, the layer was heated in chemically pure nitrogen
to 1173 K, and then it was cooled to the temperature of
the experiment. After that, gasication in CO
2
at nor-
mal pressure to dierent degrees of conversion occurred.
The products were analyzed using the Beckmann tech-
nique. The specic rate of gasication was determined.
As a result of the experiments, specimens with dierent
Fig. 1. Desorption of CO after completion of gasication
of CO2 +C.
degrees of conversion were obtained. Short-time exper-
iments on determining RSA were performed with these
specimens as follows. After insignicant gasication in
CO
2
(the degree of entrainment was 0.1%), the ow of
CO
2
was replaced by a ow of chemically pure nitrogen
(200 cm
3
/min) at the reaction temperature. The in-
stantaneous continuous decrease in the CO content was
analyzed by the Beckmann technique.
A typical course of the reaction for the char of bi-
tuminous and lignite coals is shown in Fig. 1. The area
under the curve determines the active surface of the re-
acting specimen for a given degree of conversion.
The second method (temperature-programmed
desorption) was also used in experiments with a xed
layer of char of the same coals in a CO
2
ow at T = 575,
625, and 650

C. The products were analyzed on a mass-

spectrometer.
After the reaction to a desired degree of conversion,
the specimen of mass of 200400 mg was cooled down
to 393 K in the reacting gas, and then the specimen
was frozen (it is better to freeze the specimen in
an inert rather than in the test gas). The remaining
CO
2
was removed from the system by high-purity ar-
gon. Then, the specimen was heated in an argon ow
with a constant heating rate of 5 K/min up to 1273 K
and retained under these conditions for two hours for
complete desorption of CO and CO
2
. These spectra
yielded the total surface and the total C O complex
formed during gasication.
Then, the stable intermediate oxide was deter-
mined. The following mechanism of the reaction was
chosen:
C
f
+ CO
2
C(O) + CO,
C(O) C O,
C(O) CO + C
f
(C
f
is the carbon contained in the fuel). It was ad-
404 Golovina
TABLE 2
Total, Stable, and Reactive C O Complexes Formed on Char Partly Gasied in CO
2
X
C
Total C O complex, Stable C O complex, RSA, Fraction of RSA in the total
(mg C)/(g C) (mg C)/(g C) (mg C)/(g C) C O complex,%
Bituminous coal (1093 K)
0.10 12.7 7.3 5.4 42.5
0.35 23.9 16.7 7.2 30.1
0.80 72.4 63.1 9.3 12.8
Saransk char (1133 K)
0.12 2.4 0.4 2.0 83.8
0.24 2.7 0.5 2.2 81.5
0.47 4.3 0.7 3.6 83.7
0.84 6.7 1.3 5.4 80.6
Lignite (953 K)
0.14 34.7 23.1 11.6 34.0
0.48 45.2 23.3 21.9 48.2
0.87 80.9 44.1 36.8 45.5
mitted that the stable complex is in equilibrium with
the intermediate one. After gasication in CO
2
(degree
of entrainment of 0.1%) at a specied temperature and
degree of conversion, an inert gas ow was injected to
desorb the stable intermediate oxide C O formed dur-
ing gasication.
The data obtained for the total and stable com-
plexes allowed us to nd the reactive-active complex:
RSA = (total C O) (stable C O).
The change in RSA versus the degree of conversion
was determined in the experiments. The total, stable,
and reactive-active complexes for char partly gasied by
carbon dioxide are compared in Table 2.
3. Much attention is paid to determining active
reaction sites and true kinetic constants in the Ger-
man school (Karlsruhe University [7] and others). Their
principal viewpoint is that the concept of active sites for
leading heterogeneous reactions has been reliably con-
rmed, and the true kinetic characteristics and rates of
heterogeneous combustion and gasication can be de-
termined from these positions only.
In their experimental studies, Fritzland and Hut-
tinger [7] followed the mechanism
C() + CO
2
k
1

k
1
C(O) + CO,
C(O)
k
2
C() + CO.
The test results show that the heterogeneous reac-
tions C+CO
2
can be studied only by investigating the
behavior of surface oxides, which can potentially enter
the reaction on ASA; the true reaction rate is indepen-
dent of the partial pressure of CO
2
and degree of con-
version. The authors conrm that the true reaction rate
does not depend on the type of carbon in the absence
of catalytically active dopes either.
4. The reference data on heterogeneous gasica-
tion show that the large scatter of kinetic characteris-
tics of Russian coals, which reaches several orders of
magnitude, is a consequence of their determination by
normalization of the mass of the reacted fuel or carbon
per unit time of gasication to the initial mass or ini-
tial surface rather than to the reactive-active surface.
An appropriate classication of these data is an impor-
tant applied and scientic problem. Determination of
true kinetic characteristics requires, rst of all, determi-
nation of the true reactive surface for a given reaction
(C+CO
2
+O
2
and C+H
2
). These data for the reac-
tion C+CO
2
can be found in [8]. We recall that the
following relation was obtained for the constant of gasi-
cation:
K
g
= 10
12
exp
_

91,000
RT
_
[sec
1
].
For certain fuels, this general information is extremely
necessary for the norms of calculating boiler units. Con-
struction of the nonstationary diuse-kinetic theory of
combustion is also impossible without these data.
Khitrin [9] proposed a formulation of a nonstation-
ary diuse-kinetic problem. Nevertheless, taking into
account the behavior of the solid phase in the reaction
Heterogeneous Combustion and Gasication of Carbon and Solid Fuel 405
reduced to allowance for density and porosity of reacting
coal, which, as is shown above, does not allow one to de-
termine the true kinetic characteristics. Therefore, the
problem posed in [9] requires new consideration, which
implies that the system of equations that describe the
process should take into account the true reactive sur-
face and the true fraction of the material participating
in the reaction in various regimes; the primary need is
the determination of the functional relationship between
the number of active sites and the degree of conversion
of the solid phase, i.e., the dependence of the number of
active sites on the degree of conversion: C
V
f(X
C
).
This, in turn, allows one to nd the relationship between
the rate of the process and the degree of conversion:
K
g
=
1
1 X
C
dX
C
dt
= KC
V
.
Such a formulation of the nonstationary problem is
given below (see the scientic report of Energy Institute
No. 4, 1997 written by E. S. Golovina).
5. Gasication of carbon (fuel char) with allowance
for the conversion of the solid phase is a nonstationary
diuse-kinetic problem.
A spherical coal particle of radius R reacts with a
CO
2
ow. The kinetic regime and molecular transfer of
CO
2
are implied. For the rst-order reaction in the gas
and solid phases, the reaction rate is
K = KC
V
C
_
mole
cm
3
sec
g
g
_
,
where K is the reaction rate constant [sec
1
], C
V
is
the number of active sites of carbon [gram of reactive-
active carbon/gram of the total carbon in the specimen],
and C is the concentration of the gas phase [mole/cm
3
],
or the concentration of the gas phase on the reactive
surface [mole of the gas/mole of carbon]. For the zeroth
and pseudozeroth orders (excess of the oxidizer and high
pressures), we have
K = KC
V
_
g/(g sec)

.
According to the oxygen-exchange mechanism of
the reaction, we have
C + CO
2
C(O) + CO, (a)
C(O) CO, (b)
C(O) C(O), (c)
where the intermediate oxide C(O) may be stable (a) or
may form a gaseous product (b). The rate of the process
is determined by the amount of the gaseous product
formed (CO).
Diusion in the free space to a sphere of radius
r = R under nonstationary conditions in the absence of
secondary reactions in the gas phase, which is observed
in our case, is described by the equation
C
t
= D
12
_

2
C
r
2
+
2
r
C
r
_
,
where
D
12
=
2.63 10
3
_
T
3
(M
1
+ M
2
)/2M
1
M
2
p
2
12

12
T

12
is the coecient of binary diusion, p is the total pres-
sure [atm], T

12
= kT/
12
(k is the Boltzmann constant),
M
1
and M
2
are the molecular masses of the components
(in our case, CO
2
and CO),
12
and
12
/k are the pa-
rameters of potential energy of molecules 1 and 2, and

12
is the interaction potential.
If the micropores of a porous body are in operation,
the diusion coecient should also reect the Knudsen
ow. Then the diusion coecient is determined by the
expression
D
e
=

1
1/D
Kn
+ 1/D
12
,
where D
Kn
= (2/3)r
p
_
8RT/M (r
p
is the pore radius
and M is the molecular mass of a component), is the
porosity, and is the sinuosity coecient. For the inter-
nal volume of a particle, diusion of CO
2
is described
by the relation
C
i
t
=

r
(D
1,2
i
(X
C
))
C
i
r
+
2
r
D
1,2
i
(X
C
)
C
i
r
K
i
C
V
C
i
,
where C
i
is the concentration of CO
2
in the solid phase
[mole/cm
3
], C
V
is the number of active sites of carbon
[g/g], K
i
is the reaction rate constant [sec
1
], D
i
=
D
12

2
, and D
12
is the diusion in the free space; accord-
ing to the data of [10], D
i
= 2.2 10
3
_
T/T
0
_ _
cm
2
/sec

for = 0.2.
For rst-order reactions in each component, the
change in the degree of conversion X
C
(ow rate of the
solid phase) is found by the formula
X
C
t
= K
i
C
V
C
i
(1 X
C
)
M

[sec
1
],
where M is the molecular mass [g/mole] and is the
density [g/cm
3
] [M/ is measured in (g/mole)(cm
3
g)],
and C
i
M/ is the dimensionless concentration. For the
zeroth order in the gas component, we have
X
C
t
= K
i
C
V
(1 X
C
) [sec
1
].
The specic rate of gasication is
1
1 X
C
dX
C
dt
=
dm
C
dt
1
m
C
= K
g
,
where
K
g
=
1
m
C
dm
C
dt
, X
C
=
(m
C
)
0
m
C
(m
C
)
0
.
We consider the conditions for the uxes:
(a) D
12
C
r
= KC
V R
C
R
D
i
(X
C
)
C
i
r
for r = R;
406 Golovina
(b) since the reaction temperature is low and the con-
centration of CO is small, we can omit the Stefan ux
and admit the following relation at the boundary:
D
12
_
C
r
_
R
+ D
12
(X
C
)
C
i
r
=
R
dR
dt
;
(c) C
i
= C
iR
for r = R, and the value of C
V
= f(X
C
)
is determined experimentally.
The problem is solved on a computer.
6. Let us consider the latest results that attract
the researchers attention.
These studies are most completely described in pro-
ceedings of international symposia and workshops. We
cannot avoid mentioning the 27th International Sympo-
sium on Combustion (University of Colorado, August
27, 1998) [11] and the XIIth Symposium on Combus-
tion and Explosion (Chernogolovka, September 1115,
2000) [12].
The main direction of papers presented at the
XIIth Symposium in Chernogolovka deals with com-
bustion (heterogeneous and homogeneous). It should
be noted, however, that the Combustion session con-
sidered mainly condensed systems: solid-phase interac-
tion, explosives, and powders. In the present review, we
consider only the traditional technological combustion.
This topic was scarcely represented at the Symposium.
First of all, this is the paper of Babii et al. [13] on
macrokinetic constants of the processes of decomposi-
tion of NO, CO, and H
2
O in a reducing dusty medium
in the course of combustion and gasication of polydis-
perse dust. Babii et al. [13] studied the formation of
NO from nitrogen contained in the fuel, determined the
macrokinetic constant of NO decomposition on coal
K
NO
= 24.3 10
3
6344
T
_
m
3
kg sec
_
,
and showed that the laws of decomposition are inde-
pendent of the type of coal. The process of reduction of
CO
2
and H
2
O on coal was also considered, but the rate
constants for these processes were not given, though the
laws of gasication for these reactions were presented for
temperatures of 13002100 K.
For the purpose of obtaining gas synthesis, Borisov
et al. [14] considered partial oxidation of hydrocarbon
gases, methane, and a mixture of gases close to hydro-
carbon raw materials (CH
4
, C
2
H
2
, and C
3
H
8
). The
process allows one to obtain gas synthesis, a signicant
amount of heat is released thereby, and the authors re-
fer it to combustion processes. The authors performed
a thermodynamic and kinetic modeling of such a mix-
ture using the detailed mechanism of high-temperature
homogeneous reactions, which was proposed in [14].
The calculations were performed for an air mixture
with pressures of 525 atm, temperatures of 300900 K,
and air-excess coecients of 0.30.56. The calculations
showed that organization of the process in a real cham-
ber with an initial temperature of 900 K requires the
air-excess coecient to be greater than 0.45. In this
case, the time necessary for the combustion products
to reach the equilibrium composition is 10
2
sec, which
allows one to organize the process in a real combustion
chamber.
At the 27th International Symposium on Combus-
tion, much attention was paid to studying the processes
of ghting against the oxide NO. Thus, Matsunaga
et al. [15] performed an experimental and numerical
study of the inuence of hydrocarbons on NO NO
2
conversion in a ow reactor; the eects of time and
temperature were also examined. Five hydrocarbons
were used methane, ethane, ethylene, propane, and
propene: NO (20 ppm)airhydrocarbon (50 ppm), the
measurement time was 0.161.46 sec, and the tempera-
ture was 6001100 K. It was found experimentally that
ethylene and propane eectively oxidize NO to NO
2
;
methane is less eective; propane yields the best results
at lowest temperatures. It was shown by calculations
that oxidation of NO to NO
2
occurs in the reaction
NO+HO
2
=NO
2
+OH. Hydrocarbons that form the
OH radicals and the O atom in the reaction are the
most eective. Propane yields the greatest conversion
NO NO
2
for the lowest temperatures (this is 600 K in
that paper).
Carlos and Cugel [16] demonstrated the eect of
the particle size and pressure on conversion of nitro-
gen contained in the fuel to NO in the boundary layer
of an individual particle during liberation of volatiles.
The temperature eld inside the particle was nonuni-
form. The inuence of the particle size, fuel type, gas
temperature, and concentration of O
2
was studied. It
was shown that there is a tendency of NO formation
to decrease with increasing pressure for particles 80 m
in diameter burning in a gas that contains 10% O
2
(by
mass) at T = 1350 K. The values of pressure were not
given.
Chambrien et al. [17] considered the reaction
C+NO in the presence of O
2
. The reaction of NO
with pure carbon and amorphous C
13
was studied for
T = 850

C in the presence of O
2
. A preliminary study
showed that some amount of nitrogen from NO remains
on the surface of carbon in the form of the C(N) complex
and plays an important role in the reaction C+NO. The
presence of O
2
signicantly increases the reaction rate
of NO reduction, and accumulation of the C(N) com-
plex on the surface signicantly decreases with increas-
ing concentration of O
2
. The products of the reaction
between the complex C(N) and O
2
at T = 850

C are
N
2
at the early stage and NO at the late stage. Oxygen
Heterogeneous Combustion and Gasication of Carbon and Solid Fuel 407
removes the complex C(N) from the surface of carbon
and forms a gaseous product.
Aarne and Sunberg [18] studied the order of the re-
action NO C upon gasication. Since heterogeneous
interaction of NO and C is an important process in de-
composition of NC during combustion, one has to know
the order of the reaction of NO and carbon for dierent
temperatures and pressures in the kinetic regime. The
authors showed that the order of the reaction increases
from zeroth to rst with increasing temperature. At low
temperatures, the reaction rate is determined by des-
orption and is a weak function of NO concentration. At
high temperatures, this is a rst-order reaction, which
is determined by direct attacks of NO. In the interme-
diate region, the order of the reaction is determined by
the sum of two processes.
Achman and Haynes [19] used the weighting
method to study the charnitrogen reaction upon low-
temperature oxidation at T = 873 K in an oxygen (2%)
and helium environment. The products NO, NO
2
, CO,
CO
2
, N
2
, and HC in the gas phase were determined
by the spectral technique and high-speed chromatogra-
phy. Interaction of char with N yields N
2
with an in-
signicant amount of NO and HCN, which remains ap-
proximately unchanged during combustion. At low tem-
peratures, N
2
O is not formed, and the authors believe
that HCN is the primary product formed upon hetero-
geneous oxidation rather than upon slow or secondary
liberation of volatiles. According to the data of an el-
ementary analysis of partially oxidized char specimens,
nitrogen predominantly remains in char when carbon is
oxidized. The analysis showed that enrichment of char
by nitrogen is a surface eect observed with increasing
content of nitrogen. At low temperatures, enrichment
of char is mainly caused by the increase in the ratio
[NO]/([CO
2
]+[CO]).
Veranth et al. [20] considered the sources of un-
burned carbon in volatile ash obtained in combustion of
nely disperse coal with a low content of oxides NO
x
.
It was found that unburned carbon in volatile ash is
a mixture of coot and char. Laboratory analyses of
the specimens showed that the content of carbon in-
creases with decreasing concentration of NO
x
. The ex-
periments included cases with a high content of NO
x
and four cases with a low content of NO
x
, namely:
1) short stage of combustion (0.5 sec); 2) long stage
of combustion (1.5 sec); 3) combustion with a low con-
tent of NO (slow mixing); 4) stage of afterburning with
the use of carbon as an afterburning fuel. By compar-
ing the main case, where premixed coal and air were
used, with the case of a long (in time) stage of combus-
tion, it was established that NO concentration varies
from 900 ppm to less than 200 ppm, and the content
of carbon in ash increases from 4 to 30%. Volatile ash
at the stage of combustion was a mixture of large sets
of ash, porous char, and spherical particles of mineral
ash, whereas there were no large conglomerates of ash in
the afterburning region. For all laboratory conditions,
the content of carbon in particles of diameters greater
than 10 m was higher than in particles 11.25 m in
diameter.
Matsunaga et al. [15] examined the eect of re-
duction of N
2
O emission from a burning circulating
layer of the fuel by means of injection of a secondary
fuel. The study was performed in a circulating sus-
pended layer in a pilot setup 161 mm in diameter and
6.2 m high. Three types of the secondary fuel (methane,
ethane, and propane) and two injection positions (350
and 1372 mm beneath the liftup). More than 70%
of N
2
O reduction were readily reached by injection of
ethane or propane. With using methane, however, only
30% of N
2
O were reduced because of the incomplete
combustion of methane. The decrease in N
2
O emission
by injecting an arbitrary secondary fuel is always ac-
companied by a small increase in NO
x
emission. Injec-
tion of methane yields the greatest increase in NO
x
con-
centration. Numerical simulation showed than thermal
decomposition of N
2
O is less eective that the reduc-
tion of the content of N
2
O by the mechanism of radical
reactions. The calculation results show that methane is
less eective that ethane for reduction of N
2
O emission.
Feng et al. [21] studied the kinetics of NO reduction
by char. The heterogeneous reaction of NO and char
contained in coal is the basic one both for combustion
and for the processes of purication of the products after
combustion to an admissible level of NO emission. The
study of this reaction is also important for understand-
ing the mechanism of NO formation and decomposition
during coal combustion. Char of dierent types of coals
(from lignite to bituminous coals with a low content of
volatiles) was used in the experiments. The study was
performed in a laminar reactor at T = 7231173 K.
Graphite and char coal were also examined. The tem-
perature necessary for conversion of 50% NO varied
from 870 K for coal to 1100 K for graphite under iden-
tical conditions. For all chars studied, the rst order
in terms of the partial pressure of NO was observed;
the activation energy varied within 100160 kJ/mole at
low temperatures and within 190250 kJ/mole at high
temperatures. The authors believe that the dierence
is explained by the change in the reaction mechanism
or by the stage determining the process. The reactivity
of chars, apparently, depends not only on organic com-
ponents of char but also on the mineral part, rst of all,
on CaO.
408 Golovina
Marinov et al. [22] performed an experimen-
tal study of the inuence of hydrocarbons, reaction
temperature, and time on conversion NO NO
2
in a
quartz ow reactor at atmospheric pressure. Kinetic
calculations were also conducted. Five hydrocarbons
were studied: methane, ethylene, ethane, propane, and
propene. The quantities measured in the experiments
were the concentrations of components in the ow re-
actor for the mixture NO (20 ppm)airhydrocarbon
(50 ppm); the duration of an experiment varied from
0.16 to 1.46 sec, and the temperatures were 6001100 K.
The time evolution of NO, NO
2
, hydrocarbons, and in-
termediate hydrocarbons was evaluated in calculations.
The chemical mechanism included 649 reversible reac-
tions for 126 components. It was found experimen-
tally that ethylene and propane eectively oxidize NO
to NO
2
, and methane is less eective. According to
calculations, all ve hydrocarbons oxidize NO to NO
2
via the reaction NO+HO
2
NO
2
+OH, and addition of
oxidation RO
2
HORO
2
has a negative eect on the pro-
cess. Hydrocarbons that produce highly reactive radi-
cals (i.e., OH and O atom) are most eective. They fa-
vor hydrocarbon oxidation and lead to additional forma-
tion of NO
2
. On the other hand, if a hydrocarbon pro-
duces radicals, such as methyl, that suppress oxidation
by oxygen, then these radicals decrease the content of
NO. Experimental results show that the eciency of
hydrocarbons changes noticeably with temperature and
only in the region of low temperatures; propane is more
eective in the process of conversion NO NO
2
. This
capability is mainly due to hydroperoxipropyl and the
reaction of O
2
.
Certainly, the data in the present review do not ex-
haust all issues of heterogeneous combustion and gasi-
cation. The most important problem is determining
the true kinetic constants for chars of Russian coals and
composing a complete table of these data.
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