Chemical Engineering Science, Vol. 41, No. 4. pp. 877-882, 1986. ooo9-2509186$3.00 + 0.

00
P&ted in Great Britain. @ 1986. Pergamon PressLtd.

PROPAGATION OF REACTION FRONTS IN EXOTHERMIC

HETEROGENEOUS NONCATALYTIC SYSTEMS SOLID-SOLID AND SOLID-GAS

V. Hlavacek, J. Puszynski*, J. Degreve and S. Kumar

Department of Chemical Engineering

State University of New York at Buffalo
Buffalo, New York 14260, U.S.A.

*Technical University, Wroclaw, Poland

ABSTRACT

Exothermic heterogeneous noncatalytic reactions of the type solid-solid and solid-gas can be effi-
ciently used to produce new type of materials. The idea of the process is based on the self-
propagating reaction waves in the reactant mixture. Modeling of the process is suggested. com-
parison of experimentally observed phenomena with theoretical supercomputer calculation is pre-
sented.

KEYWORDS

Exothermic noncatalytic reaction; synthesis of ceramic materials; supercomputer calculation.

INTRODUCTION

There exists an important class of heterogeneous noncatalytic reactions of the type solid-gas and
solid-solid which are accompanied by a substantial generation of heat. The most important are
oxidation of metals and nonmetallic compounds, direct reaction of nitrogen or hydrogen with cer-
tain metals, synthesis of carbides, borides, sulfides or sllicides of metals (from pure compo-
nents), reduction of metallic oxIdes by carbon or aluminum, synthesis of intermetallic compounds
(e.g. Ni-Al), combustion of solid propellants and many others. In this paper, we will address
ourselves to reactions occurring without gas phase formation. Many of these reactions are of
major technological importance. Unique properties of various boron, carbm and nitrogen ceramics
will lead to increased or new applications in the area of refractories, abrasives, E-M windows,
anti reflection coatings, electronic devices, nuclear materials, bearings, military ceramics, heat
engines and energy storage.

The exothermic noncatalytic reaction can proceed through the reacting mixture in a uniform way and
the concentration of the components at any instant is almost the same everywhere (kinetic or
"sintering" regime). However, if the system was locally ignited by external means, a steep
reaction front can propagate through the mixture. Evidently, the latter phenomenon is closely
related to flame propagation in gaseous mixtures and is frequently referred to as the self-
propagating regime. Synthesis of borides and carbides of transition and rare earth metals can be
performed both in sintering and self-propagating regimes. The synthesis in the sintering regime
requires a substantial energy input, high reaction temperature and a long reaction time. On the
other hand, the self-propagating synthesis calls only for a short range initial energy input.
The reaction is self-sustaining owing to the high values of the activation energy and heat of
reaction.

MODEL FORMULATION

An assumption is made that a heterogeneous reaction occurs between two solid materials, S and M.

S(s) + M(s) + P(s)

or between S and gaseous A

S(s) + A(g) + P(s)

and that the reaction rate can be described by an integer power kinetics.

Following physical assumptions have been made:

1) A heterogeneous mixture of solid powders S and M behaves as an isotropic homogeneous system.

2) The temperature dependence of the reaction rate constant can be expressed in the Arrhenius
form. 3) Heat conduction in the solid phase can be described in terms of the Fourier law.
4) Mass diffusion of the solid reactants or products does not occur. 5) All physical properties
(density, heat capacity, effective thermal conductivity) are assumed constant. 6) The reaction

x77
878 V. HLAVACEK et al. G-l

is not accompanied by melting effects. 7) The radiation effects inside the porous layer do not
play an important role. Heat loss from the system can be described by an effective linear driving
force. 8) The reactant M is in excess so that the reaction process can be considered of the
first order with respect to S.

Gas-solid noncatalytic reactions of the type S(s) + A(g) + P(s) can be handled in a similar way if
diffusion effects are unimportant. This is satisfied for high pressure systems and thin layers of
S. The gas-solid reaction will be studied in two configurations: a) flow system, b) filtration
regime. (See Fig. la and lb.) In a flow system the gas flows over the powdered material, and the
reaction is ignited at the reactor inlet. Initially the reaction front propagates in the same
direction as the flowing gas. For a filtration regime arrangement, gas is filtered towards the
reaction zone and initially the front propagates against gas flow direction. Filtration regime
is important for synthesis of ceramic materials which can melt during the exothermic process.

The governing partial differential equations of parabolic-hyperbolic type are described elsewherel.
Because of high values of both heat of reaction and activation energy very steep reaction fronts
may occur. Within the reaction front the solution varies rapidly over a vary thin region. The
corrugated "boundary layers" on concentration and temperature profiles represent a very difficult
numerical problem. High-order compact finite-difference scheme with automatic time step control
was adopted. The calculations were performed on supercomputers Gray-1 (Los Alamos) and Cyber
CDC 205 (Univ. Purdue). The results were processed by a color graphic package DI-3000.

Typical values of physical chemical parameters are reported in Table 1.

EXPERIMENTAL

Experiments were performed in a vacuum chamber which was equipped with leadthroughs for thermo-
couples, vacuum gages, inert gas valve, electrodes and resistor holding assembly, sample supporting
rod and exhaust valve. The thermocouple wires are connected to a microcomputer through an analog
to digital convertor interface to record the temperature during ccxnbustion of the samples. The
electrodes are attached to a transformer-rheostat combination to generate and control a high
current. The experiments involved igniting ccmpact reactant pellets at one end with a high
current and monitoring the propagating fronts by a video assembly. Axial temperatures in a sample
were recorded by thermocouples. The velocity of a constant pattern propagating wave was deter-
mined by analyzing video recorded data. The velocity and temperature data are used to estimate
kinetic parameters.

RESULTS AND DISCUSSION

Solid-solid Systems

Constant pattern profiles are traveling waves propagating through the system with con-
stant velocity. For adiabatic conditions, Fig. 2 displays a system featuring constant pattern
profiles. After one end of the cylindrical sample was brought to a sufficiently high temperature,
the exothermic reaction generates enough heat to be self-sustaining. There is a heating-up time
associated with an insignificant degree of conversion of the solid reactants (cf. profile A). For
higher values of the activation energy E, the concentration profiles are steeper; for low values
of E, the propagating wave degenerates. The ccmstant pattern profile regime can also exist for a
nonadiabatic case. With the increasing value of the external cooling parameters, both the velocity
of the front and the hot spot temperature decrease. For high values of the cooling parameter the
reaction can still be ignited, but far enough from the external energy source an extinction
process occurs.

For supercritical conditions oscillatory fronts can be observed. A typical behavior in this region
is shown in Fig. 3. The temperature can overshoot the adiabatic temperature and at these high
temperatures the solid material is completely burned. This is the onset of the cooling cycle, the
temperature drops well below the adiabatic temperature and the fresh unreacted material is slowly
preheated. After the temperature of the fresh material reaches certain critical value, a new
ignition process occurs and the temperature in the reaction front exceeds again the adiabatic
temperature, etc. With increasing value of the activation energy, the profiles become very steep.
In the nonadiabatic case, an extinction of the oscillatory regime may occur. For low values of
the heat loss parameter, oscillations show similar behavior to that for the adiabatic situation.
However, for the nonadiabatic case, the maximum temperature in the reaction front can be signi-
ficantly higher. This can be easily explained since there is a lower conversion in the preheating
zone so that at the moment of ignition more solid material can react in the very narrow reaction
front. Oscillation and extinction phenomena are highly undesirable in practical applications
because of nonuniform product properties resulting from melting effects and/or thermal stresses.
To avoid these phenomena, the solid mixture should be preheated and ignited.

For a two-dimensional model, multiplicity of propagating fronts has been found. An oscillatory
front can exist which does not show any symmetry breaking in two other space dimensions. We will
call this wave a ZD-piston front (see Fig. 4). However, if the front hits a local irregularity,
the one-dimensional character of the front is lost and several two-dimensional (or three-
dimensional) corrugated reaction fronts may appear. For a case of a transverse traveling wave at
the reaction front a fingering wave results. If a transverse traveling wave exists at the reac-
tion interface a spinning (or helical) wave can be observed (cf. Fig. 5). For identical parameter
values and boundary and initial conditions, different kind of fronts (piston, fingering, rotating,
G-l Propagation of reaction fronts 879

erratic) may result, if different perturbations have been imposed. The selection of a prevailing
regime depends strongly, among other factors, on the heterogeneity of the system.

The exothermic solid-solid reaction is supposed to occur in a porous cylinder, initially comuosed
of the powders of S and M. At the time t = 0, the initial temperature To is suddenly increased
at the end of the cylinder to Tie This temperature is high enough to ignite the mixture. Differ-
ent reaction fronts, experimentally observed for various systems, are shown in a color movie.
Following fronts have been found: constant pattern profiles, oscillatory fronts, rotating fronts
and erratic behavior. Extinction and ignition processes are also shown in the movie.

Gas-solid Systems

Constant pattern profile regime is a typical regime arising for flow gas-solid systems2. The
reaction front propagates downstream and consumes completely all solid material. Under certain
cirumstances the temperature in the reaction zone keeps increastng with time as the front propa-
gates downstream. This effect is caused by a dynamic feedback of heat towards the incoming gas.
Similar effects were also observed for a rapidly deactivating bed3. Dynamic overshooting of adla-
batic temperature results in melting of the solid reactants and such regime should be avoided.
Complicated wave pattern results for systems with reacting gas shortage (Fig. 6). Preheating
temperature wave propagates downstream and reaction is ignited at the reactor exit. The reaction
front propagates upstream, however, the solid material is not completely consumed because of
shortage of reacting gas. After the reaction front reaches the reactor inlet, a new downstream
propagating wave occurs which completes the reaction process.

Similar situations can be observed for a filtration regime. The backward moving front does not
consume the solid reactant completely, and a forward moving wave appears consuming the unreacted
part of the solid reactant (cf. Fig. 7).

BEFERENCES

1. Puszynsky. J., J. Degreve, S..Kumar and V. Hlavacek (1985). Proc. of the Sumner AMS-SIAM
Conference (Ithaca).

2. Olson, K. E., D. Luss and J. R. Amundson (1968). IEC Proc. Des. Devel., 7, 99.

3. Blaum, E. (1974). Chem. Engng. Sci., 29, 2263.

TABLE1 Physico-chemical Parameters of Certain Exothermic Noncatalytic Reactions S-S and S-G

E(kJ/mol) (-AH)(kJ/kg) AT,d(K) B Y

Ti + 2B+TiB2 318.4 1034.9 2700 0.091 0.10

Hf + 2B+HfB2 398.1 1676.0 3520 0.08 0.087

2Hf + N2+2HfN 238.8 1915.5 3950 0.138 0.140

Here E is activation energy, (-AH) heat of reaction, AT,d adiabatic temperature rise, Y dimen-
sionless heat release parameter, 8 dimensionless activation energy.
880 V. HLAVACEK etal. G-l

a 6
Fig. 1. Reaction between solid phase and gas a) flow-system b) filtration regime; l-gas,
a-reactor, 3-reaction product, 4-unreacted component. 5-reaction zone, &heating element.

Fig. 2. Solid-solid reaction. Constant pattern profiles.

8.
0

4.

-4.

-8.

,,,n

Fig. 3. Solid-solid reaction. Fig. 4. Solid-solid reaction.

Oscillatory lD-fonts. ZD-piston front.
882 V. HLAVACEK et al. G-l

Fig. 7. Gas-solid reaction. Filtration regime.

profiles of temperature, concentration, density and pressure.