Chemcd Englneenngbc~ence,1058, Vol 8, pp 284 Lo 286 rergamon Pre.

ss Ltd

The temperature produced by heat of reaction in the interior of

porous particles

CHARLES D. PRATER
Socony Mobd 011 Company, Inc Research and Development Laboratory l’aulsboro, New Jersey, IJ.S A

fRecewed9 Sep&9&er 1957)

Abstract-Heat of reactron ~111 cause a temperature drfference to occur between the tnslde
and boundary of a porous partmle durmg an Internal reactron An equatmn IS derrved relating
tlus temperature difference to the reactant concentratron dfference, and It IS shown to be
mdependent of the kmetlcs of the reactron and of the partmle geometry Examples are grven of
the apphcatron of thrs equatron to yclohexane dehydrogenatron and catalyst regeneratron.
R&mm&-La chaleur de reactron prodmra une difference de temperature entre la surface lumte
et l’mteneur de partmules poreuses, au tours de r&ctxons au sem de cette partrcule Une equation
est obtenue etabhssant la relation entre cette dlfferenee de temperature et la dlff’trence de concen-
tratron des composes reagrssant Elle est lnd~pen~n~ de la cmetrque de la r&u&on et de la
forme geometnque des partzcules Les exemples d’apphcatron de cette &matron sont don&
pour Is desydrogenatron du cyrlohexane et la regeneratron de eatalyseurs
Zusammenfassung-Die Reaktronswarme erzeugt eme Temperaturdrfferenz zwrschen dem
Inneren und der Aussenselte emes porosen Tedchens wahrend emer mneren Reaktlon Es wnd
eme Glerchung abgeleltet, urn drese Temperatunhfferenz auf dre Konzentrations&fferenz des
Reaktanten zu bezrehen und es wnd gezelgt, dass sre unabhanglg von der Reaktronskmetrk
und der Terlchengeometrre 1st Fur die Anwendung dleser Glelchung werden als Bersprele die
Dehytierung von Cyclohexan und die Regeneration emes Katalysators behandelt

(T - T,) = - yQ (c, - c) (1)

MANY the reactzons whrch occur wlthm porous
of
catalytrc solids have an appreciable heat of
reaction. This heat of reaction wrll give rise to
a temperature drfference between the inside and
boundary of the catalyst particle while the
reaction is proceedmg. An estrmate of the size
of this drfference 1s needed m many catalytic
lnvestlgatlons. A c~~~~ solution of the problem
would grve the temperature as a functron of the
spatial co-ordinates of the particle. To obtain
this, a separate solution is reqmred for each
particle shape, boundary condition and kinetics.
It 1s not possible to obtam such solutions m a
closed form except for certam special cases and,
m general, numerical methods must be used
It ~111be shown that a solution can be obtained
whrch 1s vahd for all kinetics and all partxcle
geometries. This solutron grves the temperature
as a function of the concentration of reactant.
Information has been sacrificed to obtain this
generahty, namely, the temperature as a function
of co-ordmates. This solution 1s :-
where T 1s the centigrade temperature at all
pomts within the pa&& whrch have a concentra-
tion of reactant c (mole/ems)
T, IS the temperature (“C) at the surface of the
particle
c, IS the ~oncentratlon of the reactant at the
surface of the particle (mole/cm3)
AH 1s the heat of reaction (Cal/mole) (negative
values mean exothermlc reactions)
D, IS the effective dlffusrvlty of the part&e
(cm’/sec)
K 1s the thermal conduetlvlty of the partrcle
(cal/sec cm “C)
DAMKOHLER [l] and WHEELER [Zfhave mvesti-
gated the thermal effects m spherzcat part&es
and have obtamed the same equatron for thus
special case. The derivation grven below will
show that the equation holds for particles of
any shape.
The maxrmum possible temperature drfferenc9
 The temperature produced by heat of reaction m the interior of porous particles

between the inside and boundary of the particle

can be obtained at once from this equation. The (5)
maxlmum temperature for a given operating
Let u = AHDJK
condltlon will occur when c has Its smallest
possible value. This will be the concentration Smce TV1s a constant it can be taken under the
of reactant at thermodynamic eqmhbrnun dlfferentlatlon. This gives for equation (4) :
between reactants and products. Equation (1)
1s a useful tool m catalytic research and operations v2 u c_%l!!=o (6)
dt K
since the maximum temperature can be used as a
crlterlon to determine whether a more detailed Equations (2) and (3), which have sources
analysis IS desirable for a particular mvestlgatlon. and sinks of different strengths, have been
Equation (1) IS derived as follows In conven- transformed mto two equations (6) and (5) which
tlonal porous catalyst particles, dlffuslon through have the same sources and smks. This means
the pore structure of the catalyst 1s the only that the difference (f) between 0:c and T must
method operatmg m supplymg reactants to and satisfy Laplace’s equation (V”f = 0). The solu-
removing products from the region of an active tion for equations (5) and (6) 1s then :-
site mthm the particle. Thus, the dlffuslon
equation a-
ac=T+f (7)
The usual boundary condltlon is that the
temperature and concentration of reactant at
the surface of the particle are constants. Let
must be satisfied at all points wlthm the particle. their values be T, and c, respectmely. Then,
In this equation dn/dt IS the rate of disappearance on the boundary, equation (7) becomes :-
of reactant at a given point (moles/set cm”) The
UC, = T.-I-f, (8)
heat produced (or consumed) by the reaction must
be removed (or supplied) to the active site by where f, 1s a constant. Any function which
ordinary thermal conduction processes Therefore satisfies Laplace’s equation m a fnute closed
the thermal equation :- region and 1s constant on Its boundaries 1s
constant m the region. Therefore, f = f, for all
pomts wlthm the particle. Equation (7) now
KV2T--:AHd (3)
at becomes
ac=T+f, (9)
must be satisfied at all points wlthm the particle.
Ehmmatmg f, between equations (8) and (9)
These two equations, with the proper boundary
and usmg the defimtlon of CC,
condltlons, completely determine the tempera-
tures wlthm the catalyst particle. To obtain a
(T - T,) = - AZ De (c, - c) (10)
complete solution for these two simultaneous
differential equations, dn/dt must be known as
As can be seen the derlvatlon 1s independent of
a function of concentration of reactant and as
particle geometry and reactlon kmetlcs.
a function of temperature. In addition, the
geometry of the particle must be known. How-
ever, the path to be followed here m obtaining APPLICATIONS TO CATALYST SYSTEM
our solution does not require this mformatlon. Two examples ~111 be given to illustrate its
Multlplymg equation (2) by + AH/K and apphcatlon to practical catalyst systems. The
dlvldmg (3) by K, first system to be considered will be the regenera-
tion of slhca-alumma catalyst used m Thermofor
catalytic crackmg of gas 011s. This catalyst
1s m the form of slhca-alumma beads contammg

235
 C-ES D. PRATER

10 wt. per cent alumma and with an average neghgble w&h respect to further conslderatlon
particle radius of 0 12 m The beads are gradually of thermal damage to the catalyst.
fouled with carbonaceous materials m the reactor The next reaction to be consldered 1s the
and m 2030 mm require regeneration by burning dehydrogenaCon of cyclohexane over a commer-
m air. Durmg burning, the temperature m the cial platmum-alumma reformmg catalyst. This
kiln may reach ‘760°C It becomes Important to 1s an endothernuc reactlon with a A H of
know how much the temperature wlthm the + 52 54 x lo3 Cal/mole at POO’C. The condl-
beads can exceed the external temperature, tions are 400°C reaction temperature, 4 : 1
because the beads can be damaged by tempera- hydrogen to hydrocarbon ratio and 25 atmos-
tures much m excess of 76O’C. pheres total pressure The values of the constants
Coke burning wlthm catalyst particles differs for this catalyst are -
from the stationary state problem discussed
D, = 15 6 x lo-’ cm/sec2 (cyclohexane at
above m that the reaction zone moves with time
POOYZ)
mto the catalyst. However, it can be shown
that for most cases of mterest equation (1) still K = 5 3 X lOA cal/sec cm “C.
applies. The condltlons for this are (1) that the The value of the eqmhbrmm concentration of
amount of oxygen required to fill the pores of yclohexane 1s calculated from free energy data
the catalyst 1s small compared to that required given by ROSSINI et al. [5]. The calculated
to burn the coke and (2) that the time It takes maximum temperature drop possible 1s found to
for maximum possible transient temperature be 53°C which will be qmte important m kmetlc
differences to decay to a neghglble quantity 1s studies Thus further study to determme the
small compared to the time it takes to burn the actual temperature dlstrlbutlon m the partlcles
carbon on the catalyst. These condltlons are may be desirable.
satisfied for the case to be discussed. The value In the above dlscusslon, the problem of the
of ?e for oxygen at 760°C, determmed by the measurement of the particle boundary tempera-
gas flow method discussed by WEISZ and PRATE~ ture has not been consldered exphcltly. Conven-
PIP is 4 6 x 10-s cm2/sec. The value of K, tionally, the temperature measuring device 1s
taken from the studies of thermal conductlvlty located externally to the particle. The question
of various catalysts by SEHR [4], 1s 8 6 x lOA then arises as to how well the temperature
Cal/cm set “C. The heat of burning (A 2%) 1s measured by the device represents the actual
that observed m practical luln operation and temperature of the particle boundary. A con-
has a value of - 83 x 10s Cal/mole. Equation slderatlon of the particular condltlons exlstmg
(1) then yields a maximum possible temperature m a given experiment 1s needed to answer this
difference of 1 1°C. This temperature rise 1s question.

REFERENCES
r11 DAME~ELER G Z. Phys Che-m 1943A193 16
M WHEELER A Catalyszs Vol. II (Edlted by P H EMMETT) ReInhold Pubhshlng Co , New York 1955

[aI WEISZ P B and PRATER C DC Advanc Catalys 1954 6 143

141 SEHR R A To be pubhshed

161 ROSSINI F D , PITZER K S , ARNETT R. L , BRAUN R M and PIMENTEL G. C. Selected Values of Physwal and
Thermodynamu: Properkes of Hydrocarbons awd Related Compounds Carnegie Press, Pittsburgh 1953

286