Heat Transfer Limitation Calculations for Methanol to

Aromatics on Ga-modified HZSM-5 at 673 K

Notations
q: heat of reaction (J/mol CH3OH)
: reaction rate per unit particle volume (mol/m3 sec)
: bed void fraction (unitless)
: reaction rate per unit bed volume (mol/m3 sec) = (1-)
rp: catalyst pellet radius (m)
: effective particle thermal conductivity (W/m K)
T0: temperature of bulk fluid (K)
R: gas constant (J/mol K)
E: activation energy of toluene methylation (J/mol)
h: gas-solid heat transfer coefficient (W/m2 K)
Biotw: thermal Biot # at the wall (hwdp/ke)
hw: wall heat transfer coefficient (W/m2 K)
dp: catalyst pellet diameter (m)
ke: effective bed thermal conductivity (W/m K)
Tw: wall temperature (K)
R0: reactor tube radius (m)

Parameters:
8CH3OH p-xylene + 8H2O + 3H2
q

rp

T0
E
Rep
Nu
h
ke
Tw
R0
hw

233.3

kJ/mol (considering heats of formation of all the species at 673K, using

the NIST database)
4.2
mol/m3 sec, calculated from the 4% conversion data
7.1
mol/m3 sec, considering a bed void fraction of 0.4
150
m
1
W/m-K (Ref: Coquil et al., J. Applied Physics, 108, 2010)
673
K
187
kJ/mol (Ref: Arstad et al., J. Phy. Chem. B, 106, 2002)
1.6
dpv/
0.12
(0.07 Rep, for low Reynolds number) (Ref. Berg et al., Chem. Eng. Sci.
30, 1975)
394.2
W/m2K
3.5
W/m-K (Ref: Hamdhan & Clarke, Proceedings World Geothermal
Congress, 2010)
673
K
0.003175 m
20
W/m-K (Ref: mace.manchester.ac.uk)

Calculations
Criterion for the absence of intra-particle temperature gradients (Ref: Mears D.E., J. Catal. 20,
1971):

qrp 2
RT0
< 0.75
T0
E
7.33 10-3 < 0.0224

Hence, measured reaction rates should not be affected by intraparticle temperature gradients

Criterion for the absence of inter-phase (gas-solid) temperature gradients (Ref: Mears D.E., J.
Catal. 20, 1971):

qrp
RT0
< 0.15
hT0
E
1.9 10-3 < 4.5 10-3

The number on the left hand side is slightly less than the number on the right hand side so the
measured reaction rates could be affected by interphase temperature gradients (within the
accuracy of calculation of h); increasing gas flow rate (thus in affect increasing the h) or
decreasing the pellet size would help this criteria.

Criterion for the absence of inter-particle temperature gradients (Ref: Mears D.E., J. Catal. 20,
1971):
q R 0 2
RTw /E
< 0.4
k e Tw
[1 + 8rp /R 0 (Biot)w]

4.2 10-3 < 1.2 10-2

Given the accuracy of the parameters involved, it seems that the reaction rates should not be
affected by inter-particle temperature gradients, although increasing the bed thermal conductivity
(ke) by adding more sand would help strengthen the case.

Conclusions
1. The measurements are likely not affected by intra-particle temperature gradients
2. The calculations for interphase temperature criterion show that the reaction rate
calculations could be affected by heat transfer limitations, decreasing the average pellet
size or increasing the gas flow rate, thus increasing the heat transfer coefficient should
help satisfy the criteria
3. The inter-particle temperature gradients also dont seem to affect the rates, given the
accuracy of the data. But, in general adding more sand or increasing the bed thermal
conductivity (ke) should keep this criteria under control.