Hydrogen Production by the Catalytic Steam
Reforming of Methanol
Part 1: The Thermodynamics
1. C . A M P H L E T T , M . J . E V A N S , R . A . J O N E S , R. F. MANN and R. D . WEZR
Department of Chemistry and Chemical Engineering, Royal Military College of Cmtada,
Kingston, Ontario K 7 L 2 W 3
'I'he thermodynamic equilibria involved in the catalytic
steam reformation of methanol to produce hydrogen have been
examined over the ranges of pressure 101-3040 kPa, temper-
ature 400-700K and water to methanol feed ratio 1.5-0.67.
Four models have been considered based upon possible reaction
products and the equilibrium composition of each model
calculated.
The presence of methane and carbon reduce the quantity
and quality of hydrogen produced. The best condition for
hydrogen production occurs a t 500K in the model in which
carbon (soot) and methane gas are excluded and where
pressures are low, and water is in excess in the feed. To
achieve these conditions in practice the reactions for methane
formation, which is thern~odynamically favoured, and the
appearance of carbon (soot) must be inhibited.
T here is an increasing interest in the conversion of
abundant primary sources of energy to secondary
sources that can be easily stored, transmitted and
utilized. Hydrogen is one secondary type that meets
these criteria and is also non-polluting. It could be-
come a major means by which nuclear, geothermal
and solar energy are brought to the energy market.
The fuel cell is one important application and high-
purity hydrogen can be used as one of the feed gases
to such cells.
Hydrogen production from solid, liquid or gaseous
fuels is well established, the first step in this process
being the steam treatment of the hydrocarbon which
is known as reforming. A second step increases the
hydrogen yield by converting the CO produced into
CO,, the so-called shift reaction. However, as fossil
fuel supplies are depleted, synthetic substitutes will
become the source of hydrogen, and methanol is a
strong candidate for future large scale production",".
Methanol has advantages as a feed liquid to a steam
reforming process because of its low water t o carbon
ratio required, relatively low reforming temperatures
between 250-350°C, consistently high quality (sulphur
< Sppm) and ease of handlingcs'.
A thermodynamic analysis of the possible reactions
gives equilibrium compositions from which the se-
quence of reactions can be selected to maximize pro-
duction of hydrogen. Of course, such an analysis is
without regard for reaction rates or whether any
reaction will ever occur. Therefore experimental
study of the reaction kinetics is a necessary comple-
mentary tool for providing data on reaction rates and
on suitable catalysts. The ideal procedure is to select
the appropriate catalyst to promote only those reac-
tions for best yields as predicted from the thermody-
namics.
720 The Canadian Iournal of Chemical Engineering, Vol. 5 9 , December 1981
0008-4034/81/06 0720-$1.00/.15
On a 6tudib les kquilibres thermodynamiques mis en jeu
au cows du reformage catalytique du mtthaiiol par la vapeur
pour produire de I'hydrogkne, sur une gamme de pressions
absolues de 100 B 3040 kPa, de temperatures de 400 B 700 K
et de rapports eau/mtthanol dans l'alimentation de 1.5 A 0.69.
On a considbrh quatre niodkles, selon les produits de rtactions
possibles, et Yon a calculh la composition d'tquilibre pour
chaque modkle.
La pr6sence de intthane et de carbone diminue la quantitk
et la qualitt de l'hydroghe produit. La meilleure condition
pour la production de I'hydrogkne se prhsente Q 500 K pour
le niod&le dans lequel le carbone (suie) et le mbthane sont
exclus, les pressions &ant faibles et l'eau Ctant en excb dans
I'alimentation. Pour rhaliser ces conditions, il faut produire
une inhibition des reactions conduisant B la formation du
m&hane, qui est thermodynamiquement possible, et B la
formation de carbone (suie).
Houseman and Cerini'"' examined the thermo-
dynamics of the overall reaction using a fixed 2 : l ratio
of steam to methanol in the feed a t one pressure.
Dixon et alc3' also considered the thermodynamics to
examine the temperature and pressure effects on
conversion in the reforming and shift steps, but only
a t a feed ratio of steam to methanol of 1:l. We have
not been able to find a complete analysis of the
thermodynamics of all t h e reactions involved in the
steam reforming system. Undesirable side reactions
affect the yield and purity of hydrogen. In addition,
a knowledge of these conditions promoting carbon
formation is essential because of its impact on poison-
ing the catalyst.
Our research group has an experimental program
underway to investigate the effects of various cat-
alysts on the kinetics of the reactions in the steam
reforming of methanol and has also carried out a
thermodynamic analysis of the system involving its
most likely products, viz. H2,COr, CO, C H , and C. In
this paper will f i r s t be reviewed briefly the literature
of catalytic reforming of methanol f o r hydrogen pro-
duction and will be reported the results of our ther-
modynamic analysis. A subsequent paper (sub. for
pub. Can. J. Chem. Eng.) will contain the kinetic data
obtained using a Girdler catalyst.
Literature review
Research and development activities related to
methanol utilization f o r producing hydrogen are
scattered in the literature. Some of the early work
is included in general bibliographies on hydrogen
fuel^'^' and fuel cells'". There has been interest in hy-
 TABLE1 TABLE 2
EQUILIBRIUM CONSTANTS FOR MODEL 2 RAT~O
OF FUCACITY COEFFICIENTS (11, Uz, a3 (14 FOR MODEL 2

-- Pressure (kPa) 1
101.3 1013 1520
400 4.312 x lo4 6.480 X 4.949 X lo3 4.175 X 1011 400 1.007 - -
500 7.634 x 108 6.980 x 10-3 1.622 x 106 1.176 X lo6 500 1.004 1.045 1.078 1.113
600 2.221 x lo8 3.537 X 10-2 8.662 X lo7 202.6 550 1.003 1.032 1.053 1.078 1.149
700 2.447 X lo8 0.1105 1.599 X lo8 0.3809 600 1.003 1.021 1.035 1.053 1.100
650 1.002 1.018 1.028 1.038 1.071
700 1.002 1.013 1.020 1.031 1.048
- - - -
drogen from methanol"-"", especially for fuel cells. The
400
500
550
0.998
0.998
0.998
0.987
0,990
0.982
0.987
0.977
.
0.982
I -
0.958
on-board steam reformation of methanol to generate 600 0.9985 0.994 0.992 0.988 0.972
the hydrogen needed to drive a vehicle has been in-
vestigated"* *'), The study in refca3'considered feeding
650
700
400
0.999
0.9995
1.005
0.9945
0.995
1.087
0.994
0.994
1.335
0.994
0.987
-
1 0.982
0.992
-
hydrogen directly into an internal combustion engine. 500 1.002 1.031 1.058 1.087 1.144
Other possible applications have been evaluated'",*0'. 550 1.01 1.022 1.040 1.058 1.101
Many studies using a range of catalysts have been 600 1.001 1.015 1.027 1.041 1.068
carried out for the methanol reformation reaction. 650 1.001 1.012 1.022 1.030 1.052
700 1.001 1.008 1.014 1.024 1.037
Those containing copper, either as a pure metal, oxide 400 0.995 - - - -
or combined with other metal-metal oxides, make up 500 0.998 0.981 0.971 0.939 ' -
the majority of the studies. These include CU-CU 550 0.998 0.985 0.977 0.951 1 0.903
OXideSlS043) ; CuZnl4,ll"s~3X~. C~-Mn(P3,3033) , CU-AI'~'', 600
650
0.9985
0.999
0.990
0.992
0.984
0.988
cu~cr".30'3'.33." . ' Among the catalysts not containing 700 03935 0.994 0.990
copper are the metal-metal oxides of Fe-Cr'so*8s,u': Zn- ___
cr130.33). , NiAI"', Pd-AF".
Our literature search revealed that an understand-
ing of the steps involved in the steam reforming re- eb
action is lacking. Two recent kinetic s t ~ d i e s " ~ ~report
possible kinetic mechanisms, although only the data
'~' Kz = x a 2. ,

from"" are available to us. K 3 -- e&

__ P2
--a,
N2 j ....... ... . . .. ... .. . . . .(7)
Therniodynamic analysis
We have considered the possible products from the (81
steam reformation of methanol to be H2, CO,, CO,
unreacted H,O and C H 3 0 H , CH, and carbon. The where a', a?, a3 and ar a r e the ratios of the fugacity
following four models were constructed beginning with coefficients (see Table 2), i.e. fugacity divided by
the simplest containing only the primary products and total pressure, of the pure components at the tem-
ending with one containing all possible components perature and total pressure P in t h e appropriate sys-
except the higher alcohols. There is evidence that the tem and N is the total number of moles present a t
reaction involving the methanol itself is in two stages equilibrium, i.e. :
- decomposition to carbon monoxide and hydrogen
followed by a relatively f a s t conversion of the carbon N = (I +b + c + d + e +.! (9)
monoxide in a shift reaction with the steam"*'. Now if the initial number of moles of CHIOH is A
Our four models are: and the initial number of moles of H 8 0 is B then the
Model 1: equilibrium of H , , C 0 2 , CO, H P O and un- following material balance equations can be written,
reacted CH,OH
Model 2: model 1 plus C H , forC a + c + e + . ! = A (10)
Model 3: model 1 plus carbon for0 a + b + 2 c + e = A + B (11)
Model 4: model 1 plus CH,and carbon
Equilibrium compositions for each species in each
for H 4a 26 + +
2d 4 j = 4A + + 2B (121
model were derived from a combination of equations Rearranging equations (10) - (12) we have:
involving mass balances and t h e equilibrium constants.
c+f=A-(a+e)=a (13)
Model 2 is chosen to illustrate the methods and equa-
tions involved. In all models, a catalyst is needed to b+2c=(A+R)-(a+e)=fl (14)
promote reaction a t the relatively low temperatures
considered.
b + 2f = (2A + B) - +
( 2 ~ d) = 15)
Model 2 To solve for the individual components we initially
assume t h a t a = d = e = 0
+
CH30H HzO 3Hz +
COz (1)
+
C02 H2 CO H20 + (2) thus Equation (13) becomes c +f = a (a = A) . (13l)
CHsOH s CO LHz + 13) +
Equation (14) becomes b 2c = fl (fl = A + B ) (14')
CO +
3H2 CHI H20 + (4) Equation (15) becomes b 21 = y (7= 2A + B) + (15l)
By letting the equilibrium moles of C H 3 0 H , H 2 0 , CO,, Now 2 x (13') + (14') + (16') gives
H,, CO and C H , be a, b , c , d, e, and f respectively,
then the equilibrium constants for Equations (1)-(4)
(see Table 1) can be represented by:

(5) Equation (13l) givesf = oc - c ( = ~ initially

Thc Canadian Journal of Chemical Engineering, Vol. 5 9 , December 1981 721

 0
c
NO CARBON
REGION

500 -

o*6Q
I
CARBON REGION -I
- MODEL 4 I
I
I

I I I
I _I
I
0.5 I.o 1.5
FEED RATIO - moles H 2 0 : CH,OH
Figure 1 - Limiting conditions for deposition of carbon -
iiiodel 3 with temperature as a function of feed ratio. ( j =
osol I
SO0
I
600
, 0
101.3, k = 1013, I = 2026, m = 10.13 kPa). T/ K
Figure 2 - Mole fraction of H, as functions of T, P and
feed ratio - model 1. ( j = 101.3, k = 1013, 1 = 2026 kPa;
moles H20: CH,OH - -1.5:1, - - - 1:1,
1:15 -

a (= T-) initially.. . (181

I 1 I
70 li 600 700
400 500 600 700 400
T/K T/K
Figure 3 - Mole fraction of H2 as functions of T, P and Figure 4 -
Percent conversion of CH,OH as function of T’,P
feed ratio - nindel 3 . (j, k, 1 and moles H,O:CH,OH as for and feed ratio - model 1. (j, k, 1 and moles II,O:CH,OH as for
Figure 2). Figure 2).

722 The Canadian Joirrnal of Chemical Engineering, V d . 5 9 , 1)rrenaIwr 1981

 0.70
MODEL 2

0.60-- ---

Yn20 -
l.
<
0.50 -

e i- f I . I

0.20 t-

400 500
T/ K
600

Figure 5 - Mole fraction CO, H,O and CO, as functions

700
0.08

400
-.- 6

600
- 700
of T, P and feed ratio - model 1. (j, k, I and moles H,O: 500 T/K
CH,OH as for Figure 2).
Figure 6 - Mole fraction CO,,'CH, and H,O as functions of
T, P and feed ratio - model 2. (j, k, 1 and moles H20:CHaOH
as for Figure 2).
5 A . ..
Ilence h' = a + h + c + d + e +f =
I
initially (9)

For all models, equilibrium concentrations were

(191
y = Kncd
(21)
a?b
we now have first approximations for the 7 unknowns.
Now a , /j and y values may now be calculated
from Equations (13), (14) and (15) respectively, and
then new values for c, f, b and N from Equations
(16), (171, (18) and ( 9 ) , respectively. Continued
looping back t o Equation (19) eventually results in
the 7 unknowns agreeing with the previous set within
required precision. Models 1, 3 and 4 were analysed
in a similar way.
Results and discussion
The equilibrium compositions were determined by
solving the equations on an HP 9821A programmable
calculator using the Method of Successive Substitu-
t i o n ~ " ~ 'The
. number of iterations required to give 6
or 7 significant figure accuracy was usually 3 or 4.
solved over ranges of pressure 101-3040 kPa (1-30
a t m ) , of temperature 400-700K and of feed ratios
water to methanol, 1.5-0.67. In addition, a pressure of
10 kPa was used for models 3 and 4. The temperature
range was selected to be that compatible with fuel
cell systems. The calculations resulted in many nu-
merical results so t h a t the problem became one of
representing them in the most useful, compact and
convenient form. We have chosen to represent the
data in graphical form and discuss the implications
of the reaction conditons on the reforming process
which involves the catalyst and the fuel cell where
quantity and purity of the hydrogen are important
factors.
A. Carbon Formation
Over the temperature range considered in this study,
a catalyst is needed for the steam reformation of
methanol. Carbon deposition on the catalyst surface
will result in several undesirable side effects, all of
which affect the quantity and purity of products.
These include a loss in effective surface area, a lower-
ing of the heat transfer rate from catalyst to gas and
partial plugging of the void space within the catalyst.
The appearance of carbon may arise from decomposi-

The Canadian journal of Chemical Engineering, V o l . 59, December 1981 723

tion of CO, C H I or the reaction of CO, or CO with H,.
I t is important to know under what conditions of
equilibrium this will occur. Carbon appears only in
our models 3 and 4.
Figure 1 shows the range of conditions under which
solid carbon will appear in the systems of models 3
and 4. To prepare these plots, a fixed temperature and
pressure were selected and the feed ratio HPO:CHIIOH
calculated to correspond to zero carbon in the equilib-
rium. The 'zero carbon' lines for the various pressures
were then constructed.
For model 3 in Figure 1, large feed ratios H z 0 :
CHsOH are needed to operate within the no carbon
region and prevent its formation. When pressure in-
creases, the area of the no carbon region decreases
slightly. More solid carbon appears as the equilibrium
shifts in the hydrogen reactions with COr, CO and in
the decomposition of CO.
The situation is quite different for model 4 shown
in Figure 1 where large feed ratios H t 0 : C H d H do
not occur along the abscissa. The no carbon region lies
in the feed ratio range of 0.77 to 1.8 and between 700
to 400K a t 101 kPa (1 atm). Here an increase in
pressure increases the no carbon region as the reaction
of methane decomposition to carbon and hydrogen is
reversed. Houseman and Cerini"' show the equilibrium
composition of the decomposition of methanol versus
temperature for one feed ratio case containing water
(their Figure 4). No details are presented on the
source of the data in their Figure. They show
carbon (soot) disappearing a t 540K for a feed ratio
HzO:CHJOH of 0.5, but no pressure conditions are
given. A comparison with our Figure (1) for a feed
ratio of 0.5 shows carbon (soot) to be present a t all
pressures up to 700K. Reasons for this difference are
not clear to us.
B. Quantity of Hydrogen Produced
1. Mole fractions of hydrogen
Model 1 - Figure 2 shows that for any feed ratio
H,O:CHIOH, the mole fraction of hydrogen is greatest
a t TG500K and low pressure. In addition, the curves
for excess water in the feed, i.e. feed ratio 1.6:1, lie
below the others. This unreacted water reduces the
mole fraction of hydrogen, but not necessarily its
quantity. For model 1, the greatest quantity of hydro-
gen is produced for the excess water feed ratio a t all
temperatures and pressures and amounts to about
3 moles Hdmole methanol fed. (graph not shown) If
purification problems are overcome, then the best
operating conditions (i.e. optimum) to produce the
most hydrogen are those with excess water in the
feed a t low pressure and T - 500K. A comparison
of our results with Dixon et al'", whose fixed feed
ratio is a special case of our general model 1, shows
complete agreement.
Model 2 - For the temperature range examined
by us, the appearance of methane results in the
mole fraction of hydrogen rising to 18% occurring a t
700K and 10lkPa. As the pressure is increased to
1013 and 2026 kPa a t 700K, the mole fraction drops
to 6% and 5% respectively. Should this model prevail
in practice, to increase the mole fraction of hydrogen
to levels achieved in model 1 would require T > 700K,
which may be undesirable for direct fuel cell applica-
tion. In this model, a variation of the feed ratio
affects the mole fraction of hydrogen by only a small
amount.
Model 3 - The appearance of solid carbon reduces
by a factor of 2-3 compared with model 1 the mole
724 The Canadian lotcrnal of Chemical Engineering, Vol. 5 9 , December 1981
fraction of hydrogen for all feed ratios. See figure 3.
As in model 1, the excess water case is associated
with the lowest mole fraction of hydrogen. The moles
of hydrogen per mole methanol fed vary from 0.8 to
1.0 and are similar for all feed ratios and independent
of temperature and pressure. In calculating the various
compositions for this model 3 containing carbon, the
thermodynamics alone have been considered and the
catalyst activity does not enter into any of these
calculations.
Model 4 - Carbon and C H , are present here and
dramatically reduce the mole fraction of hydrogen
from that of model 1. In model 4, hydrogen yields are
favoured a t low pressures, but a s in model 2 high
temperature favours higher mole fractions of hydro-
gen in the product. At 101 kPa, the mole fraction of
hydrogen rises to 10% a t 700K.
2. Methanol conversion
Model 1 - Figure 4 shows methanol conversion
versus temperature at various feed ratios and pres-
sures. The following features emerge, viz.
i ) pressure effect is least significant a t highest tem-
peratures for all feed ratios;
ii) best conversions occur a t low pressures with ex-
cess water in the feed;
iii) at low pressures, the temperature effect is min-
imal between 400 and 500K and negligible above
5OOK.
From Figure 4, it can be seen that the conditions
for greatest hydrogen production i.e. 500K, 1 atm,
excess water in feed, are also the conditions for
greatest C H 3 0 H conversion.
Models 2 to 4 - Methanol conversion of 100%
results a t all temperatures, pressures and feed ratios
(graph is not shown). However, hydrogen production
is much lower than in model 1 especially in models 2
and 4 where C H , is the major product.
The conversion of CHIOH for model 1 based on
thermodynamics is greater than 95% at temperatures
above 400K. atmospheric pressure (Figure 4 ) . The
only available published set of experimental data is
for a model similar to our model 1 (48), where the
highest conversion of CHsOH occurred a t 480K, at-
mospheric pressure. For their catalysts, conversion
did not exceed 16%. Clearly. the thermodynamics
offer the incentive for developing better catalysts.
3. Moles H , produced per mole of CH,OH fed (graphs
not shown)
Increasing the quantity of H I produced per mole
of feed leads to an increase in the efficiency of pro-
ducing the hydrogen. The greatest amount is obtained
in all 4 models when water is in excess in the feed.
Temperature increase causes a slight decrease in moles
of hydrogen per mole of methanol from a maxima of 3
to 2.8 for model 1, 1 to 0.95 for model 3, but an in-
crease from 0 to 0.6 for models 2 and 4. In these latter
two models, hydrogen production is very low indeed.
An increase in pressure had no effect on models 2-4,
but results in decreased H 2 per mole methanol in
model 1 from 3 to 2.9. 2.9 to 2.6 and 2.6 to 2.2 for
feed ratios of H.O:CHsOH of 1.5:1, 1:l and 1:1.5
respectively.
C. Impurities in the Hydrogen
Model 1 - The optimum conditions for quantity of
H p production have been shown to occur a t 1 atm,
SOOK with. a water rich feed, Figure 5 shows for
these optimum conditions the mole fractions of CO.
 0.50

MODEL 4

*0"
0
I
..",
0, I I
3
0.30

0.IC
\
\ I I I
'\i 4 3 500 600 700

I
\
T IK
\
\ Figure 8 - Mole fraction HIO, CH, and CO, as functions of
.-.
T, P and feed ratio - model 4. (j, k, I and moles HzO:CH,OH
as for Figure 2).

moderately and that of C H , decreases moderately.

yc
0.20
\ ing the methane steam reaction to the right to pro-
I 1
400 500 600
T/ K
Figure 7 - Mole fraction C and H,O as functions of T, P
and feed ratio - model 3. (j, k, I and moles HPO:CH,OH as for
Figure 2).
H,O and COz to be approximately 176, 12% and 21%
respectively. An increase in temperature causes an
increase in CO, but a corresponding decrease in CO,.
Insofar as fuel cell operation is concerned, i t is the
CO gas that is most undesirable and that should be
removed. Our optimum condition for hydrogen pro-
duction occurring at low temperature is fortuitously
the condition for lowest levels of CO produced.
When CO per mole of CHsOH fed is plotted against
temperature (not shown here), there are 0.02 moles
CO per mole of CH&H fed a t 1 atm, 500K with excess
water in the feed. As temperature rises to 700K, the
moles of CO per mole of CHsOH fed rises to 0.27.
For models 2, 3 and 4, the moles of CO per mole of
CHsOH never exceed 0.014 for all feed ratios and
this maximum occurs at 700K.
Model 2 - The appearance of CHa has resulted in
the virtual disappearance of CO to values of mole
fraction between lo-' and lo-'. It has been noted
above that the optimum conditions for hydrogen pro-
duction in model 2 occur at 1 atm and T>700K. As
temperature is increased, the mole fraction of water
drops sharply in Figure 6, that of CO, increases
This is consistent with temperature increase shift-
\ duce CO, and H p rather than CO and H , (the reverse
of Equation ( 4 ) ) .
1
CH4(g) -k 2H20(g) = c02(g) 4H2(g) + . (22)
Model 3 - For the pressure and temperature ranges
considered, the maximum level of CO, is about 2.5%
and of CO about 0.2%. These values are attained at
1 atm and 700K. The equilibrium reaction determin-
ing the amount of carbon is likely,
C(S) + 2H2OW = con (g) + 2Hz(g) (23)
For a given feed ratio as temperature rises, the mole
fraction of water and carbon should fall. This is borne
out in Figure (7).
Model 4 - The mole fractions of H20,C o p and C H ,
for this model are shown in Figure 8 as a function of
temperature. For the conditions where carbon soot
is not present, i.e. water rich feed, T>500K, 1 atm
in Figure 1, this model shows similarities to model 2
as one would expect. Compare Figure 6 with Figure 8.
conclusions
1. The optimum conditions for producing hydrogen
in quantity occur for model 1 at low pressure, 400GT
<500K and excess H,O in the feed. The upper limit on
the moles of H , produced per mole CHJOH fed is 3,
which is very close t o that under optimum conditions.
2. Model 3 can be made thermodynamically to behave
as model 1 by adding an excess of water a t T>500K,
thereby preventing carbon soot formation.

The Canadian Journal of Chemical Engineering, Vol. 59, December 1981 725
3. Models 2 and 4 show CH, p r e d o m i n a t i n g in the
product a n d t o increase the q u a n t i t y of hydrogen pro-
duced requires t e m p e r a t u r e s greater than 700K.
4. Thermodynamically we have shown i n models 2 &
4 that the presence of C H , reduces the q u a n t i t y a n d
quality of H 2produced. W h e n significant CO, a n d HI
are present, C H , must b e a m a j o r product since the K
value at 500K f o r Equation (22) i s l.lxlO-* (61).
Therefore, t o achieve the conditions of model 1 f o r
optimum H, production, catalysts must be f o u n d that
f a v o u r these reactions and inhibit C H , formation.
Acknowledgment
The authors wish to acknowledge the contributions of D. Baker and
C. Thomas to the calculations. The research for this work wan
supported by the Department of National Defence, Contribution
NO. aao-81s.
Nomenclature
‘A = initial moles CH30H
a = CHsOH concentration ht equilibrium
, a4 = ratio of fugacity coefficients, ie. fugacity divided
a l , a ~(13.
by total pressure of the pure components at the
temperature and total pressure P for each model.
B = initialmoles HzO
b = Ha0 moles a t equilibrium
c = COZmoles a t equilibrium
d = Hz moles a t equilibrium
e = CO moles a t equilibrium
f = CH, moles a t equilibrium
y = mole fraction in the gas phase
K 1 = equilibrium constant, kPa2
KZ = equilibrium constant, dimensionless
K I = equilibrium constant, kPa2
K c = equilibrium constant, kPa-*
N = total moles
P = total pressure, kPa (atm)
a = equation (13)
0 = Equation (14)
y = Equation (15)
References
( 1 ) “Alcohols a s Alternate Fuels f o r Ontario”, Can. SOC.
Chem. Eng. & Can. SOC.Mech. Eng. Symp., Toronto,
Nov. (1976).
( 2 ) “Building a New Base f o r Methanol”, Can. Chem.
Proc. 61, 76 (1977).
( 3 ) Dixon, A.G., Houston, A.C., and Johnson, J.K., “An
Automated Generator f o r the Production of Pure
Hydrogen from Methanol”, Paper 729161, 7th
IECEC, 1084 (1972).
(4) Houseman, J., Cerini. D.J., “Onboard Hydrogen Gen-
eration f o r Automobiles”, Paper 769001, 11th IECEC,
6 (1976).
( 5 ) Hydrogen Fuels, A Bibliography, US. Department
of Commerce, TID-3358, Feb. (1976).
( 6 ) Fuel Cells - A Bibliography, Technical Information
Center, Energy Research and Development Adminis-
tration, TID-3359, June (1977).
( 7 ) Heffner, W.H., Veverlea, A.C. and Skaperdas, G.T.,
“Hydrogen Generating Plant based on methanol de-
composition. Design for submarine fuel cell use”.
Fuel Cell Systems, Advan. Chem. Ser. 47, 31.8 (1966).
( 8 ) Gould, R.F. (ed.) , “Fuel Cell Systems - 11”, Advan.
Chem. Ser. 90 (1969).
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Manuscript received October 22, 1980; accepted for pub-
lication J u n e 24, 1981.
* * *
727