Chemical Engineering Communications, 204:141148, 2017

Copyright # Taylor & Francis Group, LLC

ISSN: 0098-6445 print/1563-5201 online
DOI: 10.1080/00986445.2016.1245186

Hydrogen Production by Steam Reforming of Commercially

Available LPG in UAE
S. AL-ZUHAIR1, M. HASSAN1, M. DJAMA1, and A. KHALEEL2
1
Chemical Engineering Department, College of Engineering, UAE University, Al-Ain, UAE
2
Chemistry Department, UAE University, Al-Ain, UAE

Steam reforming of commercially available LPG using Ru=Al2O3 and Ni=Al2O3 catalysts has been studied at temperatures
between 573 and 773 K. Ru=Al2O3 catalyst showed higher rates of reaction and lower activation energies of the three main
components of LPG, compared with Ni=Al2O3. However, Ni=Al2O3 catalyst showed a better H2:CH4 selectivity. The
activation energy of n-butane was the lowest over Ru=Al2O3, whereas over Ni=Al2O3, propane had the lowest activation
energy. The activation energy of i-butane was always the highest over both catalysts, which suggests that both catalysts
performed better with unbranched molecules. A slight increase in activation energy was observed, when each component of
the LPG mixture was studied separately as a pure gas, compared with being mixed in LPG. At a constant temperature of
773 K, hydrogen production yield and H2:CH4 selectivity were determined using Ru=Al2O3 at different steam:carbon (S:C)
ratios and LPG ow rates. It was found that the yield and selectivity increased with the increase in S:C ratio and the decrease
in the ow rate. The highest yield of 0.64 was achieved using S:C ratio of 6.5 and a LPG ow rate of 50 mL min1. The work
provides valuable information on steam reforming of pure components of LPG, compared with when they are in the mixture.
The comparison is done using conventional steam reforming catalyst, Ni=Al2O3, and compared with Ru=Al2O3. The observed
trends and variations in reaction rates, in pure and mixed gases, indicated that the mechanism of steam reforming of a
hydrocarbon mixture depends on its composition.
Keywords: Hydrogen; Kinetics; LPG; Ni=Al2O3; Ru=Al2O3; Steam reforming

Introduction About 50% of the worlds feedstock for H2 production

Recently, hydrogen (H2) has appeared as a clean alternative
energy source to the existing fossil fuels source. It can be
directly combusted in an internal engine or electrochemically
transformed to electricity in a fuel cell. Both methods do not
produce harmful emissions (Armor, 1999; Seo et al., 2002;
Song, 2002), but fuel cell systems are signicantly more
energy efcient and cleaner than conventional energy sys-
tems (Crespo et al., 2008). Having a hydrogen production
unit combined with a fuel cell power generator presents a
practical solution to the hydrogen storage problem, because
an efcient hydrogen storage technology and distribution
networks are still lacking (Dagani, 2002).
Currently, steam reforming of hydrocarbons is the most
broadly used technology to produce bulk quantities of H2,
with natural gas and liqueed petroleum gas (LPG) being
the primary sources (Seo et al., 2002). Steam reforming gives
the highest yields of hydrogen in the product stream compared
with other production techniques (Rostrup-Nielsen, 1984;
Pena et al., 1996), but the process requires a considerable
heat input.
Address correspondence to S. Al-Zuhair, Chemical Engineering
Department, College of Engineering, UAE University, P.O.
Box 15551, Al-Ain, UAE. E-mail: s.alzuhair@uaeu.ac.ae
comes from natural gas (Scholz, 1993), most of which is
discovered in accumulations far away from industrial
complexes or produced from off-shore platforms. In
addition, about 11% of this gas is re-injected to reservoirs
as a secondary recovery method to increase oil production,
and 4% is ared or vented due to the scarcity of gas
utilization plants or pipeline networks for gas transmission.
On the other hand, LPG is more practical for application in
remote sites as well as for domestic uses, because it can be
obtained easily through a wide distribution network or in
cylinders. For safety reasons, traces of sulfur compounds
are usually added, as odorants, to LPG prior to distribution.
These sulfur compounds need to be effectively removed,
usually by adsorption, as they poison the steam reforming
catalysts (Crespo et al., 2008).
Although studies on steam reforming of methane are
available in open literature, limited studies were reported
on steam reforming of larger hydrocarbons, such as
n-butane. Issues of concern that have been investigated
include coke formation over Ni and Ni-Mo catalysts during
n-butane steam reforming (Kepinski et al., 2000; Borowiecki
et al., 2002), and activity=selectivity aspects of Ni, Pd, and Pt
catalysts (Wang and Gorte, 2000, 2002). The kinetics of
steam reforming of n-butane using Pt and Ni=Al2O3 catalyst
at temperatures between 578 and 678 K has also been
142
Fig. 1. Schematic diagram of the steam reforming experimental setup.
reported (Avc et al., 2004). However, hydrogen production
from a pure component is uneconomical, and a mixture of
hydrocarbons, as in LPG, is usually used. Nevertheless,
hydrogen generation from LPG is rarely studied, and the
study of the kinetics of steam reforming from LPG is still
lacking. Therefore, the objective of this study is to investi-
gate steam reforming of commercially available LPG using
Ni=Al2O3 and Ru=Al2O3, and compare it to the steam
reforming of its pure components.
The composition analysis of the LPG available in UAE
showed that it consists mainly of propane (50.6 mol%),
i-butane (18.7 mol%), and n-butane (29.7 mol%). The
amounts of other hydrocarbons, such as ethane and
pentanes, are less than 1%. The overall equations that
describe the steam reforming, combined with gas shift
reaction, for propane and butane(s) are shown in Equations
(1) and (2), respectively.
C3 H8 6H2 O 10 H2 3 CO2 1 catalyst was deactivated, because it is highly active in oxygen
C4 H10 8H2 O 13H2 4CO2 2 of the catalyst was done by gradually supplying diluted
Methanation reaction also occurs simultaneously with
steam reforming, which is described by Equation (3)
CO 3H2 CH4 H2 O 3 monitored to make sure that no sulfur escapes into the steam
Materials and Methods
Chemicals
LPG was obtained from a local petrol station, ADNOC,
UAE. N2, air, and hydrogen cylinders, of high purity, were
obtained from Abu Dhabi Oxygen Company, UAE.
Ni=Al2O3 catalyst and BASF Ni5256E desulfurization
adsorbent were kindly provided by JX-NRI, Japan.
Ru=Al2O3 catalyst was obtained from Sigma Aldrich, USA.
Experimental Setup
The steam reforming reaction setup was kindly provided by
JX-NRI. It mainly consists of a desulfurizer, a steam
reformer, a condenser, a drain separator, and a catalytic
combustor. In addition, the setup is equipped with a water
S. Al-Zuhair et al.
injection pump, a water tank, and a vaporizer in order to
supply steam to the reformer. A schematic diagram of the
setup is shown in Figure 1.
To remove the sulfur compounds, the LPG was rst
passed, at a specied ow rate, through a desulfurizer, which
is a stainless steel spindle-shaped double-end Swagelok
cylinder vessel, packed with BASF Ni5256E catalyst. The
temperature of the desulfurizer was maintained at 200 C
using a heating mantle. The desulfurizer was rst lled
completely with passive catalyst. Care was taken to avoid
any space that may serve as an escape channel for untreated
gas, which could then poison the reforming catalyst. The cata-
lyst was trapped between two stainless steel meshes on both
sides. Before use, the desulfurizer was heated up to 200 C at
a rate of 10 C min1, under N2 ow of 10 mL min1
mL-catalyst1 and was kept at this temperature for 1 h. Once
activated, the desulfurization catalyst was always kept under
N2 atmosphere when not in use. Before discharge, the spent
environment and may catch re upon air contact. Passivation
oxygen or air (1 mol%) in N2 until heat generation in the
desulfurizer subsides. Throughout the experiment, the sulfur
contents in samples withdrawn from a sampling port situated
after the desulfurizer, and before the steam reformer, were
reformer.
Steam reformer is a 1=200 stainless steel pipe that con-
tained steam reforming catalyst, and could be heated up to
800 C. Stainless steel was shown to be inert under the
reaction conditions (Avc et al., 2004). The temperature
inside the reactor was controlled by a surrounding electric
heater. Two types of catalysts were used in this work,
namely Ni=Al2O3 and Ru=Al2O3. A predetermined amount
of reforming catalyst was placed above a spacer over a
spring. Another spacer was placed on top of the catalyst
bed, and secured by another spring.
The condenser is a jacketed stainless steel coil, cooled by
supplying running water to the outer jacket. The drain
separator is a jacketed vessel, and used to condense and
separate the unreacted water from the product gas. The
drain separator was also cooled by running water. The
combustor, equipped with a heater and an air blower
that supplies ample amont of air, was used to burn produced
combustible gases, such as H2 and CH4.
Hydrogen Production by Steam Reforming
Experimental Procedure
Kinetics Study
In this part, 2 g of fresh catalyst particles were placed in the
reformer reactor. The selected small amount occupied a
small differential volume within the reactor. The differential
volume allows assuming the catalyst bed to be isothermal
and have a constant concentration and negligible axial dis-
persion. The reactor temperature was adjusted to the desired
value under pure nitrogen ow. Once the reaction tempera-
ture was reached, nitrogen ow was stopped and steam and
LPG were introduced into the reaction system at a steam:-
carbon (S:C) ratio of 4.5. The liquid water ow rate used
to produce the required steam was determined from the total
carbon input ow rate, using Equation (4)

MWw
Qw 4:5Fi 3xpropane 4xbutanes in q
w Supplies, UAE, was used to calibrate the GC.
where Qw is the volumetric ow rate of water (mL s1),
xpropane and xbutane(s) are the mole fractions of propane
and butane(s), respectively, MWw is the molecular weight
of water (g mol1), qw is the density of water (g mL1)
and Fi is the total input ow rate (mol s1), determined from
the ideal gas ow, as given by Equation (5)
 
101:3  103
Fi QLPG 5 used to calibrate the GC.
8:314  298
where QLPG is the input volumetric ow rate of LPG
(mL s1). To determine the activation energy, the reaction
rate was determined at different temperatures in the range
of 573 and 773 K using three ow rates of LPG, namely
50, 75, and 85 mL min1.
A carbon material balance was used to determine the
output molar ow rate exiting the reactor, as shown in
Equation (6)


Fi 3xpropane 4xbutanes in
Fo
6
3xpropane 4xbutanes xCO2 xCO xmethane out
where Fo is the total output molar ow rate (mol s1), xCO2 ,
xCO, and xmethane are the mole fractions of CO2, CO, and
methane, respectively. Once the output molar ow rate
was determined, the conversions were determined using
Equation (7)
xAi Fi  xAo Fo
XA
xAi Fi
where xAi and xAo are the mole fractions, of propane,
i-butane, or n-butnae, in the input and output streams,
respectively.
Effect of Steam:Carbon Ratio
At a constant temperature of 773 K, 5 g of Ru=Al2O3 cata-
lyst was used to test the effect of different S:C ratios (in
the range of 4.5 and 6.5) and LPG ow rate (in the range
of 50 and 85 mL min1) on hydrogen production yield and
143
selectivity. As suggested by the overall reactions (Equations
1 and 2), the yield was determined using Equation (8).
xH2 ;out Fo
H2 yield
8
Fi 10xpropane 13xbutanes in
Analysis
To analyze the hydrocarbons in the LPG, a GC (Varian,
CP-3800) equipped with a FID detector and a Rt1-Alumina
BOND=MAPD column was used. The detector, injector,
and column temperatures were set at 100, 250, and 80 C,
respectively. Helium was used as a carrier gas, and a gas mix-
ture of standard alkanes (methane 1%, ethane 1%, propane
1%, i-butane 1%, n-butane 1%, i-pentane 1%, n-pentane
4 1%, and N2 balance at 7 bar), obtained from Nahla Medical
To analyze the inorganic gases, a GC (Shimadzu, 2010)
equipped with a TCD detector and an MS-5A column was
used. The detector, injector, and column temperatures
were set at 100, 100, and 80 C, respectively. The column
temperature was kept at 70 C for 2 min, then increased to
80 C at a rate of 5 C min1. Argon was used as a carrier
gas, and a gas mixture (CO2 10%, H2 10%, CO 10%, and
N2 balance), obtained from Nahla Medical Supplies, was
Gas chromatograph (Shimadzu, GC-2014) equipped with
FPD detector was used to determine the sulfur compounds.
The detector and injector temperatures were set at 150 C
and 250 C, respectively. The column temperature was kept
at 6000 C for 1 min, then increased to 250 C at a rate of
10 C min1. Helium was used as a carrier gas and a gas
mixture of standard sulfur compounds (H2S 10%,
COS 10%, ethyl mercaptan (EM) 10%, ethyl sulde 10%,
TBS 10%, thiophene 10%, and N2 balance), obtained from
Nahla Medical Supplies, was used to calibrate the GC.
Results and Discussion
Kinetics Study
Different ow rates of LPG and steam, with a constant S:C
ratio of 4.5, were passed through the reformer, packed with
2 g of Ru=Al2O3 or Ni=Al2O3 catalysts at different tempera-
tures. The high ratio of S:C ratio was selected to avoid coke
formation. A ratio of 2.5 is recommended for methane steam
reforming (Rostrup-Nielsen, 1984), and therefore, at the
7 selected ratio of 4.5, coke deposition was not detected over
both catalysts under the conditions used.
The production rates of H2, CO2, and CH4 at tempera-
tures between 573 and 773 K are presented in Table I. For
both catalysts, the production rate of the three products
increased with temperature, which is due to the increased
catalytic activities. The hydrogen produced over Ru=Al2O3
was considerably higher than that produced over
Ni=Al2O3, under the same operating conditions.
Equations (1) and (2) are the overall reactions, which con-
sist of two main reactions shown by Equations (9) and (10):
144 S. Al-Zuhair et al.

Table I. Production rate (103 mol min1) of CO2, CH4, and H2 at different temperatures and ow rates of LPG using 2g of
Ru=Al2O3 and Ni=Al2O3 catalysts, at S:C ratio of 4.5
Catalyst Ru=Al2O3 Ni=Al2O3

Temperature (K) 573 623 673 723 773 573 623 673 723 773
LPG ow rate of 50 mL min1
CO2 0.65 1.06 3.33 2.62 3.34 0.00 0.01 0.17 0.96 1.50
CH4 0.88 1.88 1.68 3.22 2.68 0.02 0.02 0.03 0.10 0.13
H2 1.55 2.22 2.23 6.45 9.3 0.01 0.08 0.60 3.04 4.86
H2:CH4 1.76 1.18 1.33 2.00 3.47 0.50 4.00 20.00 30.40 37.38
LPG ow rate of 85 mL min1
CO2 0.33 1.14 2.16 3.74 5.35 0.00 0.02 0.14 0.47
CH4 0.34 1.38 4.21 4.79 4.25 0.02 0.02 0.03 0.05
H2 0.77 2.33 6.96 11.0 12.2 0.01 0.07 0.58 1.5
H2:CH4 2.26 1.69 1.65 2.30 2.87 0.50 3.50 19.33 30.00

Steam reforming : Cn Hm nH2 O n m=2H2 nCO where rA is the rate of reaction of component A
9 (mol s1 g-catalyst1), xAi is the input molar fraction of
Water  gas shift : CO H2 O H2 CO2 10
Under the conditions used in this work, the product mix-
ture was free of CO, which is mainly due to removal of pro-
duced CO by the watergas shift and methanation reactions
(Rostrup-Nielsen, 1984). In addition, when operating at
temperatures below 500 C, as in this work, a higher equilib-
rium conversion of the exothermic gas shift reaction is
encountered. This is a desirable feature, as CO, in quantities
as low as 10 ppm, interfere with fuel cell operation and can
deactivate the Pt-based anode and cathode (Trimm and
O nsan, 2001).
In a differential volume element, the rate of reaction in a
packed bed reactor approaches that in a contineous stirred
tank reactor (CSTR), as given by Equation (11)
XA
rA
11
Wcat =Fi xA;i
component A, and Wcat is th weight of catalyst (g).
Therefore, the conversions of propane, i-butane, and
n-butane were determined at different input ow rates, and
were drawn versus Wcat=FixA,i. Figure 2(a) and (b) show
examples of the results for n-butane using Ru=Al2O3 and
Ni=Al2O3 catalysts, respectively. The trends for the other
two components were similar to those shown in Figure 2.
The initial rate of reaction was determined, at each
temperature, from the slope at Wcat 0, of XA versus
Wcat=FixA,i curves, similar to the ones shown in Figure 2.
When considering the initial rate of reaction, the effect of
products formation would be negligible. Therefore, the pro-
duct concentration does not appear in the power-function
expression (Equation 12) used to describe the intitial rate
of reaction (Avc et al., 2004)
 
E a
rA ko Exp Phydrocabon PbH2 O 12
RT

Fig. 2. Conversion of n-butane in LPG mixture at different temperatures and ow rates using 2 g of: (a) Ru=Al2O3, and
(b) Ni=Al2O3 catalysts, at S:C ratio of 4.5.
Hydrogen Production by Steam Reforming
Fig. 3. Arrhenius plot for evaluating activation energy of steam reforming of LPG using 2 g of: (a) Ru=Al2O3, and (b) Ni=Al2O3
catalysts, at S:C ratio of 4.5.
Since the S:C ratio was kept constant, the mole fractions
of the reactants (and hence the partial pressure) can then be
assumed the same for all runs, and Equation (12) can be
rearranged as shown in Equation (13)
 
E
rA ko Exp 13
RT
where ko is a constant dened by Equation (14)
ko ko Pahydrocabon PbH2 O 14
The activation energy of each reactant was then
determined from the slope of ln(rA) versus 1=T line, as
shown in Figure 3(a) and (b), using Ru=Al2O3 and Ni=
Al2O3 catalysts, respectively. The results in Figure 3 show
that for both catalysts, increasing the temperature resulted
in increasing the initial rate of reaction. However, the initial
rate of reaction on Ru=Al2O3 catalyst was higher than that
on Ni=Al2O3. Transition metals are known for their ability
to activate chemical bonds in molecules through possible
interaction between their d-orbitals and antibonding
molecular obritals of the adsorbed molecules on the surface
leading to weaker bonds and eventually bond cleavage. For
their known properties in breaking of bonds in hydrocar-
bons, Ni catalyst has been the most widely employed
catalyst, among other non-noble metals, for steam reforming
(Avc et al., 2004). However, at temperatures lower than
500 C, its activity has been relatively low, especially for
the reforming of larger molecules (Ishihara et al., 2005).
Several noble metal-based catalysts have been proposed as
alternative catalysts, and Ru catalyst was the one with better
catalytic properties; by comparing catalysts made of group
810 metals supported on oxides, such as Al2O3 (Gallo
et al., 2012). In addition, Ru showed lower coke deposition
and has a lower cost compared with other noble metals
(Gallo et al., 2012). Furthermore, Ru catalyst show a higher
activity for steam reforming of hydrocarbons than Ni cata-
lyst (Kikuchi et al., 1974), especially at temperature lower
than 500 C (Ishihara et al., 2005). The higher reactivity of
145
Ru catalyst compared with Ni catalyst can be attributed to
the larger atomic radius of Ru and therefore, more diffuse
d-orbitals allowing them to interact more readily with mol-
ecular orbitals of adsorbed molecules. On the other hand,
the smaller size of Ni atom and the higher radial penetration
of its d-orbitals makes its d-electrons more core-like and less
able to contribute to back-bonding with adsorbed molecules.
Low-temperature steam reforming allows for lower thermal
input into the steam reformer. In addition, if the operating
temperature of the steam reformer can be decreased,
waste heat from high-temperature fuel cells can be expected
to cover the energy demand for steam reforming.
Low-temperature steam reforming also contributes to a
reduction in thermal deactivation rates of the catalyst, due
to sintering, which suppresses coke formation (Namioka
et al., 2011).
On the other hand, methane was produced by both
catalysts at all temperatures. Table I shows the change in
the selectivity (dened as the ratio of the hydrogen
production rate to the methane production rate). A notable
difference in the selectivity was observed over both catalysts.
The high selectivity is a desirable feature, because hydrogen
is consumed in the production of methane, as shown in
Equation (3). Despite having a lower conversion, Ni=
Al2O3 shows better selectivity than Ru=Al2O3. In catalytic
reactions, such an inverse relationship between conversion
and selectivity is very often encountered. This is mainly
because pushing a reaction into a condition that favors more
reactants conversion may enhance the formation of unde-
sired products, which results in lower selectivity. This
explains the lower selectivity over Ru=Al2O3, since at same
conditions, the conversion over the Ru=Al2O3 is signicantly
higher than that over Ni=Al2O3. Which suggests that these
conditions also favor higher production of the undesirable
product. In addition, although coke formation did not occur
in our work, due to the high S:C ratio used, Ni catalyst is
known for high tendency of coke formation, especially with
higher hydrocarbons, which means it has a lower chance
for the formation of other carbon compounds, and hence
higher selectivity to hydrogen is expected. The lower coke
146 S. Al-Zuhair et al.

formation tendency and higher conversion over Ru catalyst Similar to the observations reported for zeolite, where both
on the other hand are associated with the formation of other intracrystalline diffusivity and external surface resistance are
carbon products leading to lower selectivity to hydrogen important, it can be deduced that a linear molecule diffuses
(Zhao et al., 2015). more easily through the interparticle pores of alumina
It was also found that the temperature effect on the selec- compared with a branched molecule of similar molecular
tivity was less over the Ru=Al2O3. The selectivity is dened weight.
by Equation (15) Avci et al. (2004) tested the steam reforming of pure
n-butane over 0.2%Pt15%Ni=Al2O3 catalyst and determi-
rH2 ko;H2 expEH2 =RT f1 Pi ened E=R value to be 9705 K. This value is very close to
15 the one determined in this work using Ni=Al2O3 catalyst,
rCH4 ko;CH4 expECH4 =RT f2 Pi
which was 9670 K. The Ru=Al2O3 catalyst superiority was
further proven by the lower activation energies of all three
where and rCH4 are the rates of production of H2 and CH4,
components compared with those found using Ni=Al2O3.
respectively, ko;H2 and ko;CH4 are the pre-exponential
Due to its superiority, all subsequent experiments were done
functions of H2 and CH4, respectively,EH2 and ECH4 are
using Ru=Al2O3 catalyst.
the activation energies of H2 and CH4, respectively, f1 and
The synergic effect of the mixture of hydrocarbons found
f2 are different functions in terms of partial pressures, Pi.
in LPG was assessed by comparing the initial rates of steam
Changing only the temperature and leaving everything else
reforming of LPG mixture to those of pure components,
constant, the selectivity can be represented as a function of
using Ru=Al2O3 catalyst, and the results are shown in
temperature as given in Equation (16)
Figure 4. A comparison between the results of pure
  components and the LPG mixture showed that reaction rate
rH 2 EH2  ECH4
C exp 16 of propane in the mixture was higher than that of the pure,
rCH4 RT except at the highest temperature at which it was higher for
pure propane. Whereas, the reaction rates of butane(s) in
where C is dened by Equation (17) pure form were higher than those in the mixture. It was

interesting to see that the reaction rate of i-butane
ko;H2 f1 Pi approaches that of n-butane when used pure. This suggests
C
17
ko;CH4 f2 Pi that the Ru=Al2O3 catalyst has similar activity toward both
butane(s), but in a mixture, n-butane competes better than
Over both catalysts, the selectivity increased with i-butane for the active sites on the catalyst.
temperature. Similar trend was also found for steam To explain this behavior, it should be noted that the
reforming of pure n-butane over Ni and PtNi catalysts. molar ow rates of the components in the mixture are lower
This suggests that EH2  ECH4 is positive (i.e., than their ow rates when they are used in pure form, at the
EH2 > ECH4 ) as shown in Equation (16). same total ow rate, due to their lower concentration in the
On the other hand, the higher sensitivity of selectivity former case. If the three components have the same afnity
toward temperature over Ni=Al2O3 suggests that the differ- toward the active sites on the catalyst, then one should
ence between the activation energies, EH2  ECH4 , over Ni= expect to witness no difference in their respective rates,
Al2O3 is larger than that over Ru=Al2O3. whether they are in the mixture or pure, at the same total
It was also found that the initial rate of reaction of molar ow rate. However, this is not the case, and the results
propane was the highest using both catalysts, followed by
n-butane. The initial rate of i-butane was always the lowest,
which suggests that both catalysts perform better on straight
molecules compared with branched ones. The conversion
also increased with the reduction in ow rate, due to the
increased residence time. However, this effect subsided as
the residence time increased. The high activation energy of
i-butane can be attributed to the shape of the molecule. It
is generally accepted that the activation energy is affected
by both chain length and structure. A branch on a molecule
increases the activation energy, compared with straight
molecules, mainly due to the increase in the diffusion of acti-
vation energy (Karger et al., 2012). This diffusion activation
energy of i-butane on zeolite was reported to be 31 kJ mol1,
more than double that of n-butane, which was reported to be
11.7 kJ mol1 only. The porosity of alumina is mainly due to
interparticle pores, and hence the diffusion is mainly con-
trolled by external surface resistance. Since linear molecules Fig. 4. Arrhenius plot for evaluating activation energy of steam
always show better diffusion, this implies that the external reforming of pure components using 2 g of Ru=Al2O3 catalyst,
surface resistance is expected to be lower for such molecules. at S:C ratio of 4.5.
Hydrogen Production by Steam Reforming 147

show that, propane competes on binding with the active sites

better than the butane(s). Therefore, when propane was used
in the mixture, the ratio of catalyst active sites available for
propane would be higher (due to their lower concentration
in the mixture), compared with when the entire ow rate
comprises of only propane. However, butanes, due to the
competition of propane, show lower reaction rates in the
mixture compared with being the only gas in the feed where
there is no competition effect. This increase was more
evident with i-butane compared with n-butane, because
i-butane seems to be the least effective in competing on the
active sites, which is further conrmed by having the highest
activation energy. Hence, when used in pure form the
i-butane molecules have a chance to engage with the entire
available active sites, without any competition with both,
propane or n-butane. Fig. 5. Effect of S:C ratio on hydrogen yield at different LPG
The increase in the reaction rate of pure iso-butane ow rates using 5 g of Ru=Al2O3 catalyst, at 773 K.
indicates that its conversion when pure follows a mechanism
that is different from that when it is mixed with other hydro-
carbons. It is believed that the presence of propane and
n-butane in the mixture competes for and blocks particular
active sites that when available would drive iso-butane
conversion via a different mechanism, which is the case when
it is the only gas in the feed. This interesting observation
stimulates further investigations for better understanding
of the mechanisms under both conditions.
The activation energy of each reactant was determined
from the slope of ln(rA) versus 1=T, as shown in Figure 4,
and the results are shown in Table II. It was found that
the activation energies of pure i-butane and n-butne were
still the highest and lowest, respectively, as in the case of
LPG mixture over the same catalyst. The activation energies
of the three components were higher when they were pure
compared with when they were mixed in LPG. This can be
Fig. 6. Effect of S:C ratio on H2:CH4 selectivity at different
referred to the enhanced possibility of multilayer adsorption
LPG ow rates using 5 g of Ru=Al2O3 catalyst, at 773 K.
of a pure component resulting in kind of condensation on
the surface. In other words, there is a chance that a molecule
from the gas phase interacts with an adsorbed, partially acti- ow rate, in the range of 50 and 85 mL min1, were tested,
vated, molecule when a pure component exists. On the other and the results are shown in Figure 5. The selectivity of
hand, this gas phaseadsorbed molecules interaction would H2:CH4 over Ru=Al2O3 catalyst was also determined, and
be less favored in the presence of different components. the results are shown in Figure 6. It can be seen that both,
the yield and selectivity, generally increase with the increase
in S:C ratio. This is expected as increasing the steam input
Steam:carbon Ratio pushes the reaction forward. It can be also seen that the yield
The yield of hydrogen production, dened by Equation (8), and selectivity increased with the decrease in the ow rate,
was determined using 5 g Ru=Al2O3 catalyst at 773 K. which is due to the increased residence time.
Different S:C ratios, in the range of 4.5 and 6.5, and LPG
Conclusion
Table II. Calculated E=R values of propane, i-butane, and
n-butane mixed in LPG, or in pure form, from the slopes of Steam reforming of commercially available LPG was inves-
ln(rA) versus 1=T lines, using 2g of Ru=Al2O3 and Ni=Al2O3 tigated using two catalysts, namely Ru=Al2O3 and Ni=
catalysts, at S:C ratio of 4.5 Al2O3. The effect of temperature, between 573 and 773 K,
on the rate of products formation and H2:CH4 selectivity
Component Propane i-Butane n-Butane was investigated. Coke and carbon monoxide formation
was not observed at S:C ratio of 4.5. The Ru=Al2O3 showed
LPG with Ru-Al2O3 4820 5341 4089
a superior performance in terms of products formation, but
LPG with Ni-Al2O3 7749 9423 9670
showed lower performance toward H2:CH4 selectivity. The
Pure components with Ru-Al2O3 6000 8471 5252
activation energies of the three components were determined
148 S. Al-Zuhair et al.

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