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CATALYTIC CONVERSION OF METHANE TO

HYDROGEN USING NICKLE CATALYST IN A


PALLADIUM MEMBRANE REACTOR
Rakesh Kumar ,Rajat Punia,Rohit Kumar
November 2015

Submitted to:Dr. K.K.Pant


Department of chemical Engineering
IIT Delhi

Introduction

Hydrogen has been gaining favor as a suitable alternative to petroleum as


an energy source. Because of the large number of methods of its production there has been an increasing interest in developing products that utilize
hydrogen as a energy source. For a short term coal and another domestic
resources can also be used to produce hydrogen, thereby reducing the immediate pressure to import overseas petroleum. Hydrogens high specific energy
density of 120 MJ/kg makes it favorable for many applications, and it is a
potential alternative to the current oil-based energy production methods in
industrial and automobile sectors.
Hydrogen is produced by various methods like water electrolysis, by
natural gas reforming,from the biomass or by the solar thermal dissociation
of water at high temperature,by dry (with CO2) reforming, by wet (with
H2O) reforming, partial oxidation of methane,catalytic cracking of methane
using a variety of alumina-supported nano-scale mono and binary metal
catalysts or over nickel gauze.Also their are different types of reactors that
are used like periodic reactor,packed bed reactor,fixed bed tubular reactor
etc that are used in the production of hydrogen.Hydrogen production using
steam reforming of methane with nickle catalyst appears as an alternative
process due to its low raw material cost and the favourable balance energy
especially when done in membrane reactors. In this process, methane reacts
with steam to produce a mixture of hydrogen,carbon dioxide and carbon
monoxide. This reaction is highly endothermic and is performed in the
presence of a catalyst such as nickel at high temperature (800-1000 C), high
pressure(20-40 bars) and steam-to-carbon ratio varying between 1.8 and 4
but use of membrane reactor decreases the high temperature required in this
process.

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2.1

Importance/Applications of Hydrogen
Industrial Uses

Hydrogens primary industrial uses have been in ammonia production and oil
refining. Ammonia, which consumes half of the globally-produced hydrogen,
is produced by reacting atmospheric nitrogen with hydrogen. It is used in
fertilizer manufacturing, industrial refrigeration. Ammonia is also used in
cleaning and sanitizing applications. Hydrogen is also used in the oil refining
process, an application which accounts for about 352 to produce gasoline and
diesel fuel, and also aids in sulfur removal. Reformed hydrogen is also used to
reduce other atmospheric pollutants, such as nitric oxides (NOx) and other
hydrocarbon fuel emissions. Both sulfur and NOx are key contributors to
acid rain, which is extremely detrimental to the regional climate. Increased
focus in sulfur and NOx reduction has increased the demand for hydrogen
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production. Other uses for hydrogen which drive demand for production
include metallurgy, chemicals and pharmaceuticals, glass and ceramics, food
and beverages and electronics.

2.2

Fuel Cells

A well-known technology for converting the hydrogen into electrical energy


is the fuel cell. Fuel cells have been gaining popularity in recent years due
to their zero-emission, whereby hydrogen is reacted with oxygen in the presence of an electrolyte to produce electricity with pure water as the reaction
byproduct. Because fuel cells convert the chemical energy provided by a fuel
directly into electrical energy, they can be about twice as efficient as conventional technologies that rely on a combustion step to convert the chemical
energy into thermal energy before the subsequent conversion step to electrical energy, losing about 70conversion (with the remaining 40attain energy
conversions of up to 90automotive market, which has potential revenues of
up to $ 252B.

Literature Review

Methane steam reforming involves three reactions two reversible reactions:


the reforming reaction(I)and the Water-Gas-Shift reaction(II).The third one
is the global reaction(III). Reaction I and III are endothermic, but the water
gas shift reaction is exothermic.
The reactions are as follows:

CH4 + H2 O CO + 3H2

H = 206 kJ/mol

(1)

CO + H2 O CO2 + H2

H = 41 kJ/mol

(2)

CH4 + 2H2 O CO2 + 4H2

H = 165 kJ/mol

(3)

Since Steam reforming is a highly endothermic process ,in order to achieve


near equilibrium conversion, steam reforming in conventional technology is
conducted on a supported nickel catalyst and at high temperaure.For Examle,if steam reforming is done in a multi-tubular reactor operated at a
temperature of 850C, a pressure ranging from 1.6 to 4.1 mPa, and a steam
to methane ratios between 2 and 4 . Methane conversion is usually around
78Likewise if done in packed bed reactor,under the following conditions:
supported nickel catalyst (Ni/Al2O3), the catalyst mass=0.012-0.020g, pressure=1atm, temperature=500C (moderate pressure and temperature) and
with steam to methane ratio in the range of 2-6.The conversion of methane
always increases with steam to methane ratio. From the above two examples,it is showed that in general it is not possible to obtain satisfactory
conversions of methane at moderate temperatures,because the reforming
reaction is endothermic and thermodynamically favoured by a high temperature and a low pressur.Therefore, the use of membrane based separation
process could make it possible to increase the conversion in the reforming
process also it is a possible way to liberate this reaction from the equilibrium limitation and thus attain a high methane conversion at lower temperatures is by the use of membrane reactors. The membrane continuously
removes the hydrogen produced in the catalytic reaction zone thus pushing
the chemical equilibrium and allowing higher methane conversion at a lower
temperature .As an additional advantage ,the membrane reactor offers the
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possibility of supplying hydrogen with same conversion degree in high purity.The membranes used in catalytic reactors are generally characterized
with a high permeability, a good selectivity of separation and are stable to
the temperature of the reaction especially in the presence of gas. The hydrogen separation membranes used in these membrane reactors are of two
kinds: porous Vycor glass, or palladium or its alloys. The limitation to
achieve a desired conversion forms a disadvantage of the membrane reactor
using porous Vycor glass membrane, in which gas separation is based on the
Knudsen diffusion. On the other hand, the palladium membrane reactor can
attain high levels of conversion (even 100 percent ),but it has a disadvantage
of low efficiency or low rate of reaction.

Design Equations of Reactor

Methane reforming involves three reactions (1),(2) and (3) which are used
in design of reactor.

Assumptions made for the Reactor


Steady state operation
Non-isothermal conditions
Plug-flow on both reaction and permeation zones
Intrinsic kinetics for methane steam reforming and water gas shift reactions
No boundary layer on membrane surfaces
The kinetic model for the reaction on a N i/M gAl2 O4 catalyst is based
on a LangmuirHinshelwood reaction mechanism in which the rate expressions for reactions (1),(2) and(3) are given by

R1 =

R2 =

k1
2.5
PH


PCH4 .PH2 O

3 .P
PH
CO
2
K1


(4)

DEN 2
k2
PH2

PCO .PH2 O
DEN 2

PH2 .PCO2
K2

i
(5)

k3
3.5
PH
2

R3 =

PCH4 .PH2 2 O

4 .P
PH
CO2
2
K3


(6)

DEN 2

DEN = 1 + KCH4 .PCH4 + KCO .PCO + KH2 .PH2 +

KH2 O .PH2 O
PH2

(7)

where Fi0 is the flow rate of component i in the feedstock (mol/h); ki is the
rate constant of reaction i; Ki is the equilibrium constant of reaction i or
adsorption coefficient of component i; Pi is the partial pressure of
component i (atm); andRi is the rate of reaction i (mol/h gcat).
Partial pressures for each component are given by
PCH4 = (1 XCH4 ).

FH2 O
XH2 O .
=
FCH4

(8)

PH 2 O

#
FH0 2
XH2 .
=
0
FCH
4

(9)

"

PH2

PCO = XCO .

(11)

PCO2 = XCO2 .

(12)

PT

=
1+

FH2 O
FCH4

0
FH

2
0
FCH
4

(10)

(13)

+ XH2 XCH4 XH2 O + XCO + XCO2

The dimensionless flow rates of component i relative to initial flow rate of


methane on the reaction side and the dimensionless flow rate of hydrogen
on the permeate side relative to initial flow rate of methane are given by

XCH4 = 1

FCH4
0
FCH
4

(14)

XH2 O = 1

FH2 O
FH0 2 O

(15)

XH2 =

FH2
0
FCH
4

(16)

XCO =

FCO
0
FCH
4

(17)

XCO2 =

FCO2
0
FCH
4

(18)

The dimensionless flow rate of hydrogen in the permeate side relative to


initial flow rate of methane is given by

YH2 =

FHP2S
0
FCH
4

(19)

The rate of change of each component along the reactor length is given by

b .V
dXCH4
= 0 (R1 + R3 )
dz
FCH4

(20)

dXH2 O
b .V
= 0 (R1 + R2 + 2R3 )
dz
FCH4

(21)

b .V
dYH2
dXH2
= 0 (3R1 + R2 + 4R3 )
dz
dz
FCH4

(22)

dXCO
b .V
= 0 (R1 R2 )
dz
FCH4

(23)

dXCO2
b .V
= 0 (R2 + R3 )
dz
FCH4

(24)


dYH2
2.Rm .L.
=
. PH0.52 Pp0.5
0
dz
.FCH4

(25)

where A is the cross-sectional area of the tube (m2 ); G0i is the flow rate of
component i in the feedstock (mol/h m2 ); Pp is the hydrogen partial
pressure in the permeate zone (atm); Rm is the radius of the membrane
(m); is the permeance of the membrane (m3 /m h atm0.5); d is the
membrane thickness (m); b is the catalyst density (g/m3 )
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The temperature gradient along the reactor length is given by

P
dT
2.kT . (TW T ) + Ri . (Hi ) .b
=
dz
Cp .g .us

(26)

where CP is the heat capacity (J/g K); kT is the heat transfer coefficient
(J/h m2 K); rT is the radius of the reaction tube (m); TW is the wall temperature (K); uS is the superficial velocity (m/h); H is the heat of reaction
(J/mol); g is the gas density (g/m3 )

The kinetic parameters for the reaction, equilibrium constants and membrane permeance are presented in Table 1. The simulated operating conditions are presented in Table 2.

Parameter
k1
k2
k3
kCH4
kH2O
kH2
kCO
K1
K2
K3

Pre-Exponential Factor
4.2248*101 5(mol

atm0.5/g h)
h)
1.0202*101 5(mol atm0.5/g h)
6.65*104 atm1
1.77*105
6.12*109 atm1
8.23*105 atm1
7.846*1012 atm2
1.412*102 atm2
1.11*1011 atm2
2.889*101 mol/m.h.atm.5
1.955*106 (mol/g

Ea or H
240.1
67.13
243.9
-38280
88680
-82900
-70650
220200
-37720
182400
-70650

Table 1: Kinetic parameters for methane steam reforming


A numerical problem can arise from the initial value of hydrogen in the
feedstock, which if zero (hydrogen-free feedstock), will generate a division
by zero in the reaction rate equations. This problem is overcome by setting
a very small value for hydrogen partial pressure at the inlet of the reactor.
Differential Eqs. (19), (20), (21), (22), (23), (24) and (25) were solved
numerically by a 5th order RungeKuttaGill method.

Methane Flowrate[mole/hr]
Water/Methane Ratio
C02/Methane Ratio
Hydrogen /Methane
Nitrogen /Methane
Total Pressure[atm]
Catalyst Density[gcat /m3 ]
Reactor Length[m]
Tube Internal Radius[m]
Tube External Radius[m]
Membrane Radius[m]
Membrane Thickness[m]

5200
3.358
0.056
0.122
0.164
29
2355.2
20
.1016
.1322
0.0203
2.0X105

Table 2: Operating conditions and reactor parameters

Result and Discussion

The major advantage of the membrane reactor is the enhancement in conversion of the equilibrium-limited reaction as a result of selective hydrogen
removal. As observed in Fig. 3, the utile(advantageous) reactor length for
a conventional reactor is about 1012 m, after which the reaction reaches
equilibrium. In membrane reactors the utile reactor length can be over 20
m since the equilibrium is shifted by hydrogen removal. Fig. 3 shows a
lower partial pressure of hydrogen throughout the membrane reactor than
in the conventional reactor, indicating hydrogen removal from the reaction
zone and thus, the shift of the reaction towards the products. The figure
also shows an increase in CO and CO2 partial pressures.

5.1

Influence of temperature

Temperature plays an important role in methane steam reforming, especially


at middle temperatures (from 800 to 900K) where the membrane reactor displays a greater conversion of methane compared to the conventional reactor
(Fig. 4a). At 850 K, there is an additional conversion of 22.8 percent if
compared to the conventional reactor. At temperatures below 800K the
conversion is low, but the difference among reactors is increased and the
membrane is responsible for an increase of 28.2 percent on the conversion.
At temperatures higher than 950K the conversion on both reactors is high
enough so the membrane only increases the conversion in 3.1 percent .
Figure 4b shows the fraction of hydrogen that is removed from the reaction zone at different temperatures. Lower temperatures favor the permeance of hydrogen, which easily permeates through the membrane leading
to a high fraction of hydrogen in the permeation zone.Figure 4b shows the
fraction of hydrogen that is removed from the reaction zone at different
temperatures. Lower temperatures favor the permeance of hydrogen, which
easily permeates through the membrane leading to a high fraction of hydrogen in the permeation zone.
The removal of hydrogen from the reaction side decreases with the increase in temperature. From 750 K to 850 K (middle temperatures), a
decrease in the hydrogen content in the permeate zone is observed due to
the lower capacity of the membrane in removing hydrogen from the reaction
side. Above 850 K a new increase in the hydrogen content in the permeate
zone is observed. This increase is mainly due to the higher reaction rate
that increases the partial pressure of hydrogen in the reaction side leading
to a larger hydrogen partial pressure gradient between the reaction and the
permeate zones, which causes a higher hydrogen removal.

(a)

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(b)
(Fig. 4. Influence of temperature in the reactor performance, (a) methane
conversion, (b) fraction of produced hydrogen that goes to the permeate
zone.)

5.2

Influence of H2O/CH4 ratio

Methane steam reforming usually proceeds in the presence of an excess of


steam to prevent carbon deposition over the catalyst surface and to enhance
steam reforming. The effect of molar steam-to-methane (H2O/CH4) ratio
was examined by varying this ratio from 1.5 to 4.5. Results for two different
temperatures are shown in Fig. 5. The higher water/methane ratio in the
feedstock favors higher conversions, but at the expense of increasing the
H2/CO ratio, which increases considerably at low temperatures (Fig. 5b).
If hydrogen in excess if undesirable, such as for GTL(Gas to Liquid)
processes, the reactor should be run preferably at low water: methane ratios,
which can result in the formation of free carbon.
Free carbon deactivates the catalyst and therefore is undesirable, but free
carbon formation can be avoided by recycling part of the hydrogen steam
from the permeate zone to the entrance of the reactor. This additional
hydrogen feed contributes to avoiding conditions favorable to solid carbon
formation.

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(a)

(b)
(Fig. 5. Influence of watenmethane ratio in the reactor performance, (a)
methane conversion and (b) H2/CO ratio (P = 29 atm))

5.3

Influence of Pressure

Higher pressure and thus, increase of hydrogen partial pressure on the reaction side increases the driving force for hydrogen permeation, resulting
in an enhancement of the methane conversion. As shown in Fig. 6, higher
pressures contribute to an increase in the hydrogen mass transfer from the
reaction zone to the permeate zone. Low operating pressures (below 10 atm)
do not offer great advantages and the membrane reactor performs much like
the conventional reactor.

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(Fig. 6. Scheme of the membrane reactor)

Conclusion

The methane steam reforming was studied from a modeling point of view in a
membrane reactor and a conventional reactor. Simulation results show that
different parameters affect methane conversion and H2 /CO ratio, such as
temperature, operating pressure, and membrane parameters such as membrane thickness, membrane permeance and membrane tube diameter. In a
conventional system an increase in the operating pressure causes a decrease
in methane conversion, but in a membrane reactor an increase in the operating pressure corresponds to an increase in methane conversion, since allows
for a greater partial pressure gradient between the reaction and permeate
zone, thus contributing to shift the equilibrium towards the products.
As such, the membrane reactors are a good alternative to produce syngas for GTL processes or pure hydrogen. Operating conditions can be set to
control the H2 /CO ratio to a desired value, removing H2 through the membrane. High conversions at mild temperatures can be achieved reducing
capital and operational costs.

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CP
Fi
Fi0
FiP S
ki

Nomenclature
heat capacity [J/g.K]
flow rate of component i [mol/h]
flow rate of component i in the feedstock [mol/h]
flow rate of component i in the permeate side [mol/h]
rate constant of reaction i
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Ki
kT
L
Pi
Pp
PT
Ri
Rm
T
TW
uS
V
Xi
YH2
z

H
b
g

equilibrium constant of reaction i or adsorption coefficient of


component i
heat transfer coefficient [J/h.m2.K]
membrane tube length [m]
partial pressure in the reaction zone [arm]
hydrogen partial pressure in the permeate zone [arm]
total pressure in the reaction zone [arm]
rate of reaction / [mol/h.gcat]
radius of the membrane [m]
temperature [K]
wall temperature [K]
superficial velocity [rn/h]
reactor volume [m3]
conversion of component i or dimensionless flow rate of component i
relative to initial flow rate of methane
dimensionless flow rate of hydrogen in the permeate zone relative to
initial flow rate of methane in reaction zone
dimensionless reaction tube length
permeance of the membrane [mol/m.h.atm0.5]
membrane thickness [m]
corrected pressure [arm]
heat of reaction [J/mol]
catalyst density [g/m3]
gas density [g/m3]

References

Modeling of methane steam reforming in palladium membrane reactorF.A.N Farnandez and A.B Soares JR.(36:155-161)2006
Methane Steam Reforming Reaction Behaviour in a Packed Bed Membrane Reactor -Lemnouer Chibane and Brahim Djellouli ( Vol.2,No.3,June
2011)
Steam reforming of methane in a hydrogen-permeable membrane reactorShigeyuki Uemiya*, Noboru Sato, Hiroshi Ando, Takeshi Matsuda and Eiichi Kikuchi 1991 ( 223-230)
Heat and Mass Transfer Correlations for Steam Methane Reforming in NonAdiabatic, Process- Intensified Catalytic Reactors-Adam Stephen Kimmel
Membrane Reactor for Hydrogen Production-AIChE 2008 Annual Meeting, Philadelphia, PA

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Contributions of Members

All have made almost equal contributions .

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