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Introduction
2
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
2
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
Literature Review
CH4 + H2 O CO + 3H2
H = 206 kJ/mol
(1)
CO + H2 O CO2 + H2
H = 41 kJ/mol
(2)
H = 165 kJ/mol
(3)
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.
Methane reforming involves three reactions (1),(2) and (3) which are used
in design of reactor.
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
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)
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)
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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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
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
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
(a)
10
(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
11
(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.
12
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.
7
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
13
Ki
kT
L
Pi
Pp
PT
Ri
Rm
T
TW
uS
V
Xi
YH2
z
H
b
g
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
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