Fuel Processing Technology 91 (2010) 600612

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Fuel Processing Technology

j o u r n a l h o m e p a g e : w w w. e l s ev i e r. c o m / l o c a t e / f u p r o c

Hydrogen production from urea wastewater using a combination of urea thermal

hydrolyserdesorber loop and a hydrogen-permselective membrane reactor
M.R. Rahimpour , H.R. Mottaghi, M.M. Barmaki
Department of Chemical Engineering, School of Chemical and Petroleum Engineering, Shiraz University, Shiraz71345, Iran

a r t i c l e i n f o a b s t r a c t

Article history: This work presents novel application of palladium-based membrane in a wastewater treatment loop of urea
Received 5 September 2009 plant for hydrogen production. Urea wastewater treatment loop is based on combined thermal hydrolysis
Received in revised form 1 January 2010 desorption operations. The wastewater of urea plant includes ammonia and urea which in the current
Accepted 1 January 2010
treatment loop; urea decomposes to ammonia and carbon dioxide. The catalytic hydrogen-permselective
membrane reactor is proposed for hydrogen production from desorbed ammonia of urea wastewater which
Keywords:
much of it discharges to air and causes environmental pollution. Therefore hydrogen is produced from
Hydrogen production
Hydrogen-permselective membrane
decomposition of ammonia on nickelalumina catalyst bed simultaneously and permeates from reaction side
Catalytic reactor to shell side through thin layer of palladiumsilver membrane. Also a sweep gas is used in the shell side for
PdAg membrane increasing driving force. In this way, 4588 tons/yr hydrogen is produced and environmental problem of urea
Urea wastewater plant is solved. The membrane reactor and urea wastewater treatment loop are modeled mathematically and
Wastewater treatment the predicted data of the model are consistent with the experimental and plant data that show validity of the
model. Also the effects of key parameters on the performance of catalytic hydrogen-permselective
membrane reactor such as the temperature, pressure, thickness of PdAg layer, conguration of ow and
sweep gas ow ratio were examined.
2010 Elsevier B.V. All rights reserved.

1. Introduction
Hydrogen is a major industrial commodity used as a feedstock or
intermediate in a wide range of chemical, petrochemical and
metallurgical processes. Although hydrogen is the most abundant
element in the universe, elementary hydrogen gas is hardly found on
earth [1,2]. It is therefore necessary to extract hydrogen from either
water or hydrocarbons. Existing hydrogen production is mainly based
on biological processes, electrochemical water electrolysis, or chem-
ical methods [3]. Chemical methods dominate the market for
commercial hydrogen production. At present, approximately 95%
hydrogen is generated by steam/partial oxidation reforming of natural
gas and coal gasication [4,5]. Ammonia-based hydrogen production
is another approach that can be promising for a safe and affordable
way for generating hydrogen. Ammonia stores 17.6 wt.% hydrogen
and does not contain carbon atoms that can cause coking or carbon
monoxide and carbon dioxide production [6,7].
In some petrochemical production plants such as ammonia and
urea production plants, excessive amount of ammonia is being
emitted to the atmosphere or discharged with wastewater efuent
streams, it is considered as one of those harmful pollutant constitu-
ents that seriously damage the environment [8,9]. In urea plants
Corresponding author. Tel.: +98 711 2303071; fax: +98 711 6287294.
E-mail address: rahimpor@shirazu.ac.ir (M.R. Rahimpour).
having capacity of 1500 tons of urea per day, roughly 750800 tons of
water has to be discharged as a wastewater stream from the process
per day. Such a stream generally contains about 29 wt.% ammonia,
0.86 wt.% carbon dioxide and 0.31.5 wt.% urea [10,11].
Discharging this wastewater from urea plants still presents
problem of water pollution as well as loss of urea and raw materials
such as ammonia. While in the past decade, 100 ppm of urea and
100 ppm ammonia were considered acceptable for wastewater of
urea plants, but today's requirements mostly call for a maximum
concentration of 10 ppm for both of them [12]. Economically, it is
preferred to remove and recover the urea and/or ammonia from the
wastewater. The simultaneous thermal hydrolysis and stripping is an
existing technique to achieve wastewaters with ammonia and urea
levels below 1 ppm [10]. Nevertheless, in some urea plants, much of
ammonia vents to the atmosphere. As active chemical species,
ammonia in the atmosphere oxidizes and when it is washed out by
rain, it forms nitric acid. As a consequence, acidic rain increases
acidication problem in soil and ground water [13]. Besides, due to its
high solubility in water and to its chemical reactivity, ammonia is
considered cause for eutrophication of surface water and also for the
depletion of oxygen in receiving water lakes and rivers [14,15].
Urea removal from wastewater of modern and conventional urea
plants was studied more thoroughly [1619]. Nowadays higher and
higher demands are put onto new separation technologies due to
stricter product quality requirements, environmental legislation,
energy efciency demands and needs for cost reduction. In order to

0378-3820/$ see front matter 2010 Elsevier B.V. All rights reserved.
doi:10.1016/j.fuproc.2010.01.006
 M.R. Rahimpour et al. / Fuel Processing Technology 91 (2010) 600612
meet these ever increasing needs there is a tendency to combine
processes to a hybrid process. In a membrane reactive separation
system a separation process is combined with reaction process, but
both processes are fully integrated and incorporated into one piece of
equipment. The application of membrane conversion technology in
chemical reaction processes is now mainly focused on reaction
systems containing hydrogen and oxygen, and is based on inorganic
membranes such as Pd and ceramic membranes [20].
Palladium-based membranes have been used for decades in
hydrogen extraction because of their high permeability and good
surface properties and because palladium is 100% selective for
hydrogen transport [21]. These properties would make palladium-
based membranes such as PdAg membrane very attractive for use
with petrochemical gases. Catalytic membrane reactor has been the
subject of numerous recent investigations such as steam reforming of
methane, dehydrogenation reactions, partial oxidation of methanol
synthesis and GTL technology [2239].
In the present work, novel application of membrane reactor in
wastewater treatment loop of urea plant for hydrogen production has
been investigated. In this loop a thermal hydrolyser is used for urea
decomposing, and two desorbers are used for removal of ammonia
and carbon dioxide. For decomposition of desorbed ammonia, the
catalytic hydrogen-permselective membrane reactor has been sug-
gested. This membrane reactor produces hydrogen and decreases
ammonia pollution.
Rahimpour and Asgari studied the ammonia removal and
hydrogen production from purge gases of an ammonia plant in the
catalytic hydrogen-permselective membrane reactor [20,40]. Until
now, the published information in literature about urea and ammonia
removal from industrial wastewater of urea plants is very little
detailed and patented [11], especially in ammonia removal. However,
Fig. 1. Process wastewater treatment system with membrane reactor. The boundaries are shown for the material balance equations.
601
there is no information available in the literature regarding applica-
tion of catalytic hydrogen-permselective membrane reactor in urea
plants to ammonia removal besides hydrogen production. Therefore,
we decided to study more thoroughly this phenomenon.
2. Process description
Fig. 1 shows a schematic diagram of a wastewater treatment loop
of the modern urea plant including proposed membrane reactor [10].
It mainly consists of a rst desorber column, which reduces the
ammonia and carbon dioxide contents. This column operates at a low
pressure which facilitates the desorption process. Then the efuent is
warmed up and fed into the hydrolysis reactor, where urea is
decomposed to ammonia and carbon dioxide. The residence time in
hydrolyser is approximately 1 h. Hydrolyser is operated at relatively
medium pressures (20 bar) resulting in a temperature of about
200 C. In the liquid outlet of hydrolyser the urea content is decreased
to ppm level. The temperature level in the hydrolyser is maintained by
the injection of high pressure (HP) steam. In the second desorber
column again operating at low pressure the ammonia and carbon
dioxide contents are decreased to ppm level. The stripping in the
second desorber is done by using life low pressure (LP) steam injected
in the bottom.
Vapors from the hydrolyser and second desorber are used for the
stripping in the rst desorber. The overhead vapors of the rst
desorber which contain ammonia, carbon dioxide and water are
condensed in a submerged reux condenser. Residual NH3 in the
separator off-gas should be removed. Then temperature and pressure
of off-gas after passing the heater and compressor are 550 C and
36 atm. This stream is fed into the catalytic hydrogen-permselective
membrane reactor which ammonia decomposes to hydrogen and
602 M.R. Rahimpour et al. / Fuel Processing Technology 91 (2010) 600612

nitrogen components. Two processprocess heat exchangers decrease Table 1

the needed high pressure (20 bar) and low pressure steam amounts Equilibrium constant parameters [46].

considerably. Finally, treated efuent is used as a boiler feed water or Function Parameters
further used in cooling equipment.
U1 U2 U3 U4

ln K2 31,363 64.26 0.0595 482.11

3. Theory
ln K3 11,046 5.19 0.01115 51.47

3.1. Urea hydrolysis

The overall reaction of urea hydrolysis is as follows below [41,42].

3.2. Decomposition rate of ammonia
NH2 CONH2 H2 O2NH3 CO2 1
The process of urea hydrolysis consists of two sequential steps. In Ammonia over Ni/Al2O3 catalyst decomposes to hydrogen and
the rst step, ammonium carbamate is formed by the reaction nitrogen.
between urea and water:
NH3 1=2N2 3=2H2 10
kJ Ammonia decomposition/synthesis rate equation on a solid
NH2 CONH2 l + H2 OlH2 NCOO + NH4 H298 = 23 :
mol catalyst is assumed to obey TemkinPhyzev mechanism [47].
2 Corresponding rate equation was generally accepted by many authors
[48,49]. This reaction rate equation is:
In the next step, the ammonium and carbamate ions react to yield 2
2
! 3
!1 3
carbon dioxide and ammonia in liquid phase, while the vapor and PNH3 PN PH2
liquid phases are at equilibrium: rNH3 = k4 22 5 11
PH3 2 Keq 2
PNH 3

kJ
H2 NCOO + NH4 2NH3 l + CO2 l H298 = 84 3 where:
mol
k = k0 expE = RT: 12
CO2 lCO2 g 4

The rst term within the brackets of the rate equation is ammonia
NH3 lNH3 g 5 decomposition while the second term is the rate of ammonia
synthesis. There are three kinetic parameters in the rate equation,
Reaction (2) is the rate controlling step and its rate is considered as
the pre-exponential factor k0(mol/m3 s Pa 0.674), the activation
the overall rate of urea hydrolysis [41,42]. For chemical reactions in
energy E and . These parameters were measured experimentally for
thermodynamically non-ideal systems, as shown elsewhere [43,44],
NH3 decomposition over Ni/Al2O3 catalyst on the pressure range 929
the rate becomes:
to 3549 kPa for a wide range of NH3 and H2 ratios [50]. A value of 0.674

   was obtained for . The resulting Arrhenius-type relationship for the
1 1
R = kf a1 a2 a3 a4 = kf 1 C1 2 C2 3 C3 4 C4 6 rate constant is:
K2 K2
!
19 2:304 105
where kf is the forward reaction rate constant (kf =k0 exp (E/RT)) and k = 5:744 10 exp : 13
RT
K2 is the equilibrium constant of reaction (2). ai, i are the activity and
activity coefcient of species i, respectively. Ci is the molar concentration
of species i. The experimental values of the pre-exponential factor and The thermodynamic equilibrium constant Keq dened by Harrison
the activation energy in the Arrhenius expression of k f are and Kobe according to the following equation [51]:
k0 = 3.75 107 m3/kmol h and E = 87,780.3 kJ/kmol, respectively [45]. !
1 2250:322 5
The equilibrium constants for reactions (2) and (3) are dened as Log = 0:85341:51049l logT25:8987 10 T
Keq T
follows:
8 2


 + 14:8961 10 T : 14
x3 x4 3 T; X4 T; X
K2 T = r=2 7
x1 x2 1 T; X2 T; X

! ! 3.3. Permeability of PdAg membrane

x5 x26 5 T; X26 T; X
K3 T = r=3 8
x3 x4 3 T; X4 T; X The composite membrane used in this study is made of very thin layer
of palladiumsilver alloy. The membrane is deposited as a continuous
layer on the outer surface of thermo stable support. The permeation rate
where the activity coefcient of each species in the reacting solution
of hydrogen through the PdAg membrane [QH (mol/s)] is assumed to
can be calculated from thermodynamic model which is summarized
obey FickSieverts' law [52,53], then:
in Appendix A. The following functional form:
 
A

 1=2 1=2
Q H = Q 0 PH;t PH;s 15
U1;r
ln Kr T = + U2;r ln T + U3;r T + U4;r 9
T
where Q 0 is the permeability constant of hydrogen gas through the
was adopted to describe the temperature dependence of the r membrane (mol cm/(cm2 s atm1/2)); A is the membrane area available
reaction equilibrium constant [41,46]. In the above equation, Ur is a for ow; and is the lm thickness of the membrane. The permeation
constant related to reaction of number r where tabulated in Table 1. rate of hydrogen is directly proportional to the difference in square
 M.R. Rahimpour et al. / Fuel Processing Technology 91 (2010) 600612 603

roots of the upstream and downstream hydrogen partial pressures.

The permeability constant of hydrogen gas (Q 0) through PdAg lm
obey the Arrhenius law and can be expressed as follows [54,55]:


9 6:38
Q 0 = 3:2027 10 exp 16
RT

where, R is universal gas constant and T is absolute temperature.

Generally, Eq. (15) is known as Richardson equation.

4. Model development

In this section the hypothesis and necessary equations for

developing the steady state model of the urea and ammonia removal
section of urea plant which result in hydrogen production are
described. First of all the models representing the process behaviors
are needed. The process has nine unknown streams that are output
liquid stream of rst desorber, output vapor stream of rst desorber,
output liquid stream of hydrolyser, output vapor stream of hydrolyser,
output liquid stream of second desorber, output vapor stream of
second desorber, off-gas stream, separated liquid stream and output Fig. 2. Schematic diagram of the multi-stage well-mixed reactor model.
stream of membrane reactor. The mole fractions of all components are
unknown, but the specication of the reux stream is similar to the
separated liquid stream. The reux ratio is constant and wastewater
rent urea thermal hydrolyser. The equations related to the steady
feed and off-gas streams values are known.
state behavior of the urea thermal hydrolyser are summarized in
In this study, simulation of the wastewater treatment loop was
Table 2. Since the column is generally operated at the medium
done based on the following assumptions:
pressure, the vapor fugacity coefcients can be estimated with the
Reactions of hydrolysis take place only in the liquid phase. PHS equation of Nakamura et al. [56].
The loop operates at steady state condition.
Each stage of hydrolyser is perfectly mixed stirred-tank reactor (CSTR).
4.2. Simulation of the desorbers (second and fth boundaries)
Each CSTR operates adiabatically.
Phase equilibrium is achieved in each stage.
In the desorption part, the liquid stream containing water,
Vapor holdup in hydrolyser is assumed to be negligible (hydrolyser
ammonia and carbon dioxide is passed downward through the
is full of liquid).
desorber column, countercurrent to the hot gas or LP steam entering
The volatility of urea and ammonium carbamate is negligible, so the column at the bottom. In this stage, ammonia and carbon dioxide
there are only three molecular components including H2O, NH3 and
are transferred from the liquid stream to the gas phase. This provides
CO2 in the vapor phase. treated water, with low ammonia content, passing out of the column
CO2 is not dissolved in the liquid phase in desorbers. In fact, it could
bottom.
only be condensed with ammonia to form ammonium carbamate in
In the desorber column, carbamate decomposition takes place,
the liquid phase.
which can be considered at equilibrium reaction, and then ammonia
and carbon dioxide are stripped off from the liquid phase to the gas
4.1. Simulation of the hydrolyser (third boundary)
phase. An equilibrium-stage model with Murphree efciency is
extended to simulate the desorbers. Also, for rst desorber, stage 1
For modeling of reactive separation columns, the equilibrium and
can be a partial condenser. The equations related to the steady state
the non-equilibrium (NEQ) stage models are available in the
behavior of the desorbers are summarized in Table 2.
literatures. In this study, due to lack of the data of transfer properties
for carbon dioxide and ammonia under the hydrolyser operating
conditions, we attempt to develop the equilibrium-stage model that is 4.3. Simulation of the heat exchangers (rst and fourth boundaries)
based on rigorous thermodynamic model.
A schematic illustration of an equilibrium stage is provided in There are no phase changes in the heat exchangers and the
Fig. 2. Vapor from the below stage is brought into contact with liquid equations related to the steady state behavior of the heat exchanger
from the above stage. The feed to the urea thermal hydrolyser consists are represented in Table 2.
of liquid (water rich) stream entering from the top and pure HP steam
stream entering from the bottom as the stripper. While the hydrolyser 4.4. Simulation of the membrane reactor (sixth boundary)
is full of liquid, the movement of bubbles through the liquid phase
causes mixing in the liquid phase. Moreover, there are several A schematic of catalytic membrane reactor for ammonia decom-
perforated plates at different levels inside the hydrolyser in order to position is shown in Fig. 3. This reactor is considered as two concentric
prevent back mixing and further mixing between the two phases. pipes. The inner pipe is catalytic reaction side and the other pipe is
As noted above, for simulation purposes, the urea thermal shell side. The inner tube supports a dense lm of PdAg and the outer
hydrolyser can be approximated as a series of continuous multi- one is the non-permeable shell. The materials are owing through the
stage stirred-tank reactors (CSTRs). Rahimpour et al. [17,18] and reaction and shell sides in co-current and countercurrent ow modes.
Barmaki et al. [19] considered respectively, the co-current and Ammonia over Ni/Al2O3 catalyst converts to nitrogen and hydrogen
countercurrent urea thermal hydrolyser as a sequence of continuously permeates through PdAg membrane reactor.
stirred-tank reactor (CSTRs). The same approach has been adopted in A mathematical model is considered to describe shell and tube
the present study for the hydrodynamic behavior of the countercur- catalytic membrane reactor behaviors. Mass balance for each component
604 M.R. Rahimpour et al. / Fuel Processing Technology 91 (2010) 600612

Table 2
Model equations.

Section Equation Description

Urea thermal hydrolyser
(each CSTR)
Ammonia and carbon dioxide
desorbers (each stage)
Membrane reactor
Heat exchangers
Mi, j Vj + 1yi, j + 1 + Lj 1xi, j 1 + i,2HjRov j + i,3w Vjyj Ljxj = 0 i = 1, , M Mass balance equations (M)
Ei, j Ki, jxi, j yi, j = 0 j = 1, , N Phase equilibrium equations (E)

2 

x5; j x 5; j T; X26; j T; X
Ec; j K3; j T x3; j x6;4; jj 3; j T; X4; j T; X = 0 Chemical equilibrium equations (E)
M M
Sxj xi;j 1 = 0 Syj yi;j 1 = 0 Summation equations (S)
i i
M M M M
Hj Vi; j + 1 Hi;v j + 1 + Li;j1 Hi;l j1 Vi; j Hi;v j Li; j Hi;l j =0 Heat balance equation (H)
i i i i
P1 ptop p1 = 0, Pj pj pj 1 pj 1 = 0 j = 2, , N Hydraulic equations (P)
Mi, j Vj + 1yi, j + 1 + Lj 1xi, j 1 + i,3w Vjyj Ljxj = 0 i = 1; ; M Mass balance equations (M)
j = 1; ; N
Ei, j EMi, j(Ki, jxi, j yi, j + 1)/(yi, j yi, j + 1) 1 = 0 Phase equilibrium equations with
Murphree efciency (E)
M M
Sxj xi; j 1 = 0 Syj yi; j 1 = 0 Summation equations (S)
i i
M M M M
Hj Vi; j + 1 Hi;v j + 1 + Li; j1 Hi;l j1 Vi; j Hi;v j Li; j Hi;l j =0 j = 2, , N Heat balance equation (H)
i i i i
P1 ptop p1 = 0, Pj pj pj 1 pj 1 = 0 Hydraulic equations (P)
M M M
Hj Vi;1 Hi;1
v
Vi;c Hi;c
v
Li;c Hi;c
l
QC = 0 Heat balance equation for the partial condenser
i i i
dFit d2
dz
= dQ
dz
i
+ i rNH3 4 Tube side mass balance equations (M)
dFis
dz
= F dQdz
i
Shell side mass balance equations
(FhCPhTh)L (FhCPhTh)0 Qh = 0 Energy balance for hot stream
(FcCPcTc)L (FcCPcTc)0 Qc = 0
Qc = UcAc(TM Tc) Energy balance for cold stream
Qh = UhAh(Th TM)

was written in both the reaction side (tube side) and shell side. The off-gas streams, reux ratio, hydrolyser and desorber pressures and
permeation rate from tube to shell for hydrogen was considered. These temperature, pressure and ow rate of membrane reactor feed.
conservation equations were derived according to the following 2. Initial guess for unknown parameters. An initial guess is made for
assumptions: all unknown parameters. In this section, guess values for all
composition and ow rates and temperatures are made by trial and
Steady state ow
error in an attempt to optimize these values.
One dimensional ow
3. Initial guess for Xurea. When a guess is made for urea conversion in the
Pressure drop is negligible because the pressure is approximately
hydrolyser, the model is solved and new values are obtained for Xurea.
high and tube length is small.
The purpose of the computer programming is to reach the end, while
Ideal gas behavior
the difference of new and old values of Xurea approaches zero.
Surface reaction is rate limiting.
4. Solving the heat exchangers model. When the heat exchanger
Plug ow is considered in both tube and shell side.
equations are combined with together, a nonlinear algebraic
The differential material balance equations on species i for the system of equations is obtained. This nonlinear algebraic system
tube and sell sides of both co-current and countercurrent ow of equations should be solved. Newton's method is used to solve
catalytic membrane reactor are given in Table 2. The sign is positive the nonlinear equations [57]. In this model, the inlet temperature
for co-current and is negative for countercurrent ow. of the hot streams is unknown, and this value is calculated by the
second desorber model for rst heat exchanger and the hydrolyser
5. Numerical solution model for second heat exchanger later, i.e., this temperature is
rstly guessed and then corrected by trial and error.
The model consists of ordinary differential and nonlinear algebraic 5. Solution of the desorbers model. The set of nonlinear equations are
equations. Fig. 4 shows the owchart and trend for solving the model. solved by Newton's method [57]. For rst desorber, input stream to
The solution procedure includes the following steps: the fth stage and input vapor from the bottom of tower are
unknown, which are calculated by the hydrolyser model and
1. Input data for calculation. The input data for calculation consists of
second desorber model later, i.e., the temperature and component
the specications of the feed wastewater, LP steam, HP steam and
ow rates are rstly guessed and then corrected by trial and error.
Also a partial condenser is treated as an equilibrium stage and
separated liquid stream is computed from reux ratio. When the
output liquid hydrolyser stream ow rate and temperature are
known, the calculation relevant to second desorber is used to
obtain outlet streams ow rates, composition and temperatures.
For this column, LP steam enters from the bottom.
6. Solution of the hydrolyser model. The basic structure of the model
is consisted of nonlinear algebraic equations of mass and energy
conservative rules of both the vapor and liquid phases, which have
to be coupled with equations of the kinetic model and auxiliary
correlations. These nonlinear equations are solved by iterative
Fig. 3. Cross-section of a countercurrent ow catalyst bed membrane reactor. techniques using Newton's method [57].
 M.R. Rahimpour et al. / Fuel Processing Technology 91 (2010) 600612 605

Table 3
Wastewater feed and HP steam and LP steam specications [10].

Wastewater feed LP steam HP steam

Temperature (C) 60 141.7 307.9

Pressure (kg/cm2) 2.7 3.1 20.3
Component molar rate (kmol/h)
Water 1740.6 468.5 86.9
Urea 8.996
CO2 44.88
NH3 170.38

A boundary value problem is solved for the countercurrent ow

since the tube and shell side boundary conditions are at opposite ends
of the tube. The shooting method converts the boundary value
problem to an initial value one. In this method, the unspecied initial
conditions of the system differential equation are guessed and the
equations are integrated forward as a set of simultaneous initial value
differential equations. At the end, the calculated nal values are
compared with the boundary conditions and the guessed initial
conditions are corrected if necessary. This procedure is repeated until
the specied terminal values are achieved within small convergence
criterion. Boundary conditions for countercurrent case for species i
are:

t t
Fi = yif Fin at z=0 20

s s
Fi = Fin at z = L: 21

6. Model validation

In this work, modeling of the modern treatment loop was

performed and its verication was carried out by comparison of the
model results with the plant data. The input data of the modern
treatment section of urea plant have been summarized in Table 3.

Table 4
Comparison of calculated results of wastewater treatment loop with the observed plant
data [10].

Stream Component molar rate (kmol/h) Temperature

(C)
H2O NH3 CO2 Urea

Output liquid of Plant 2037.6 19.55 1.3 8.996 128.5

rst desorber Calc. 2067.8 18.94 1.37 8.996 129
Fig. 4. Flowchart for solving the model.
Error 1.5 3.1 5.4 0 0.4
(%)
Off-gas Plant 77.3 172.5 55.2 89
Calc. 74.72 177.14 52.7 90.7
Error 3.3 2.7 4.5 1.9
7. Computation of Xurea. At this step, new value for urea conversion is
(%)
obtained with Eq. (17) and compared with the old value. Output liquid of Plant 2067.3 33.63 0.216 b 5 ppm 207
hydrolyser Calc. 2102.6 32.71 0.2 207.7
Xurea = Ff xf 1Fe xe 1 = Ff xf 1 17 Error 1.7 2.7 7.4 4 ppm 0.3
(%)
Output vapor of Plant 48.16 3.91 10.08 194.2
8. At nal step, ordinary differential equations of permselective hydrolyser Calc. 43.12 4.07 10.09 193.4
Error 10.4 4.1 0.1 0.4
membrane reactor were solved by using fourth order RungKutta
(%)
method. For co-current ow mode an initial value problem was Treated efuent Plant 2080.4 1 ppm 0.0 b 5 ppm 88.1
solved. The boundary conditions for co-current case for species i liquid Calc. 2140.5 0.91 ppm 0.0 4 ppm 90
are: Error 2.9 9 0.0 2.1
(%)
t t Output vapor of Plant 455.3 0.216 33.62 131
Fi = yif Fin at z = 0 18 second desorber Calc. 430.6 0.2 32.7 130.6
Error 5.4 7.4 2.7 0.3
s s (%)
Fi = Fin at z = 0: 19
606 M.R. Rahimpour et al. / Fuel Processing Technology 91 (2010) 600612

Table 5
Comparison of ammonia decomposition between model and Gobina data at T = 873 K,
P = 36 atm for countercurrent mode.

Dimensionless Ammonia conversion (%) Error (%)

length (L/L0)
Gobina data Simulation results

0.0625 3 3.07 2.3

0.125 18.4 18.57 1
0.35 93 92 1
0.625 100 99.6 0.6
1.0 100 100 0

Table 6
Input data for comparison between model and Gobina data [27].

Volume of the catalyst bed (cm3) 6.689

Palladiumsilver lm thickness (cm) 6 10 4
Diameter of catalyst pellets (cm) 0.150.2
Catalyst density (kg/m3) 510
Surface area of catalyst (m2/kg) 190,000
Void fraction 0.4
Pressure of synthesis gas (atm) 36.0
Pressure of sweep gas stream (atm) 1.0
Fig. 5. Comparison of co-current membrane and thermodynamic equilibrium reactors
Flow rate of synthesis gas (cm3/min) 350.0
at different pressures.
Flow rate of sweep gas (cm3/min) 300.0
Tube length (cm) 14

equilibrium one if we choose the proper conditions. Ammonia

Table 7 conversion is dened as:
Summary of input parameters used for catalytic membrane reactor simulation.

10 10 4 t t
Palladiumsilver lm thickness (cm) FNH3 ;in FNH3 ;out
Diameter of catalyst pellets (cm) 0.150.2 Ammonia conversion = t 100%: 22
Catalyst density (kg/m3) 510
FNH 3 ;in

Surface area of catalyst (m2/kg) 190,000

Void fraction
Pressure of sweep gas stream (atm)
Flow rate of synthesis gas in tube (mol/min)
Flow rate of sweep gas in shell (mol/min)
Tube diameter (cm)
The model results and the corresponding observed data of the plant
have been presented in Table 4. It was observed that, the steady state
model performed satisfactorily well under the industrial conditions and a
good agreement was obtained between the plant data and the simulation
data which conrm that the proposed model can be considered suitable
and reliable. Also the model of membrane reactor was veried against
results that were presented by Gobina et al. [27]. Table 5 shows that there
is insignicant error for countercurrent ow. The base data for simulation
in order to comparison are presented in Table 6. The ratio of L/L0 is the
dimensionless reactor length and the Gobina data are experimental.
7. Result and discussion
Typical parameters used in the membrane reactor simulation are
listed in Table 7. The composition of the inlet tube stream is based on the
off-gas of wastewater treatment loop of urea plant in Khorasan
petrochemical company [10]. The simulation results were plotted as
proles of the dependent parameters versus independent variables. In
addition, the effects of different parameters such as temperature, tube
side pressure, sweep gas ow ratio, conguration of membrane,
membrane thickness and membrane diameter on the ammonia removal
and hydrogen production performances were investigated.
7.1. Comparison between thermodynamic equilibrium reactor and
membrane reactor
0.4
1.0 In lower temperatures the rate of ammonia decomposition is small
4.8 and decreasing pressure of tube side decreases the ammonia conversion
4.2 in membrane reactor while the thermodynamic equilibrium conversion
5.8
increases. As the pressure in tube side decreases, the driving force for
hydrogen permeation decreases and consequently, the conversion in
membrane reactor decreases. The result shows that at low pressure and
temperature the ammonia conversion in membrane reactor is lower
than thermodynamic equilibrium one. Fig. 5 demonstrates under the
simulation conditions in Table 7, the increase of temperature improves
the rate of reaction, leading to more conversion of ammonia and
consequently more hydrogen production. The main reason that
ammonia conversion in membrane reactor is lower than thermody-
namic equilibrium one, is at low temperature and pressure hydrogen
permeation decreases and there is not enough residence time for more
decomposition of ammonia in the tube side. This phenomenon can be
explained according to Damkhler number (Da) and permeation
number (). Tsuru et al. [58] presented the effects of Damkhler number
(ratio of reaction rate to feed ow rate) and permeation number (ratio
of permeation to the feed ow rate) on methane conversion in catalytic
membrane reactor for methane steam reforming. In fact, ammonia
conversion increases with an increase in Damkhler number (Da). The
increase in Da number allows a local equilibrium in the reaction side as
result of the high reaction rate compared with the feed ow rate, and
increases ammonia conversion. Also an increase in permeation number
, which can be achieved either by large hydrogen permeability or by
decreasing the feed ow rate, enhances ammonia conversion. Therefore,
ammonia conversion (consequently hydrogen production) increases
beyond the thermodynamic equilibrium conversion when Damkhler
number and permeation number increase. The tube lengths used for
comparison were 600 cm.
7.2. Comparison between xed bed and membrane reactor

Fig. 5 shows that the ammonia conversion (consequently hydrogen) Fig. 6 shows the effect of the presence of hydrogen-permselective
in catalytic membrane reactor will be higher than thermodynamic membrane in catalytic reactor at 800K temperature. As understood,
 M.R. Rahimpour et al. / Fuel Processing Technology 91 (2010) 600612 607

Fig. 6. Comparison of conversion in membrane and xed bed reactor.

permeation rate of hydrogen in conventional xed bed reactor is zero

and with respect to equilibrium of reaction; ammonia conversion at
these conditions is less than the membrane reactor. On the hand, due
to the permeation of hydrogen in membrane reactor, the thermody-
namic equilibrium shifts to the right and ammonia decomposition
occurs. Sweep ratio is dened as the ratio of the ow rate of sweep gas
in the shell side to the feed inlet ow rate. Complete decomposition of
the ammonia cannot be achieved for membrane reactor without
sweep gas due to the fact that the shell side and tube side hydrogen
partial pressures become equal. Using a sweep gas in shell side
decreases the hydrogen partial pressure and consequently increases
the driving force for hydrogen permeation and shifts the thermody-
namic equilibrium toward hydrogen production. In this gure
ammonia conversion for membrane reactor with sweep gas, is higher
than the membrane reactor without sweep gas, in other expression a
smaller tube length of membrane is required when the sweep gas in
the shell side is used.
Fig. 7. Effect of pressure on hydrogen recovery: (a) co-current mode; (b) countercur-
rent mode.
7.3. Effect of tube side pressure

Considering equation of hydrogen permeation (Eq. (15)), higher
tube side pressure at constant shell side pressure causes higher rate of
hydrogen permeation which shifts thermodynamic equilibrium to
enhance ammonia decomposition. Fig. 7 demonstrates hydrogen
production is inuenced by pressure variation at tube side directly.
Enhancement of pressure at the tube side advances the reaction
toward hydrogen production along two co-current (Fig. 7(a)) and
countercurrent (Fig. 7(b)) membrane reactors. Increased pressure at
the tube side makes a proper difference between the partial pressures
of hydrogen at the tube and shell sides. As can be shown in these
gures if pressure increases, in countercurrent mode less length of
membrane is necessary according to the maximum hydrogen
production or decomposition of ammonia. Therefore at higher
pressure the feed can enter in smaller tube but the quantity of
hydrogen recovered exceed at the near end of the tube relative to
lower reactor pressure which had started the reaction in longer tube.
Also the value of hydrogen in co-current membrane system which
permeates along the reactor is less than countercurrent mode.
increases, the rate of ammonia decomposition and hydrogen permeation
increases. These gures demonstrate that at higher temperature, less tube
length for maximum hydrogen recovery is required for countercurrent
mode. Therefore at higher temperature the feed enters in smaller reactor
and at the end of reactor we arrive to the more recovery.
7.5. Effect of membrane reactor diameter
Fig. 9 presents the reactor diameter effect on hydrogen production in
membrane reactor in co-current and countercurrent modes. Increasing
reactor diameter implements two effects on membrane performance:
decreasing space velocity and increasing membrane area. If the space
velocity reduces, there is more residence time in membrane reactor for
hydrogen production from ammonia decomposition. With increasing
membrane area, hydrogen permeates more. So as result, the hydrogen
production rises when the reactor diameter increases.
7.6. Effect of PdAg membrane thickness

7.4. Effect of tube side temperature
Fig. 8 shows that when temperature increases, the hydrogen
production increases in reactor. Since the reaction is endothermic, the
temperature has direct impact on hydrogen production. As temperature
To enhance the hydrogen production in membrane reactor,
thickness of the membrane should be reduced. Pd-based membranes
have a high selectivity for hydrogen but the rate of hydrogen
permeation in Pd membrane is low. To overcome this problem
many efforts have been made to reduce the thickness of the Pd-based-
608 M.R. Rahimpour et al. / Fuel Processing Technology 91 (2010) 600612
Fig. 8. Effect of temperature on hydrogen recovery: (a) co-current mode; (b) countercurrent
mode.
membrane reactor by producing a thin layer of palladium on a support
like alumina and stainless steel. Larger pores and the high selectivity
of the Pd-based membrane to hydrogen make it possible to obtain
both high permeability and selectivity. Fig. 10 illustrates the effect of
membrane thickness on hydrogen production in the co-current and
countercurrent congurations of membrane reactor. The increase in
the membrane thickness causes an increase in the resistance of
hydrogen permeation. As can be seen, according to the maximum
production of hydrogen, the reduction of membrane thickness from
10 m to 6 m can decrease 200 cm of membrane reactor.
7.7. Effect of sweep ratio
The effect of sweep ratio (ratio of shell side ow rate over tube side
ow rate) was studied in co-current and countercurrent membrane
reactors by changing its value from 0 to 1. As can be seen from Fig. 11,
enhancing of sweep ratio increases shell side ow rate and decreases the
hydrogen partial pressure. Therefore, hydrogen can permeate more from
tube to shell side and consequently shifts the thermodynamic equilibrium
toward simultaneous hydrogen production and ammonia decomposition.
Fig. 9. Effect of reactor diameter on hydrogen recovery: (a) co-current mode; (b) counter-
current mode.
7.8. Effect of inlet ammonia concentration in membrane reactor
As changes of operating variables of wastewater treatment such as
ow rates of HP steam, LP steam or temperature and composition of
main feed, the composition and ow rate of membrane reactor feed
change. The corresponding changes have an effect on hydrogen
production. Fig. 12 shows the increase of ammonia concentration in
membrane reactor feed enhances hydrogen production along the co-
current and countercurrent congurations of membrane reactors;
especially slope of increasing is sharp between ammonia mole
fractions of 0.20.4 in countercurrent mode. Also, hydrogen produc-
tion in countercurrent mode is more than co-current mode.
8. Conclusion
In the present work, the catalytic membrane reactor was proposed
to install in the wastewater treatment loop of the urea plant in
industrial scale. Both wastewater treatment system and membrane
reactor were modeled mathematically. In this wastewater treatment
loop, catalytic membrane reactor decomposes ammonia and much
 M.R. Rahimpour et al. / Fuel Processing Technology 91 (2010) 600612
Fig. 10. Effect of membrane thickness on hydrogen recovery: (a) co-current mode;
(b) countercurrent mode.
amount of it vents to air and causes air pollution. Ammonia
decomposition results in hydrogen production which is very
benecial from an economic point of view. It has been shown that
maximum hydrogen production can be attained by utilizing catalytic
membrane reactor, while it is impossible by equilibrium or xed bed
reactor due to thermodynamics limitation. Moreover, the results of
models of wastewater treatment loop and catalytic membrane reactor
were compared with real data of the plant and experimental data,
respectively. In both cases, good consistency was observed. Effect of
the changes of some key parameters on the performance of catalytic
membrane reactor was studied such as pressure, temperature, ow
rate or sweep ratio, membrane thickness and reactor diameter.
Generally, it was observed the positive effects on hydrogen produc-
tion by increasing the pressure, temperature, membrane reactor
diameter, sweep ratio and reducing membrane thickness. In addition
the sensitivity of the hydrogen production rate on the composition in
the feed gas mixture of membrane reactor was found to be an
important factor in the operation of such a system. Also results have
shown that countercurrent membrane reactor has superiority
relative to co-current membrane reactor. This approach can separate
609
Fig. 11. Effect of sweep ratio on hydrogen recovery: (a) co-current mode; (b) counter-
current mode.
4588 tons/yr hydrogen from wastewater treatment loop of urea plant
that is used in fuel cells and other hydrogen applications. Other
advantages of membrane reactor application are combining reaction
and separation in a single unit operation, low energy consumption
and smaller reactor length.
Acknowledgment
The authors would like to thank Khorasan Petrochemical Company
for providing valuable process and technical data.
Appendix A. Thermodynamic equation
In this study, the thermodynamic framework to describe liquid
activity coefcients of molecular and ionic species in NH3CO2H2O
urea system is based on the model developed by Isla et al. [41]. The
volatility of urea and ammonium carbamate is negligible and ions
cannot leave from the liquid phase to the vapor phase. As follows in
Table A.1, the extended UNIQUAC equation consists of three items.
610 M.R. Rahimpour et al. / Fuel Processing Technology 91 (2010) 600612

d tube diameter of membrane reactor (cm)

E activation energy (kJ/kmol)
Ec, j residual function for chemical equilibrium relation for
carbamate on the jth tray
Ei, j residual function for phase equilibrium relation for compo-
nent i on the jth tray
EM Murphree tray efciency
Fe molar ow rate of hydrolyser efuent (kmol/h)
Ff molar ow rate of hydrolyser feed (kmol/h)
Fit molar ow rate of component i in tube side of membrane
reactor (mol/s)
Fis molar ow rate of component i in shell side of membrane
reactor (mol/s)
s
Fin molar ow rate of sweep gas in membrane reactor (mol/s)
Hi liquid holdup on stage j (m3)
Hvi, j enthalpy of component i in vapor phase on stage j (kJ/kmol)
Hli, j enthalpy of component i in liquid phase on stage j (kJ/kmol)
H heat of reaction (kJ/kmol)
Hj residual function for total heat balance on the jth tray
I ionic power in Table A.1
Ji permeation rate of component i in membrane reactor (mol/s)
J0 permeation rate constant (mol cm/cm2 s atm1/2)
k Ammonia decomposition rate constant (mol/m3 s)
Keq equilibrium constant of ammonia decomposition (Pa)
k0 pre-exponential factor of ammonia decomposition rate
(mol/m3 s Pa 0.674)
Ki, j equilibrium constant of urea hydrolysis
K0 pre-exponential factor of urea hydrolysis rate constant (m3/
(kmol h))
kf the forward reaction rate constant (m3/(kmol h))
Kr equilibrium constant of reaction r dependent on temperature
l Axial position in membrane reactor (cm)
L tube length of membrane reactor (cm)
Lj mole ow rate of liquid on stage j (kmol/h)
Li, j liquid mole ow rate of component i on stage j (kmol/h)
li Parameter of UNIQUAC equation in Table A.1
M number of components
Fig. 12. Effect of inlet ammonia concentration on hydrogen recovery: (a) co-current Mi, j residual function for material balance for component i on
mode; (b) countercurrent mode.
the jth tray
mi molality of the ionic species i referred to 1000 g of mixed
Table A.1 solvent (kg/(kg soln))
Parameters of extended UNIQUAC model [41]. N number of stages
Parameter Expression Pi partial pressure of component i in reaction side of
i(T, x) ln i(T, x) = ln Ci (X) + ln RE DH membrane reactor (atm)
i (T, X) + ln i (X, T)
  PH,t hydrogen partial pressure in reaction side of membrane
v
Ci (X) ln Ci X = ln Xii + Z2 qi lnii + li Xii j Xj lj
2 3 reactor (atm)
! PH,s hydrogen partial pressure in shell side of membrane reactor
6 m m
vj ij 7
RE
i (T, X)
6
ln i T; X = qi 41 ln vj ji m
RE 7
j=1
5
j = 1 vk kj
(atm)
k=1
Pj pressure of stage j (atm)
qi X i
vi vi = j qj Xj Pj pressure drop (atm)
i i = ri Xi
j r j
Xj ptop pressure at the top of the column (atm)
qi UNIQUAC surface parameter of component i
2 r i qi r i 1
Z
li li =
  Qc Heat transfer from the hot gas in the heat exchanger (kW)
aij
ij ij = exp ; aii = ajj = 0
    QC condenser duty (kJ/h)
T

Mi 1 + bI =2  2 ln 1 + bI 1=2
1
iDH(T, X) ln DH
i T; X =
2A
b3
1
1= Qh Heat transfer from the cold gas in the heat exchanger (kW)
1 + bI 2

2  AI
1=
QH Permeation rate of hydrogen through the PdAg membrane
DH ln DH
i T; X = zi
2
i (T, X) 1=

1
1 + BI 2
(mol/s)
I I = 2 mj zj 2
Q0 Permeation rate constant (mol cm/(cm2 s atm1/2))
Z Z = 35.2 0.1272T + 0.00014T2
ri UNIQUAC volume parameter of component i
rN H3 ammonia decomposition rate (mol/m3 s)
R universal gas constant (kJ/(kmol K))
Appendix B. Nomenclature Rj rate of reaction (2) on the jth tray (kmol/(m3 h))
Sxj residual function for summation relation in liquid phase on
A membrane area (cm2) the jth tray
Ci concentration of component i (kmol/m3) Syj residual function for summation relation in liquid phase on
CPi specic heat of the stream in heat exchanger (kJ/kmol K) the jth tray
 M.R. Rahimpour et al. / Fuel Processing Technology 91 (2010) 600612 611

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