i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 6 ( 2 0 2 1 ) 2 1 9 5 3 e2 1 9 6 4

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A novel tubular membrane reactor for pure

hydrogen production in the synthesis of
formaldehyde by the silver catalyst process

S.M. Jokar a,*, M.R. Keshavarz b, M. Zhubin c, P. Parvasi a, A. Basile d

a
Department of Chemical, Petroleum and Gas Engineering, Shiraz University of Technology, Shiraz, Iran
b
Department of Chemical Engineering School of Chemical and Petroleum Engineering, Shiraz University, Shiraz, Iran
c
Department of Polymer Science and Catalysts, Faculty of Engineering, Iran Polymer and Petrochemical Institute,
Tehran, Iran
d
CNR-ITM, c/o University of Calabria, Via Pietro Bucci, Cubo 17/C, 87030, Rende, CS, Italy

highlights

The silver process for formaldehyde production in a formaldehyde plant was modeled.

A novel tubular membrane reactor was modeled for formaldehyde synthesis.

The simultaneous production of pure H2 (500 kg/d) and formalin (1000 t/d) was achieved.

The process temperature decreased by 650  C to 420  C by membrane reactor.

article info abstract

Article history: Formaldehyde-based chemistry plays a significant role in the production of different ma-
Received 14 October 2020 terials. In this work, attempts have been made to revamp a silver catalyzed formaldehyde
Received in revised form plant by applying membrane technology. The conventional silver catalyst packed
31 January 2021 bed reactor was replaced by a shell and tube membrane reactor. A steady-state one-
Accepted 8 April 2021 dimensional model was applied to evaluate the performance of the proposed membrane
Available online 30 April 2021 process. The model was validated with experimental results from the plant.
The effects of various parameters including reactor pressure, feed temperature, and
Keywords: membrane thickness on the membrane reactor were investigated. Results showed that the
Formaldehyde effect of feed temperature on production rates was negligible. The increase in pressure
Silver process and decrease in membrane thickness, however, leads to increase products. The simulta-
Membrane reactor neous production of 100 tonnes/day of formalin 37% (37 wt% formaldehyde in water) and
Pure hydrogen 500 kg/day pure hydrogen achieved by the proposed process. Furthermore, the exiting
reactor temperature can be reduced to 420  C which is significantly lower than the con-
ventional method (650  C).
© 2021 Hydrogen Energy Publications LLC. Published by Elsevier Ltd. All rights reserved.

* Corresponding author.
E-mail address: jokar@sutech.ac.ir (S.M. Jokar).
https://doi.org/10.1016/j.ijhydene.2021.04.042
0360-3199/© 2021 Hydrogen Energy Publications LLC. Published by Elsevier Ltd. All rights reserved.
21954 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 6 ( 2 0 2 1 ) 2 1 9 5 3 e2 1 9 6 4
Introduction
Formaldehyde is one of the most essential basic chemicals
and is involved for the generation of thousands of industrial
and consumer products [1].
Formaldehyde and its derivatives such as formaldehyde
resins are widely applied in various industries including
plywood, car body parts, medical, and textile industry. It is one
of the world’s most ubiquitous volatile organic compounds
(VOCs) with the systematic IUPAC name of Methanal. It is
extremely reactive and readily decomposes in the presence of
air and sunlight [2,3]. An aqueous solution of water and
formaldehyde, including 40% formaldehyde by volume or
37% formaldehyde by mass, is called “Formalin”. Generally, to
prevent oxidation, formalin is stabilized with a small amount
of methanol [4].
Formaldehyde production processes
Currently, two technologies are applied to the formaldehyde
production. The methanol oxidation-dehydrogenation pro-
cess by silver catalyst and the catalytic direct oxidation pro-
cess by iron-metal oxides [5,6].
The silver process is carried out at the atmospheric pres-
sure within a temperature range of 600 Ce720  C. The silver
process for formaldehyde production proceeds by the
following two reactions:
CH3 OH%HCHO þ H2 DH ¼ 83:7 kJ=mol
1

CH3 OH þ O2 %HCHO þ H2 O DH ¼ 156kJ mol
2 (FBR) and are expected to ameliorate the performance of FBRs.
The metal oxide process only results in the one-step
oxidation of methanol (equation (2)) [7].
The metal oxide process exhibits some advantages such as
low operating temperatures (250ºC-400  C) and high methanol
conversion to formaldehyde (98e99%) [7]. Furthermore, this
process consumes much less methanol in comparison with
air and therefore, preserves the reaction condition outside the
explosive limit [8e10].
Despite the silver process displays some drawbacks
compared with the metal oxide process, it is a cheaper process
as the ability to operate with excess methanol results in reduced
units and utilities than the metal oxide process which requires
excess air [11,12]. In addition, the catalysts could be regenerated
in silver process which leads to lower catalyst costs [12].
Therefore, the silver process continues to grow, because of all
the advantages it brings to the formaldehyde production plants.
There have been various scientific attempts to produce
formaldehyde using both processes. Most of the researches
dedicated to the catalyst modification [13e17].
Kim et al. [18] experimentally studied the selective oxida-
tion of methanol to formaldehyde in Fe-Molybdenum fixed
bed reactor. In this regard, they observed that an increase in
the residence time increase the yield and selectivity of form-
aldehyde. It happened due to the subsequent oxidation of
formaldehyde to carbon monoxide.
In 2017, Gribovskii et al. [19] built a setup to work on the
oxidation of methanol to formaldehyde in a microchannel
reactor (MCR) filled with industrial FeeMo catalyst. They
proposed that MCR exhibits a safe reaction condition even
with 12 mol% methanol in the feed mixture which is within
the explosive limit (explosive range of methanol-oxygen
mixtures) and could increase the formaldehyde productivity
by 10-times. They indicated that due to the high rate of
heat and mass transfer, MCRs have competent liability for
exothermic reactions.
The simultaneous production of hydrogen and anhydrous
formaldehyde in a fixed bed of Ag2O/g-Al2O3 Nano-catalysts
was studied by Said and El-Aal [20]. By adding Ag2O to
g-Al2O3, they achieved a 100% methanol conversion with 100%
formaldehyde yield at relatively low temperatures (330  C).
Lervold et al. [21] analyzed the catalytic activity and
morphology of electrolytic silver catalysts for partial oxidation
of methanol to formaldehyde in the presence of different
atmospheres such as oxygen, nitrogen, carbon monoxide and
hydrogen. They discovered that those silver particles exposed
to an oxygen-free atmosphere, remained intact compared to
the fresh catalyst.
The membrane reactor technology for formaldehyde
production
Membranes are widely employed for the separation of an
individual component (e.g. hydrogen, CO2, CH4, H2S and etc.)
from gas mixtures [22e26]. The membrane reactor (the
membrane in a chemical reactor) is defined as an apparatus
that allows simultaneous chemical reaction and membrane-
(1) based separation.
Recently, membrane reactors (MR) have been exhibited
several advantages over the conventional fixed bed reactors
(2)
Aside from all assets of MRs, their main two advantages are as
follows [27]:
1. Simultaneous occurrence of desirable chemical reaction
and membrane separation
2. Selective removal of specified reactants
The dehydrogenation reaction of methanol to formalde-
hyde suffers from thermodynamic limitations due to its high
exothermicity. Although high temperature favors the dehy-
drogenation reaction and leads to an increase in methanol
conversion, it decomposes the formaldehyde and forms
byproducts. Membrane reactors provide the opportunity to
defeat these limitations by extracting of the products from the
reaction zone and letting the reaction take place efficiently at
lower temperatures [28e32].
Some experimental and modeling investigations have
been carried out in support of the advantages of MRs for
formaldehyde production through methanol dehydrogena-
tion [31,33e35]. For instance, Song et al. [36] performed the
experimental and modeling study on a membrane reactor for
silver process. The reactions were performed over the tem-
perature range of 300e400  C and at atmospheric pressure.
A porousVycor glass membrane was applied to separate
hydrogen from the reaction products. The higher conversions
were achieved using an extended space time and a greater
membrane area. Their study has not only showed the elevated
 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 6 ( 2 0 2 1 ) 2 1 9 5 3 e2 1 9 6 4
equilibrium shift by separating the hydrogen through the
membrane, but also introduced a MR as an economical alter-
native [36].
A zirconia/R-alumina porous membrane packed with the
MoeCoeBeO/SiO2 catalyst were used to investigate the se-
lective oxidation of methane to formaldehyde in a work pre-
pared by Yang et al. [37]. The membrane reactor performance
was experimentally analyzed at atmospheric pressure and
temperature range of 610e690  C. The process was modeled to
study the effects of reaction process operation conditions
and membrane pore sizes on the performance of the MR.
A higher selectivity to the desired product were observed in
MR compared with conventional method. However, they
concluded that a more permselective and controllable mem-
brane should be used to replace the zirconia/R-alumina
porous membrane to obtain more significant enhancement
of formaldehyde yield [37].
In 2002, Diakov et al. [34] carried out a combined
experimental-modeling investigation to study the methanol
oxidative dehydrogenation reaction in the presence of FeeMo
oxide catalyst by means of a conventional FBR, a packed-bed
membrane reactor (PBMR) with methanol as the permeating
gas and a packed-bed membrane reactor (PBMR) with oxygen
as the permeating gas. They implemented a PMBR model to
demonstrate the one-dimensional permeation of oxygen and
methanol through the membrane and compared the perfor-
mance of PMBR and FBR under the same operating condi-
tions. They determined the reaction kinetics using the
experimental FBR data with a plug flow model and concluded
that the performances of the three reactors are in the order
of: PBMR with methanol as the permeating gas < FBR < PBMR
with oxygen as the permeating gas [34]. In a complementary
attempt in 2003, they optimized both PBMRs and FBR in
terms of formaldehyde yield for an identical mass of FeeMo
oxide catalyst, and compared the optimal performances
of the three reactors. They implemented an experimentally
authenticated steady-state plug flow PMBR model for a wide
range of operating conditions and concluded that related
reactor performances are remarkably affected by the oper-
ating conditions. In completion of their previous work in
2002, they concluded that the optimal yields for the
three mentioned reactors are in the order of: PBMR with
methanol as the permeating gas < FBR < PBMR with oxygen as
the permeating gas [35]. Shelepova et al. (2018) [31] used a
two-dimensional non-isothermal model to study the dehy-
drogenation of methanol in the presence of a copper-silica
catalyst in a tubular membrane reactor. The MR configura-
tion consisted of two concentric tubes. They used a 6 mm
Palladiume23 wt% Silver alloy to increase the hydrogen
permeation and prevent the hydrogen embrittlement effect
[31]. Simultaneously, with the dehydrogenation of methanol
in the presence of CueSiO2 catalyst in the inner tube, the
permeated hydrogen takes part in the oxidation reaction with
the oxygen. They proposed that these coinciding reactions
(dehydrogenation and oxidation) result in a methanol con-
version of 87% at 125  C [31].
In another study, besides their prior mathematical model
to describe the simultaneous reaction in the inner and the
outer tubes, they theoretically studied the effect of two types
of gas heating on the formaldehyde yield: (1) Heating the
21955
reactor outer wall to 150  C, and (2) Heating the inlet gas flows
to the inner and the outer tubes to 100  C and 83  C, respec-
tively. In this study, they achieved 77% and 72% formaldehyde
yield for the two conditions presented respectively [29].
As mentioned above, attention in only a few studies, has
been paid to the way in which the formaldehyde conversion
increased by the membrane technology. Unfortunately,
no single study is dedicated to membrane application in the
silver process. The silver process produces a high amount of
hydrogen. By using the MR, the produced hydrogen could be
captured as a byproduct of formaldehyde production.
In this work, one-dimensional steady-state mathematical
models for conventional FBR and MR for silver process have
been theoretically investigated. The effect of some process
parameters on the performance of MR were studied and
compared with FBR.
Process description
Conventional silver fixed bed reactor for formaldehyde
synthesis
The schematic of the silver process for the methanol conver-
sion to formaldehyde in a formaldehyde plant is shown in
Fig. 1. Generally, vaporized methanol is superheated and
mixed with heated air and steam to form a gaseous mixture of
methanol in air, in which the inert gas (nitrogen, CO2 and
water) varying in composition does not throughout the
explosion-limit range [38]. The mixture passes through a
methanol converter, which is a 25e30 mm thick bed of silver
crystals. The bed consists of silver crystals with a defined
range of particle sizes. To achieve near-complete conversion
of methanol and restrain the formation of by-products
(such as formic acid, carbon dioxide and carbon monoxide),
methanol feed is mixed with steam. Moreover, also the
downstream products of the silver bed is immediately
cooled by an adjacent cooler (shell and tube heat exchanger)
which is immediately placed under the silver bed [34].
Besides Eqs (1) and (2), which are the main reactions, form-
aldehyde is thermally subject to decomposition resulting in
undesirable products which decrease methanol conversion
(Eq (3) and (4)). The significant and beneficial role of adding
steam and product cooling in increasing catalyst lifetime, is
indispensable [12].
HCHO þ O2 %CO2 þ H2 O DH ¼
 520kJ = mol ðDecomposition to CO2 Þ (3)
HCHO%CO þ H2 DH ¼ 10kJ=mol ðDecomposition to COÞ (4)
About 50e60% of the formaldehyde is produced by the
exothermic methanol oxidation reaction (Eq. (2)) and the rest
of formaldehyde is formed by the methanol dehydrogenation
reaction (Eq. (1)) [15]. Eqs. (2) and (3) are exothermic overall
and heat is produced through the thickness of the silver bed.
The hydrogenation reaction is strikingly affected by the
operating temperature. In this regard, an increase in temper-
ature from 400  C to 700  C will double the methanol conver-
sion from 50 to 99% [7]. After the gaseous product from the
21956 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 6 ( 2 0 2 1 ) 2 1 9 5 3 e2 1 9 6 4

Fig. 1 e Process flow diagram of conventional silver FBR for formaldehyde synthesis [7].

silver bed is cooled, it proceeds through an absorber packed

column in which the gaseous mixture condenses and the tail Mathematical model
gas is removed from the top of the absorber. By injecting
quenching water, a high concentration formaldehyde solution The steady-state modeling for conventional and membrane
is extracted from the bottom of the column [39]. The extracted formaldehyde reactors is provided in this section.
tail gas includes H2, CO and CO2 (mostly hydrogen). This tail For modeling purposes, the gradients of temperature and
gas (containing hydrogen) is fed to a steam generator and concentration between the solid and gas phases are neglected
combusted to produce steam. The burnt tail gas has no envi- and the phases equations are mixed based on Rezaie et al.‘s
ronmental and health consequences [7]. It is vividly implied work [40]. They showed that the behavior of the gas phase is
that instead of combustion of hydrogen to produce heat, heat very close to that of the corresponding solid phase behavior
can be stored (as hydrogen) which has more economic flexi- under industrial conditions [40].
bility [7,39].
Industrial conventional fixed bed reactor
Silver packed bed membrane reactor for formaldehyde
synthesis The operating and geometrical parameters of the industrial
conventional silver reactor model are listed in Table 2.
Fig. 2 shows the configuration of the MR for formaldehyde The mass balance is written as:
synthesis. A packed bed membrane reactor is a revamped dFi X
model of an FBR. The tubular membrane reactor assembly in ¼ hrj rB i ¼ CH3 OH; O2 ; HCOH; H2 O; H2 ; CO; CO2 (5)
dz j
Fig. 2 comprises two concentric tubes. In this assembly, the
reactor can be considered as a shell and tube system. The tube where Fi is the molar flow rate of component i, h is effective-
wall act as a hydrogen-selective membrane which permits ness factor of the catalyst, rj is reaction rate of component j
hydrogen to permeate to the shell side based on the hydrogen and rB is the bed density.
differential pressure between the shell and tube. The feed- The energy balance could be written as follows:
stocks (methanol, water vapor, inert gases) are fed to the tube
P
4   P
8  
side (reaction zone). The reaction takes place and the pure H2 hrB rj DHf ;j AC  Cpi dFi
T  Tref
dz
is passed to the shell side. Formaldehyde and water are pro- dTreac j¼1 i¼1
¼ (6)
duced in the tube side and vaporized with the exothermic dz P
8
Cpi Fi
reaction heat. i¼1
 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 6 ( 2 0 2 1 ) 2 1 9 5 3 e2 1 9 6 4 21957

Fig. 2 e Process flow diagram of the membrane reactor for formaldehyde synthesis.

where Treact is the temperature of the reaction zone, DHf,j is the

enthalpy change of reaction i, and AC is the cross section area
Table 1 e Thermodynamic and rate constants for
equations (16)e(19) [42]. of the reaction zone with boundary conditions:
 
8774 (20) z ¼ 0; Fi ¼ Fi feed ; Treac ¼ Tfeed (7)
K1 ¼ 0:278  exp 12:5 
T
 
7439 (21) where Fi feed and Tfeed are the molar flow rate of component i
K01 ¼ exp  17:29 þ
T and the temperature of the reaction zone feed stream.
 
12500 (22)
K2 ¼ 0:278  exp 16:9 
T
  Membrane reactor
15724 (23)
K02 ¼ exp 25 
T
  An element with length Dz, is considered as shown in Fig. 3.
120:5 (24)
k3 ¼ 1:0482 exp
RT The mass and energy balances of the reaction zone (tube
 
80000 (25) side) can be written as:
KB ¼ 988:15  exp 
RT
   
165 121000 (26) dFi X
KC ¼ exp  exp  ¼ hrj rB i ¼ CH3 OH; O2 ; HCOH; H2 O; N2 ; CO; CO2 (8)
R RT dz j
5
k4 ¼ 9:93  10 (27)
qffiffiffiffiffiffiffiffiffiffi qffiffiffiffiffiffiffiffiffiffi 
dFH2 X
¼ hrj rB  aH Amem ptube
H  pshell
H (9)
dz j

Table 2 e The operating and geometric parameters of the P

4   P
8  
industrial conventional silver reactor. hrB rj DHf ;j AC  Cpi dF
dz
i
TTref þpDto Utube ðTtube Tshell Þ
dTreac j¼1 i¼1
Parameter Value ¼
dz P
8
Cpi Fi
Bed diameter in the industrial conventional fixed bed 150 i¼1
reactor (cm) (10)
Bed length in the industrial conventional fixed bed 2
reactor (cm) where aH is hydrogen permeability, and ptube
are hydrogen
H pshell
H
Reactor pressure (bar) 2 partial pressures in reaction and shell zones, and Dto is the
Feed temperature (ºC) 125 outside diameter of the tube side.
Formaldehyde mole fraction in the reactor outlet stream 0.19
In equation (9), aH could be calculated from equation (11).
21958 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 6 ( 2 0 2 1 ) 2 1 9 5 3 e2 1 9 6 4

P0:5
O
PHCOH
k3 KB 2
0:5
PH O
R3 ¼  2
2 (18)
1 þ K0:5
C PO2
0:5

R4 ¼ k4 P2:8
HCOH (19)

Thermodynamic and reaction rate constants for equations

16e19 over a silver catalyst are presented in Table 1.

Numerical solution

The modeling codes were prepared by MATLAB 2016a. The

modified Rosenbrock method (ode23s) was used to solve the
set of stiff ordinary differential equations (ODEs). 100 nodes
were assisted for ODEs solution. The methanol conversion
was calculated based on the following equation:

feed product
FCH3 OH  FCH3 OH
XCH3 OH ¼ feed
 100 (28)
FCH3 OH
Fig. 3 e An elemental volume of the membrane silver
reactor.
Results and discussions

In this section, the proposed MR is modeled based on the real

  plant data collected from a formaldehyde plant located in a
p+H Ea
aH ¼ 2 exp  (11) suburban area of a city in Iran.
d RT

In this equation p0H2 is the pre-exponential factor Industrial conventional fixed bed reactor
pffiffiffiffiffi) and Ea is the activation energy (9180 j/mol).
(3.45  105 2molm s bar
R is the universal gas constant, and T is the bulk temperature At first, the industrial conventional fixed bed reactor model is
[41]. A stainless-steel supported palladium membrane is validated with plant data (Fig. 4). The validated model is then
assisted for modeling considerations based on our previous applied to estimate and optimize the performance of a
work [41]. The boundary conditions for the reaction side are as membrane silver reactor. The reactor bed of the existing
follows: formaldehyde reactor for silver process with a thickness of
2 cm was extremely low. Therefore, the reactor outlet is the
z ¼ 0; Fi ¼ Fi feed ; Treac ¼ Tfeed (12) only experimental data that can be obtained for model vali-
The mass and energy balance equations for the shell side dation (Fig. 4 (a)). Therefore, the model was also checked
are as follows: with the experimental results obtained by Qian et al. [43] for
qffiffiffiffiffiffiffiffiffiffi qffiffiffiffiffiffiffiffiffiffi  different residence times (Fig. 4 (b)).
dFH2 As can be seen in Fig. 4, a good consistency was found
¼ aH Amem ptube
H  pshell
H (13)
dz between the outcomes of model prediction and experimental
results.
dTperm CpH2 dFi
ðTtube  Tshell Þ þ pDto Utube ðT  Tshell Þ
¼ dz
(14)
dz CpH2 FH2 Membrane silver reactor
Likewise, the boundary conditions for the shell side could
The operating and geometrical parameters of the membrane
be written as follows:
silver reactor model are listed in Table 3. The membrane
z ¼ 0; FH2 ¼ FH2 sweep ; Tperm ¼ Tsweep (15) reactor parameters are chosen to give an almost equal form-
aldehyde mole faction to that achieved by the conventional
Reaction kinetics reactor.
Fig. 5 shows the formalin 37% (37 wt% formaldehyde in
The corresponding rate equations for formaldehyde synthesis water), formaldehyde mole fraction and the pure hydrogen
reactions (Eqs (1)e(4)) are [42]: production rate for the MR. As shown in this figure, the pro-
posed MR could achieve the same formaldehyde mole fraction
K1 PCH3 OH
R1 ¼ (16) as 0.19 in the industrial conventional fixed bed reactor.
1 þ K01 PCH3 OH
90 tonnes/day of formalin 37% produces in this system. On the
other hand, 470 kg of pure hydrogen per day removed from
0:278 þ K2 PCH3 OH
R2 ¼ (17) the product stream.
1 þ K02 PCH3 OH
The temperature distribution and methanol conversion in
the reaction side along the length of the MR are shown in
 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 6 ( 2 0 2 1 ) 2 1 9 5 3 e2 1 9 6 4
Fig. 4 e Comparison of modeling and (a) plant data for the
industrial conventional fixed bed reactor (b) experimental
results obtained by Qian et al. [43] (GHSV ¼ 1.5 £ 104 h¡1,
bed diameter ¼ 150 cm, bed length ¼ 2 cm, reactor
temperature ¼ 550  C, reactor pressure ¼ 2 bar).
Table 3 e The operating and geometric parameters of the
membrane silver reactor.
Parameter
Tube length in membrane silver reactor (cm)
Tube inner diameter (cm) (1-inch Schedule 40)
Number of tubes
The amount of catalyst in each tube (kg)
Reactor pressure (bar)
Feed temperature (ºC)
Membrane thickness (mm)
Fig. 6. As can be seen, the exit temperature of the MR is about
420  C, which is extremely lower than that of the industrial
conventional reactor (650  C). Therefore, the MR is expected to
21959
provide a safer operating condition with a lower production
cost. Furthermore, the catalyst lifetime could be increased by
decreasing the process temperature.
Effect of reactor pressure on formaldehyde and pure
hydrogen production
The reactor pressure influences on hydrogen permeation.
Fig. 7a shows the effect of the reactor pressure on the form-
aldehyde mole fraction and pure hydrogen production rate.
The driving force of hydrogen permeation enhances as the
reactor pressure increases and then more pure hydrogen is
produced. The formaldehyde production will also rise due to
the shift effect on the thermodynamic equilibrium (Eq. (1)).
In order to compare the performance of the two reactors,
the effect of pressure on the formaldehyde mole fraction in
the industrial conventional fixed bed reactor has also been
investigated. The result is presented in Fig. 7b. Comparing
Fig. 7(a) and (b) show that, the effect of pressure on formal-
dehyde production is relatively similar for membrane and
fixed bed reactors.
Effect of membrane thickness on formaldehyde and pure
hydrogen production
Membrane thickness is an essential parameter that influences
the generation of pure hydrogen. Fig. 8 shows the effect of a
stainless-steel supported palladium membrane thickness on
the pure hydrogen production rate and formaldehyde. The
hydrogen and formaldehyde production rates decrease as the
membrane thickness increases due to the equilibrium shift
effect. This is while, for the higher thicknesses (more than
10 mm), little changes in the production rate were observed.
Effect of MR feed temperature on production rate
Fig. 9 reports the effect of the reactor inlet temperature on
hydrogen and formaldehyde production rates. As shown in
this figure, the MR feed temperature is not an effective
parameter on the pure hydrogen production rate. However,
the formaldehyde mole fraction is slightly affected by the MR
feed temperature. A 40  C rise might increase the formalde-
hyde mole fraction from 0.175 to 0.182. Consequently, the feed
temperature is considered as a futile factor for MR.
Conclusion
Value The silver process is commonly utilized by industries to pro-
72 duce formaldehyde. In this work. a novel membrane reactor
2.66 (MR) is proposed to fulfill some drawbacks of the silver pro-
100
cess. In this regard, the packed bed silver catalyst reactor was
1.5
replaced by a tubular MR filled with silver. The data were
2
125 collected from an existing formaldehyde plant and the system
5 was modeled to investigate the performance of the proposed
process. The model accuracy was checked with plant data.
The modeling results showed that the MR has the capa-
bility of reducing the process temperature from 650  C to
420  C which could decrease the process cost and increase the
catalyst lifetime. On the other hand, 470 kg/day of ultra-pure
21960 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 6 ( 2 0 2 1 ) 2 1 9 5 3 e2 1 9 6 4

Fig. 5 e Formalin (37 wt% formaldehyde in water) mass flowrate, formaldehyde mole fraction and pure hydrogen production
rate profiles for the MR (feed temperature ¼ 125  C, reactor pressure ¼ 2 bar and membrane thickness ¼ 5 mm).

Fig. 6 e Methanol conversion and reactor temperature in the reaction side along the length of the MR (feed
temperature ¼ 125  C, reactor pressure ¼ 2 bar and membrane thickness ¼ 5 mm).

hydrogen can be produced as a byproduct using the proposed
process. Whereas, this amount of hydrogen was burned as a
tail gas in a steam generator for the conventional silver
process.
Afterwards, the effect of different parameters including
pressure, temperature and membrane thickness on the MR
was evaluated. The pure hydrogen and formaldehyde pro-
duction rate increase as the pressure increases, and decrease
as the membrane thickness increases. The membrane effect is
reduced by increasing the membrane thickness. Furthermore,
the effect of temperature on the production rate was not
considerable.
The results of this study confirmed that the silver process
needs some modification. The membrane technology appli-
cation could be experienced in formaldehyde industries as an
appropriate method to improve the process efficiency.
 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 6 ( 2 0 2 1 ) 2 1 9 5 3 e2 1 9 6 4 21961

Fig. 7 e a. Formaldehyde mole fraction and pure hydrogen production rate profiles for the membrane reactor (feed
temperature ¼ 125  C and membrane thickness ¼ 5 mm). b. Formaldehyde mole fraction profile for the industrial
conventional fixed bed reactor (feed temperature ¼ 125  C).
21962 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 6 ( 2 0 2 1 ) 2 1 9 5 3 e2 1 9 6 4

Fig. 8 e Formaldehyde mole fraction and pure hydrogen production rate profiles for the membrane silver reactor (feed
temperature ¼ 125  C and reactor pressure ¼ 2 bar).

Fig. 9 e Formaldehyde mole fraction and pure hydrogen production rate profiles for the MR (reactor pressure ¼ 2 bar and
membrane thickness ¼ 5 mm).

Declaration of competing interest Nomenclature

The authors declare that they have no known competing Ac Cross-section area of reaction side (m2)
financial interests or personal relationships that could have Amem Membrane lateral surface (m2)
appeared to influence the work reported in this paper. Atube Cross-section area of membrane side (m2)
 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 6 ( 2 0 2 1 ) 2 1 9 5 3 e2 1 9 6 4 21963

Ai Inner area of reaction side (m2) [6] Piccoli RL. Kinetic study of methanol selective oxidation to
Ao Outside area of reaction side (m2) formaldehyde on iron molybdate catalyst. Research Report;
as Specific surface area (m2m3) 1992.
[7] Reuss G, Disteldorf W, Gamer AO, Hilt A. Formaldehyde. In:
Ci Concentration of component i in reaction side (J
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