Catalysis Today xxx (xxxx) xxx–xxx

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Catalysis Today
journal homepage: www.elsevier.com/locate/cattod

Thermally double coupled reactor coupling aqueous phase glycerol

reforming and methanol synthesis
Sasinun Thirabunjongcharoena, Palang Bumroongsakulsawata, Piyasan Praserthdama,
Sumittra Charojrochkulb, Suttichai Assabumrungrata, Pattaraporn Kim-Lohsoontorna,*
a
Center of Excellence on Catalysis and Catalytic Reaction Engineering, Department of Chemical Engineering, Faculty of Engineering, Chulalongkorn University, Bangkok
10330, Thailand
b
National Metal and Material Technology Center (MTEC), Pathumthani 12120, Thailand

A R T I C LE I N FO A B S T R A C T

Keywords: This study proposes a novel thermally double coupled reactor (TDCR) coupling endothermic aqueous phase
Thermally double coupled reactor glycerol reforming (APGR) with exothermic methanol synthesis (MS), utilizing heat transfer between both
CFD channels. Hydrogen (H2) source and availability are known as barriers to carbon dioxide conversion to methanol
Methanol synthesis via MS reaction. Waste glycerol could be a source of H2 through APGR reaction. The steady state TDCR model
Aqueous phase glycerol reforming
consists of two concentric channels: 1) an inner tube to which CO₂ and H₂ are fed as reactants for exothermic MS
Hydrogen production
and 2) an outer annulus channel through which glycerol and steam are supplied for endothermic APGR. The
CO2 conversion
TDCR could operate without external heat supply when two reactions were coupled. A computational fluid
dynamic (CFD) model was established to study this TDCR. APGR was assumed to be catalyzed by Pt/Al₂O₃ at
200−250 °C and 20−25 bar. MS was modeled with a Cu/ZnO/Al2O3 catalyst at 200−250 °C and 50−80 bar.
Heat transfer from the exothermic channel to the endothermic channel helped increase glycerol conversion while
methanol productivity is the same as conventional reactor. Cocurrent and countercurrent feed configurations
were compared and it was found that the cocurrent configuration offered more uniform temperature distribution
in the channel with a larger temperature difference between the two channels. On the other hand, hot spots and
cold spots were observed in the countercurrent configuration. Effects of operating conditions of both channels:
H2:CO2 and glycerol:steam ratios, inlet temperature, pressure, and total feed flow rate on reactor performance
significantly affected the performance of TDCR.

1. Introduction
Methanol is an essential chemical and primary feedstock for paraf-
fins, olefins and various organic compounds such as acetic anhydride,
acetic acid, methyl methacrylate and formaldehyde [1]. Methanol is
mainly produced from natural gas [2,3]. Therefore, each ton of me-
thanol produced generates 0.6−1 ton of carbon dioxide (CO2), which is
a greenhouse gas [4]. Therefore, direct methanol synthesis (MS) from
CO2 hydrogenation with renewable H2 is a promising alternative.
MS is generally carried out in gas phase at high pressure and tem-
perature of 50−80 bar and 200−300 °C [5,6] using Cu/ZnO/Al2O3 as a
catalyst [7,8]. As this reaction is exothermic, researchers have devised
schemes to use heat released from MS in other reactions. Mirvakili et al.
[9] simulated methanol synthesis coupled with cyclohexane dehy-
drogenation in membrane heat exchanger. Thermally coupled reactor
was reported to perform better than a conventional reactor. Heat
generated from methanol synthesis is the heat source for cyclohexane
dehydrogenation. Farniaei et al. [10] proposed a thermally coupled
reactor for methanol synthesis and dimethyl ether synthesis with dif-
ferent endothermic reactions. Exothermic reactions in inner and outer
channel releases heat to endothermic reaction, increasing methanol
conversion to 37 %. Khademi et al. [11] utilized the exothermic heat
from methanol synthesis in benzene production using membrane Pt/Ag
with thermally coupled reactor. It was reported that temperature in
endothermic reaction decreases from 230 to 217 °C, resulting in cold
spot in endothermic side, decreased methanol yield and glycerol con-
version. Increasing feed flow rate in exothermic channel reduces me-
thanol yield but help reducing temperature variation in endothermic
channel. Although MS as an exothermic reaction in thermally coupled
reactor has been reported previously, there is no report on coupling MS
with APGR in order to obtain hydrogen from the APGR.
Hydrogen (H2) source and availability is one of the barriers to CO2

⁎
Corresponding author.
E-mail address: pattaraporn.k@chula.ac.th (P. Kim-Lohsoontorn).

https://doi.org/10.1016/j.cattod.2020.03.043
Received 30 November 2019; Received in revised form 7 March 2020; Accepted 20 March 2020
0920-5861/ © 2020 Elsevier B.V. All rights reserved.

Please cite this article as: Sasinun Thirabunjongcharoen, et al., Catalysis Today, https://doi.org/10.1016/j.cattod.2020.03.043
S. Thirabunjongcharoen, et al. Catalysis Today xxx (xxxx) xxx–xxx

Nomenclature Mw Molecular weight [kg mol−1]

P Pressure [bar]
APGR Aqueous phase glycerol reforming Pc Critical pressure [Pa]
MS Methanol synthesis Pr Prandtl number [-]
TDCR Thermally double coupled reactor q Heat flux [J mol−1 m-²]
Q External heat source [J mol−1]
Symbols R Gas constant [J mol−1 K−1]
ri Rate of reaction i [kmol kg−1 s−1]
Ac Cross-section area [m²] Re Reynolds number [-]
a Heat capacity coefficient [J mol−1 K−1] S Maximum stress of material [bar]
b Heat capacity coefficient [K−1] t Time [s]
c Heat capacity coefficient [K−2] T Temperature [K]
CA Corrosion allowance [-] Tc Critical temperature [K]
Cp Heat capacity [J mol−1 K−1] v’ Volume factor of Fuller's equation [-]
D Diffusivity [cm² s−1] v Superficial velocity of fluid [m s−1]
d Heat capacity coefficient [K−3] Vc Critical volume [mˉ3 mol]
Di Diameter of reactor [m] w Acentric factor [-]
dp Catalyst particle diameter [m] z Axial reactor coordinate [m]
dP Pressure drop [bar]
E Weld efficiency [-] Greek symbols
F Volumetric flow rate [m³ s−1]
g Gravity acceleration [m² s−1] ε Bed void fraction [-]
h Reactor length [m] μ Dynamic viscosity [Pa.s]
H Heat transfer coefficient [-] ρ Density [kg m−³]
j Mass flux [-] σ Sphericity factor [-]
ki Kinetic equilibrium constant [-] ω Mass fraction [-]
K Thermal conductivity [W m−1 K−1]

conversion to methanol. Glycerol can be a source of H2 production
through steam reforming. The amount of crude glycerol produced from
biodiesel industry and other processes around the world is approxi-
mately 2.9 million tons per year and increasing. Crude glycerol can be
refined further for use in chemical production. Nevertheless, glycerol is
still oversupplied in global market [12]. Therefore, conversion of gly-
cerol to higher value products has become a pressing issue.
Steam reforming of glycerol to H2 is an endothermic reaction. The
reaction is generally carried out in gas phase at atmospheric pressure
and high temperatures in the range of 400−700 °C [13]. This leads to
high energy demand in process and degradation issue in catalyst and
balance of plant. On the other hand, glycerol reforming can also occur
through aqueous-phase glycerol reforming (APGR) at relatively lower
temperatures and moderate pressures of 200−300 °C and 20−50 bar
[14–18]. Guo et al. [14,16] studied APGR in different temperature
(200−245 °C) and pressure (18−40 bar). It was reported that high
temperature and pressure significantly affects hydrogen selectivity and
glycerol conversion. King et al. [17] reported that 89 % glycerol con-
version is achieved at 225 °C and 28 bar. The main advantages of APGR
are that no vaporization of the feedstock is required, which could de-
crease the input energy compared to steam reforming. Huber et al. [19]
investigated different noble metal (Pt, Ru, Pd and Ir) on silica support
for AGPR reaction and Pt was reported to exhibit the highest perfor-
mance among the tested catalyst. Pt/Al2O3 can be a potential catalyst
candidate for AGPR and was reported to provide glycerol conversion
around 50–60 % [20,21] with a feed glycerol to water ratio of 1:9 in
packed bed reactor. However, production of H2 from glycerol produces
CO2 as by-product. Direct utilization of CO2 with H2 obtained from
APGR can be another promising pathway for glycerol conversion with
mitigating CO2 emission.
Multifunctional reactors featuring reactions coupled with distilla-
tion, separation or heat transfer have been extensively studied [22,23].
In this study, a novel thermally double coupled reactor (TDCR) cou-
pling endothermic APGR with exothermic MS is proposed. Heat transfer
between the two reactions is enabled in this reactor and lead to more
favorable conditions for higher reactant conversion. H2 and CO2
produced from APGR can be utilized in MS for methanol production. A
computational fluid dynamic (CFD) model was established to study this
TDCR. Effects of operating conditions of both reactions: H2:CO2 and
glycerol:steam ratios, inlet temperature, and total feed flow rate on
reactor performance were investigated.
2. Model description
2.1. Reactor geometry
The TDCR in our study consisted of two concentric channels: 1) an
inner tube and 2) an outer annulus channel. Fig. 1 shows a schematic
diagram of this TDCR. The diameter of the inner channel was 16 mm
and the thickness of the annulus channel was 8 mm. The wall between
the two channels was 2 mm thick. The reactor height was 150 mm. The
inner channel was intended for MS and the outer channel was designed
for APGR.
2.2. Reaction kinetics
2.2.1. Methanol synthesis (MS)
Only MS and reverse water gas shift reaction (RWGR) in gas phase
(Eqs. (1) and (2)) was assumed to occur in the inner channel.
CO2 + 3H2 ↔ CH3 OH +H2 O ΔH298 = − 90.55 kJ mol−1 (1)
CO+H2 O↔ H2 + CO2 ΔH298 = +41.12 kJ mol−1 (2)
The rate expression for MS has been extensively studied with dif-
ferent operating conditions [1,24,26,27]. Graaf et al. [26] described the
kinetic model of MS at 15−40 bar and 210−260 °C with CuO/ZnO/
Al2O3 as a catalyst. Seidel et al. [1] developed a model of MS with Gibbs
free energy at 200−250 °C. Anton et al. [27] reported the kinetic rate of
MS at 250 °C and 50 bar when a Cu-Zn/Al-Zr fibrous catalyst was used.
Buessche et al. [24] developed a kinetic model and detailed a rate ex-
pression for MS shown in Eqs. (3) and (4) when Cu/ZnO/Al2O3 was
packed in a fixed bed reactor. In our study, the kinetics of MS were

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reaction in the MS channel was expected to transfer to the endothermic

APGR channel. Both feed streams were fed vertically from the bottom to
the top of the reactor as a base case configuration.

2.4. CFD model

2.4.1. Model assumptions

MS and APGR in TDCR were simulated with COMSOL Multiphysics
5.3a. Steady-state flows of the feed gas mixtures was solved by mass,
momentum, and energy balance equations of a discretized flow domain
of the reactor geometry. The dual reactions were simulated in a 2D-axis-
symmetric system in cylindrical coordinate. The flow regime in each
channel was assumed to be steady and laminar. The diffusion of ma-
terials and the heat conduction in direction flow axis was neglected.
The ideal gas and Peng-Robinson model were employed. The physical
properties of the chemical compounds were defined using Perry’s
Chemical Engineers’ Handbook [32], presented in Table 4. The average
of each data point is verified using Aspen 8.8.

2.4.2. Governing equations

The main equations for the simulation consisted of equation of
continuity, momentum, mass and heat of conservation, presented in
Eqs. (8)–(11) [33].
The equation of continuity:
Dρ
+ ρ (∇∙v) = 0
Dt (8)
Fig. 1. TDCR schematic drawing: (a) cross-section diagram and (b) 3D-diagram.
The conservation of momentum:
based on Eqs. (3) and (4) whose rate constants (ki) are shown in Table 1 ∂ (ρ v)
and calculated in Eq. (5). + (∇∙ρ vv) − ρg + (∇∙τ ̿) + ∇P = 0
∂t (9)
(k1 PH2 PH2 O ) − (k6 PCO2 PCO/ PH2 2 O ) The conservation of mass:
RMS =
(1 + (k2 PCO2 PH2 O ) + (k3 PH0.52 O ) + k 4 PCO2
( ))3 (3) ∂ρi
+ ∇∙j + ∇∙ (ρi v ) − ri = 0
(k5 PH2) − (k 7 PCO2 PCH ₃ OH / PH2 O ) ∂t (10)
RRWGS =
(1 + (k2 PCO2 PH2 O) + (k3 PH0.52 O ) + (k 4 PCO2)) (4) The conservation of energy:

Bi DT ∂lnρ DP
ln ki = Ai + ρCp = − (∇∙q) − (τ ̿: ∇v) − +Q
T /K (5) Dt ∂lnT Dt (11)

Eqs. (8) and (9) were used to calculate the velocity of fluid. Both
2.2.2. Aqueous phase glycerol reforming (APGR) parameters are functions of temperature [32]. The output pressure was
Glycerol and water were feedstock of APGR for hydrogen produc- obtained from Ergun’s equation, Eq. (12). In Eq. (10), mass flux is ex-
tion with CO2 as a by-product (Eq. (6)). There are reports of various side pressed Eq. (13). Di is expressed following Fuller et al. [34], Eqs. (14)
products in APGR [28–30]. Torres et al. [28] investigated the APGR in a and (15).
batch slurry reactor. Methane, ethane and propane were detected as Pressure drop by Ergen’s Equation:
gaseous by-products while ethylene glycol and alcohols were detected 150 μ (1 − ε )2F 1.75 ρ (1 − ε ) F 2
dP
as liquid products. Hitherto, rate expressions of APGR were reported as = 2 2 3
+
dz σs dp ε Ac σs dp ε 3Ac2 (12)
a first order kinetic reaction [28,31]; however, there are still contra-
dicting reports of side-reactions of APGR. Therefore, side reactions of Mass flux [35]:
APGR were neglected in this study. Iliuta et al. [25] formulated a ki-
netic model (Eq. (7)) of APGR with a Pt/Al2O3 catalyst in a trickle bed ∇Mw ∇T ⎞
j = − ⎛ρDi, mix ∇ωi + ρωi Di, mix + Di
reactor. ⎝ Mw T ⎠ (13)

C3 H8 O3 +3H2 O↔ 3CO2 +7H2 ΔH298 = +128 kJ mol-1 (6) Diffusivity of each component [34]:

60000 Table 1
RAPGR = 2.678exp ⎛− ⎞ CC3 H8 O3
⎝ RT ⎠ (7) Rate constants for methanol synthesis [21].
variables Ai Bi

2.3. Operating conditions k1 −29.87 4811.2

k₂ 8.147 0
A Cu/ZnO/Al2O3 catalyst for MS was packed in the inner channel, k3 −6.452 2068.4
through which CO2 and H2 were supplied. A Pt/Al2O3 catalyst for APGR k4 −34.95 14928.9
k5 4.804 −11797.5
was packed in the outer channel, to which glycerol and steam were fed.
k₆ 17.55 2249.8
Operating conditions of the MS and APGR channels are presented in k7 0.131 −7023.3
Tables 2 and 3, respectively. Generated heat from the exothermic

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Table 2 Hdp Re 0.89

= 0.057 ⎛ ⎞ Pr 1/3 (22)
Base case operating conditions of MS [21]. K ⎝ ε ⎠ (18)
Parameter Value Unit
νdp ρ ⎞
Re = ⎜⎛ ⎟
Feed mole composition ⎝ μ ⎠liquid (19)
CH3OH 0.00
CO2 0.03
μCp
H2 0.82 Pr = ⎛⎜
⎞⎟

H2O 0.00 ⎝ λ ⎠liquid (20)

CO 0.04
Ar 0.11
Inlet Temperature 220 °C 2.4.3. Simulation method
Inlet pressure 50 bar
The mathematical equations for the CFD model were divided into
Total feed rate 0.003 mol s−1
Catalyst: Cu/ZnO/Al₂O₃ three parts. For Part I, MS was calculated at the surface of the solid
Density 1775 kg m−3 catalyst. A constant bed void fraction was maintained for the entire
Fixed bed porosity 0.5 length of the reactor. For Part II, APGR was calculated with three
Pellet diameter 0.0005 m
phases (gas-phase products, liquid-phase reactants and solid catalyst).
For Part III, heat transfer through the solid wall was determined.
Numerical solutions were obtained with the finite element method in
Table 3
COMSOL Multiphysics version 5.3a. The mesh resolution was free tri-
Base case operating conditions of APGR [22].
angular with a mesh area of 0.0012 m2 and 1416 elements. Before the
Parameter Value Unit simulation, a mesh-independence analysis has been conducted.
Feed mole composition
CO2 conversion or glycerol conversion can be calculated by Eq. (21)
C3H8O3 0.1 where M is mass of CO2 or glycerol. Methanol and hydrogen yield can
CO2 0 be calculated by Eq. (22). In order to validate the CFD model, the mole
H2 0 fraction results from our work were compared with those from re-
H2O 0.9
ference works [24,25]. The accuracy of the CFD model was defined in
Inlet Temperature 220 °C
Inlet pressure 20 bar Eq. (23).
Total feed rate 0.022 mol s−1 Minlet − Moutlet
Catalyst: Pt/Al₂O₃ Conversion (%) = × 100
Density 1200 kg m−³
Minlet (21)
Fixed bed porosity 0.37
Pellet diameter 0.003 m
Mproduct outlet
Yield (%) = × 100
Mtheoretical reactant inlet (22)

Xi − Xi, ref
Table 4 Error (%) = × 100
Physical properties of all components. Xi, ref (23)
CO2 H2 CO H2O CH3OH C3H8O3
3. Results and discussion
Mw [g molˉ¹] 44.01 2.016 28.01 18.015 32.04 92.094
Tc [K] 304.21 33.19 132.92 647.13 512.64 850.00
Pc 106 [Pa] 7.39 1.32 3.49 21.94 8.14 74.02 3.1. Model validation
Vc [mˉ3 mol] 0.095 0.064 0.095 0.056 0.117 2.64 × 10−4
w [-] 0.224 −0.215 0.048 0.343 0.566 1.320 Simulation for model validation was performed for the MS and
a 22.26 29.11 28.16 32.24 19.0 211.1
APGR channels separately in adiabatic model, i.e. no heat transfer be-
b 10−2 5.981 −0.1916 0.1675 0.1923 9.152 –
c 10−5 −3.501 0.4003 0.5372 1.055 −1.22 –
tween channels. Fig. 2. compares the mole fraction profiles of the MS
d 10−9 7.469 −8.704 −2.222 −3.595 −8.039 – channel simulated in our work with those of Bussche et al. [24]. Only
small variations were present. Minor features such as a brief drop in the
mole fraction of CO2 and a slight increase in the mole fraction of H2O at
1 0.5

Dij =
(10−9)(T1.5) ( 1
m1
+ m2 ) a reactor length of approximately 0.6 mm were also reproduced rather
well. Therefore, the model accuracy was assured at an average error of
P (v′1.5
1 + v′1.5
2 ) (14) only 0.88 % based on average of all components.
The CFD model of the APGR channel was validated with the work of
1 − yi Ion et al. [25] in which APGR was carried out in a trickle bed reactor
Di = y
∑ Di with a bed of Pt/Al2O3 catalyst. Fig. 3. shows agreement between our
ij (15)
mole fraction profiles and those of Ion et al. with an average error of
The temperature profile was calculated by Eq. (11) where Cp is a 2.82 % based on all components.
function of temperature, defined by Eq. (16) [32].
Table 5
Cp = a + bT + cT 2 + dT 3 (16) Boundary conditions.

Generated heat in MS channel at high temperature transferred to Boundary Condition

APGR channel at low temperature. The convection of heat (q) was Inlet of MS-APGR channel Velocity: u = u 0
defined by Fourier’s law, as presented in Eq. (17). For endothermic Composition: ω = ω0
APGR, the heat transfer coefficient of APGR in liquid phase was cal- Temperature: T = T0
culated by Iliuta et al. [25] and presented in Eqs. (18)–(20). The Pressure: P =P0
Surface wall of MS-channel Temperature: T = TMS
boundary conditions for TDCR model is presented in Table 5.
Surface wall of APGR-channel Temperature: T = TAPGR
Outlet of MS-APGR channel Pressure: P =P0 – dP
q = − k ∇T (17)

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Fig. 2. Model validation in the MS channel: mole fraction profiles in this work vs. those of Van-Dal and Bouallou [21].

Fig. 3. Model validation in the APGR channel: mole fraction profiles in this work vs those of Iliuta et al. [22].

Fig. 4. CO2 conversion in the MS channel and glycerol conversion in the APGR channel in insulated channels mode and TDCR mode.

3.2. Independently fed channels
3.2.1. Effects of heat transfer between channels
APGR and MS were simulated in two modes: insulated channels and
TDCR. Fig. 4 shows that, in the TDCR mode, the enabled heat transfer
enhanced glycerol conversion significantly from 20 % to 84 %. On the
other hand, CO2 conversion was virtually independent from the mode
of operation. These results were attributed to the different temperature
profiles between the two modes. Fig. 5 presents the spatial average
axial temperature profiles along the reactor length. Enabling the heat
transfer between the two channels resulted in a large increase in the
temperature profile of the APGR channel but only a small decrease in
that of the MS channel. The changes in the temperature profiles led to
the favorable equilibrium shifts towards the products in both channels.
Figs. 6 and 7 show gas compositions in the MS and APGR channels in
the TDCR mode.
3.2.2. Effects of reactor material
The material for reactor construction affects the thermal con-
ductivity of the wall between the two channels. The previous simulation
of TDCR was performed with stainless steel 316 (SS-316), which can
conduct heat rather well and withstand high pressure, as the reactor
material [36]. Nevertheless, cheaper carbon steel, which provides lower
strength, offers a higher thermal conductivity of 54 W m−¹ K−¹ com-
pared to 16 W m−¹ K−¹ of stainless steel [37]. With carbon steel as the
reactor material, the heat transfer between the two channels of a TDCR
was improved (Fig. 8)
The heat flux depends on both type and wall thickness of the

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Fig. 5. Average axial temperatures in the MS and APGR channels in insulated channels mode and TDCR mode.

Fig. 6. Spatial average mole fraction profiles in the exothermic MS channel in TDCR mode.

Fig. 7. Spatial average mole fraction profiles in the endothermic APGR channel in TDCR mode.

material of construction according to the Fourier's law. The wall be- condition in the Tables 2 and 3, the lowest thickness for the TDCR is
tween endothermic and exothermic channels should be thin enough to limited at 0.6 mm, according to the Eq. (24), when P is the design
facilitate heat transfer and thick enough to withstand high pressure pressure (bar); Di is the diameter of channel (m); E is weld efficiency (-);
inside the reactor. For this study, the thickness of the reactor wall and, CA is the corrosion allowance (m) [38].
(stainless steel) was chosen at constant 2 mm, well above the lowest
PDi
thickness for the pressure inside the reactor. For the operating Thickness = + CA
2SE − 1.2P (24)

6
S. Thirabunjongcharoen, et al.
Fig. 8. Average axial temperature profiles of the MS and APGR channels with stainless steel or carbon steel as the reactor material.
Fig. 9. Temperature profile of TDCR with co-current flow configuration: (a) YZ-
Plane and (b) 3D.
3.2.3. Flow configuration
The flow configuration (co-current or counter-current) in the two
channels influences the heat transfer and reaction characteristics of a
TDCR [39]. Figs. 9 and 10 show the temperature profiles in the two
channels with co-current and counter-current flow configuration, re-
spectively. A larger temperature difference between the two channels
was observed in the co-current configuration and increased from the
bottom to the top. On the other hand, the temperature difference be-
tween the two channels in the counter-current configuration was
smaller and decreased from the bottom to the top. Hot spots and cold
spots were observed in the MS and APGR channels, respectively.
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Catalysis Today xxx (xxxx) xxx–xxx
Fig. 10. Temperature profile of TDCR with counter-current flow configuration:
(a) YZ-Plane and (b) 3D.
Moreover, the temperature distribution in any cross section was less
uniform. The results in this study corresponded well with the work of
Fukuhara et al. [39], who studied a fixed-bed dual-channel reactor and
reported that the temperature distribution of the co-current flow con-
figuration was more uniform, while hot spots and cold spots were
generated in the counter-current configuration. It was suggested that
for a counter-current configuration, a reactor with a catalyst-coated
wall is more suitable since hot spots in the center of the reactor channel
will not affect the reaction zone [39].
3.3. Effects of operating parameters
The feed reactant ratio, inlet temperature, pressure, and total feed
S. Thirabunjongcharoen, et al.
Fig. 11. Effects of operating parameters on the MS channel: (a) inlet temperature, (b) inlet pressure, (c) total feed flow rate, and (d) feed CO2:H2 ratio.
flow rate were varied from their base case values to observe their effects
on reactant conversion and H2 yield. Each operating parameter was
varied when the others were kept constant at the base case conditions.
While the conditions of one channel were studied, those of the other
channel were untouched. Figs. 11 and 12 present the effects of the
operating parameters on the performance of MS and APGR channels,
respectively.
Fig. 11(a) shows the dependence of CO2 conversion and methanol
yield on the inlet temperature of the feed stream for MS in a range of
200−250 °C. Increasing the inlet temperature decreased CO2 conver-
sion following the expectation for the CO2 conversion of exothermic
MS. The methanol yield also decreased as the inlet temperature in-
creased. In Fig. 11(b) shows the effects of the inlet pressure in a range of
50−80 bar. The CO2 conversion and methanol yield were affected in an
expected way; a higher pressure led to a large CO2 conversion and
methanol yield by a shift in thermodynamic equilibrium. Fig. 11(c)
presents decreased CO2 conversion and methanol yield as the feed flow
rate increased due to a shorter residence time. This also indicated that
mass transport was not limiting. Fig. 11(d) shows that increasing the
CO2:H2 ratio (1:25 to 1:3) decreased the conversion of CO2 and me-
thanol yield due to a shift in the chemical reaction equilibrium [40].
The CO2 conversion was rather high in excess H2 with CO2:H2 ratio
above 1:20 before sharply drop when decreasing H2 content.
Operating parameters of the APGR channel were varied in the same
ranges as those of the MS to study their effects. Fig. 12(a) shows that
both the glycerol conversion and H2 yield increased as the feed inlet
temperature increased in agreement with an expected shift of an en-
dothermic reaction. On the other hand, Fig. 12(b) presents increases in
glycerol conversion and H2 yield as the inlet pressure increased. This
clearly could not be explained by a shift in thermodynamic equilibrium.
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Catalysis Today xxx (xxxx) xxx–xxx
It was likely that glycerol presented in both liquid and gas phase in the
system. Increasing pressure could increase glycerol concentration in
liquid phase and in turn increased glycerol conversion and H2 yield.
The results corresponded with the experimental work of Garcı´ et al.
[41]. Fig. 12(c) shows decreases in the glycerol conversion and H2 yield
as the total flow rate increased and led to a shorter residence time.
Fig. 12(d) presents the reduced glycerol conversion and H2 yield after
increases in the feed glycerol:water ratio (1:9 to 1:3).
Temperature, pressure, feed flow rate and feed ratio affected the
reactor performance. In the real operation, controlling the operating
parameters of two reactions at the same time can be complicated. There
are variables should be considered such as deactivation of catalyst as
well as side reactions of MS and APGR. Especially, purities in glycerol
feed obtained from the biodiesel production should be concerned.
4. Conclusion
A steady-state heterogeneous catalytic reaction model was applied
to evaluate the performance of TDCR for simultaneous production of
methanol and hydrogen in one reactor. In TDCR, transferred heat from
exothermic MS to endothermic APGR channel helped increasing hy-
drogen yield in APGR when compared to a single APGR reactor. The
TDCR could operate without external heat supply. Inlet temperature,
pressure, feed flow rate and feed molar ratio in both MS and APGR
channels significantly affected reactor performance. Cocurrent config-
uration was preferable in TDCR, offering more uniform temperature
distribution with a larger temperature difference between the two
channels while hot spots and cold spots were observed in counter
current configuration.
S. Thirabunjongcharoen, et al.
Fig. 12. Effects of operating parameters on the APGR channel: (a) inlet temperature, (b) inlet pressure, (c) total feed flow rate, and (d) feed CO2:H2 ratio.
CRediT authorship contribution statement
Sasinun Thirabunjongcharoen: Methodology, Investigation,
Validation, Writing - review & editing. Palang Bumroongsakulsawat:
Supervision, Writing - review & editing. Piyasan Praserthdam: Project
administration. Sumittra Charojrochkul: Supervision. Suttichai
Assabumrungrat: Supervision. Pattaraporn Kim-Lohsoontorn:
Supervision, Conceptualization, Visualization, Writing - review &
editing.
Declaration of Competing Interest
The authors declare that they have no known competing financial
interests or personal relationships that could have appeared to influ-
ence the work reported in this paper.
Acknowledgements
Acknowledgment is made to Thailand Graduate Institute of Science
and Technology (TGIST) fund from National Science and Technology
Development Agency (NSTDA) and CAT-REACT Industrial Project from
Thailand Science and Research Innovation (TSRI). P. Kim-Lohsoontorn
would like to acknowledge Research Cess Fund, Malaysia-Thailand
Joint Authority (MTJA), Thailand Science Research and Innovation
(TSRI) and NSTDA Chair Professor Grant from NSTDA.
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