Thermally Double Coupled Reactor Coupling Aqueous Phase Glycerol
Thermally Double Coupled Reactor Coupling Aqueous Phase Glycerol
Thermally Double Coupled Reactor Coupling Aqueous Phase Glycerol
Catalysis Today
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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 generated from methanol synthesis is the heat source for cyclohexane
dehydrogenation. Farniaei et al. [10] proposed a thermally coupled
Methanol is an essential chemical and primary feedstock for paraf- reactor for methanol synthesis and dimethyl ether synthesis with dif-
fins, olefins and various organic compounds such as acetic anhydride, ferent endothermic reactions. Exothermic reactions in inner and outer
acetic acid, methyl methacrylate and formaldehyde [1]. Methanol is channel releases heat to endothermic reaction, increasing methanol
mainly produced from natural gas [2,3]. Therefore, each ton of me- conversion to 37 %. Khademi et al. [11] utilized the exothermic heat
thanol produced generates 0.6−1 ton of carbon dioxide (CO2), which is from methanol synthesis in benzene production using membrane Pt/Ag
a greenhouse gas [4]. Therefore, direct methanol synthesis (MS) from with thermally coupled reactor. It was reported that temperature in
CO2 hydrogenation with renewable H2 is a promising alternative. endothermic reaction decreases from 230 to 217 °C, resulting in cold
MS is generally carried out in gas phase at high pressure and tem- spot in endothermic side, decreased methanol yield and glycerol con-
perature of 50−80 bar and 200−300 °C [5,6] using Cu/ZnO/Al2O3 as a version. Increasing feed flow rate in exothermic channel reduces me-
catalyst [7,8]. As this reaction is exothermic, researchers have devised thanol yield but help reducing temperature variation in endothermic
schemes to use heat released from MS in other reactions. Mirvakili et al. channel. Although MS as an exothermic reaction in thermally coupled
[9] simulated methanol synthesis coupled with cyclohexane dehy- reactor has been reported previously, there is no report on coupling MS
drogenation in membrane heat exchanger. Thermally coupled reactor with APGR in order to obtain hydrogen from the APGR.
was reported to perform better than a conventional reactor. Heat Hydrogen (H2) source and availability is one of the barriers to CO2
⁎
Corresponding author.
E-mail address: [email protected] (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
conversion to methanol. Glycerol can be a source of H2 production produced from APGR can be utilized in MS for methanol production. A
through steam reforming. The amount of crude glycerol produced from computational fluid dynamic (CFD) model was established to study this
biodiesel industry and other processes around the world is approxi- TDCR. Effects of operating conditions of both reactions: H2:CO2 and
mately 2.9 million tons per year and increasing. Crude glycerol can be glycerol:steam ratios, inlet temperature, and total feed flow rate on
refined further for use in chemical production. Nevertheless, glycerol is reactor performance were investigated.
still oversupplied in global market [12]. Therefore, conversion of gly-
cerol to higher value products has become a pressing issue. 2. Model description
Steam reforming of glycerol to H2 is an endothermic reaction. The
reaction is generally carried out in gas phase at atmospheric pressure 2.1. Reactor geometry
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 The TDCR in our study consisted of two concentric channels: 1) an
balance of plant. On the other hand, glycerol reforming can also occur inner tube and 2) an outer annulus channel. Fig. 1 shows a schematic
through aqueous-phase glycerol reforming (APGR) at relatively lower diagram of this TDCR. The diameter of the inner channel was 16 mm
temperatures and moderate pressures of 200−300 °C and 20−50 bar and the thickness of the annulus channel was 8 mm. The wall between
[14–18]. Guo et al. [14,16] studied APGR in different temperature the two channels was 2 mm thick. The reactor height was 150 mm. The
(200−245 °C) and pressure (18−40 bar). It was reported that high inner channel was intended for MS and the outer channel was designed
temperature and pressure significantly affects hydrogen selectivity and for APGR.
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
2.2. Reaction kinetics
are that no vaporization of the feedstock is required, which could de-
crease the input energy compared to steam reforming. Huber et al. [19]
2.2.1. Methanol synthesis (MS)
investigated different noble metal (Pt, Ru, Pd and Ir) on silica support
Only MS and reverse water gas shift reaction (RWGR) in gas phase
for AGPR reaction and Pt was reported to exhibit the highest perfor-
(Eqs. (1) and (2)) was assumed to occur in the inner channel.
mance among the tested catalyst. Pt/Al2O3 can be a potential catalyst
candidate for AGPR and was reported to provide glycerol conversion CO2 + 3H2 ↔ CH3 OH +H2 O ΔH298 = − 90.55 kJ mol−1 (1)
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 CO+H2 O↔ H2 + CO2 ΔH298 = +41.12 kJ mol−1 (2)
CO2 as by-product. Direct utilization of CO2 with H2 obtained from
APGR can be another promising pathway for glycerol conversion with The rate expression for MS has been extensively studied with dif-
ferent operating conditions [1,24,26,27]. Graaf et al. [26] described the
mitigating CO2 emission.
Multifunctional reactors featuring reactions coupled with distilla- 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
tion, separation or heat transfer have been extensively studied [22,23].
In this study, a novel thermally double coupled reactor (TDCR) cou- free energy at 200−250 °C. Anton et al. [27] reported the kinetic rate of
pling endothermic APGR with exothermic MS is proposed. Heat transfer MS at 250 °C and 50 bar when a Cu-Zn/Al-Zr fibrous catalyst was used.
between the two reactions is enabled in this reactor and lead to more Buessche et al. [24] developed a kinetic model and detailed a rate ex-
favorable conditions for higher reactant conversion. H2 and CO2 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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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
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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.
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 Figs. 6 and 7 show gas compositions in the MS and APGR channels in
the TDCR mode.
3.2.1. Effects of heat transfer between channels
APGR and MS were simulated in two modes: insulated channels and 3.2.2. Effects of reactor material
TDCR. Fig. 4 shows that, in the TDCR mode, the enabled heat transfer The material for reactor construction affects the thermal con-
enhanced glycerol conversion significantly from 20 % to 84 %. On the ductivity of the wall between the two channels. The previous simulation
other hand, CO2 conversion was virtually independent from the mode of TDCR was performed with stainless steel 316 (SS-316), which can
of operation. These results were attributed to the different temperature conduct heat rather well and withstand high pressure, as the reactor
profiles between the two modes. Fig. 5 presents the spatial average material [36]. Nevertheless, cheaper carbon steel, which provides lower
axial temperature profiles along the reactor length. Enabling the heat strength, offers a higher thermal conductivity of 54 W m−¹ K−¹ com-
transfer between the two channels resulted in a large increase in the pared to 16 W m−¹ K−¹ of stainless steel [37]. With carbon steel as the
temperature profile of the APGR channel but only a small decrease in reactor material, the heat transfer between the two channels of a TDCR
that of the MS channel. The changes in the temperature profiles led to was improved (Fig. 8)
the favorable equilibrium shifts towards the products in both channels. 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)
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Fig. 8. Average axial temperature profiles of the MS and APGR channels with stainless steel or carbon steel as the reactor material.
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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 It was likely that glycerol presented in both liquid and gas phase in the
on reactant conversion and H2 yield. Each operating parameter was system. Increasing pressure could increase glycerol concentration in
varied when the others were kept constant at the base case conditions. liquid phase and in turn increased glycerol conversion and H2 yield.
While the conditions of one channel were studied, those of the other The results corresponded with the experimental work of Garcı´ et al.
channel were untouched. Figs. 11 and 12 present the effects of the [41]. Fig. 12(c) shows decreases in the glycerol conversion and H2 yield
operating parameters on the performance of MS and APGR channels, as the total flow rate increased and led to a shorter residence time.
respectively. Fig. 12(d) presents the reduced glycerol conversion and H2 yield after
Fig. 11(a) shows the dependence of CO2 conversion and methanol increases in the feed glycerol:water ratio (1:9 to 1:3).
yield on the inlet temperature of the feed stream for MS in a range of Temperature, pressure, feed flow rate and feed ratio affected the
200−250 °C. Increasing the inlet temperature decreased CO2 conver- reactor performance. In the real operation, controlling the operating
sion following the expectation for the CO2 conversion of exothermic parameters of two reactions at the same time can be complicated. There
MS. The methanol yield also decreased as the inlet temperature in- are variables should be considered such as deactivation of catalyst as
creased. In Fig. 11(b) shows the effects of the inlet pressure in a range of well as side reactions of MS and APGR. Especially, purities in glycerol
50−80 bar. The CO2 conversion and methanol yield were affected in an feed obtained from the biodiesel production should be concerned.
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 4. Conclusion
rate increased due to a shorter residence time. This also indicated that
mass transport was not limiting. Fig. 11(d) shows that increasing the A steady-state heterogeneous catalytic reaction model was applied
CO2:H2 ratio (1:25 to 1:3) decreased the conversion of CO2 and me- to evaluate the performance of TDCR for simultaneous production of
thanol yield due to a shift in the chemical reaction equilibrium [40]. methanol and hydrogen in one reactor. In TDCR, transferred heat from
The CO2 conversion was rather high in excess H2 with CO2:H2 ratio exothermic MS to endothermic APGR channel helped increasing hy-
above 1:20 before sharply drop when decreasing H2 content. drogen yield in APGR when compared to a single APGR reactor. The
Operating parameters of the APGR channel were varied in the same TDCR could operate without external heat supply. Inlet temperature,
ranges as those of the MS to study their effects. Fig. 12(a) shows that pressure, feed flow rate and feed molar ratio in both MS and APGR
both the glycerol conversion and H2 yield increased as the feed inlet channels significantly affected reactor performance. Cocurrent config-
temperature increased in agreement with an expected shift of an en- uration was preferable in TDCR, offering more uniform temperature
dothermic reaction. On the other hand, Fig. 12(b) presents increases in distribution with a larger temperature difference between the two
glycerol conversion and H2 yield as the inlet pressure increased. This channels while hot spots and cold spots were observed in counter
clearly could not be explained by a shift in thermodynamic equilibrium. current configuration.
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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.
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