APPENDIX 1:

Calculation Methodology [1],[2],[3]

Mi P
ρi=
Density of component i , RT
( 1)

ρmix =Σ y i M i
Density of the mixture,
(2 )

ṅtotal RT
V̇ =
Volumetric flow rate, P
( 3)
V̇
u0 =
Velocity, A
(4 )

u¿ =ε b u 0
Superficial velocity,
( 5)

The porosity of the packed bed can be calculated from the following equation which is valid for a mono
disperse package of spheres [4],

( )
2
d cat d cat
ε b=0.4 +0.05 +0.412
d tube d tube
(6 )
Viscosity of component I [4],[5]
2
μi= A+ BT +C T
(7)

B
AT
μ DME=
C
1+
T
( 8)

Components A B C
N2 42.606 0.475 -0.0000988
 H2 27.75 0.212 -0.0000328
CO 23.811 0.53944 -0.00015411
CO2 11.811 0.49838 -0.00010851
CH3OH -14.236 0.38935 -0.00006276
H2O -36.826 0.429 -1.62E-05
C2H6O 2.86E-06 0.3975 534

Viscosity of the mixture,

μmix =
∑ y i μi √ M i
∑ yi √ M i
( 9)

Pressure drop by Ergun’s equation,

2
2(
ⅆp 1−ε b ) μ mix u ¿ ( 1−ε b ) u¿2 ρ
=−154 A −
ⅆx εb
3
d cat
2
εb
3
d cat
( 10 )

2
u ¿ d tube
Dax =Dm +
Axial Diffusivity is given by 192 D m
(11 )

Thermal conductivity of component i,

The Glenn equations for the heat capacity for the present components are implemented in Python as follows.
[6]
A B 2 3 4
Cpi= + +C+ DT + E T + F T +GT
T T
2

( 12 )
Component A B C D E F G
s
N2 2.21E+04 -3.82E+02 6.08E+00 - 1.38E-05 -9.63E-09 2.52E-12
8.53E+03
CO 1.49E+04 -2.92E+02 5.72E+00 - 1.46E-05 -1.09E-08 3.03E-12
8.18E+03
H2 4.08E+04 -8.01E+02 8.21E+00 -1.27E-02 1.75E-05 -1.20E-08 3.37E-12
H2O -3.95E+04 5.76E+02 9.32E-01 7.22E-03 -7.34E-06 4.96E-09 -1.34E-12
CO2 4.94E+04 -6.26E+02 5.30E+00 2.50E-03 -2.13E-07 -7.69E-10 2.85E-13
CH3OH -2.42E+05 4.03E+03 -2.05E+01 6.90E-02 -7.60E-05 4.60E-08 -1.16E-11
CH3OCH3 -2.69E+05 4.30E+03 -2.15E+01 8.13E-02 -8.30E-05 4.80E-08 -1.19E-11

Effective thermal conductivity,

λ eff =ε cat λ mix + ( 1−ε cat ) λ cat

( 13 )

Diffusivity of species i in the mixture,

1− y i
D i , m= N
where j ≠i
yj
∑ Di , j
j=1
( 14 )

Binary Diffusivity,

D i , j=
10−3 T 1.75
1

P¿¿¿
−
√1
Mi M j

'
where v i is the diffusion volume of each component taken¿ Perr y s handbook .

Effective diffusivity of species i in the catalyst layer ,

ε cat
D eff = ¿ (16)
τ

√
d pore 8 RT
D K ,i =
Knudsen diffusivity for species i, 3 π Mi
( 17 )
Rate Equations and Constants[2]

As reported in the following rate equations were implemented in the model equation. Reaction rates are in
[mol/kgcat/s], fugacities in [bar] and concentrations in [mol/m3] units. The parameters are given in Table S1.

( )
3
f CH OH
K CO f CO f 2H − 3

(f )
2 1
2
H2 K eq, 1
R1=k 1 ( 18 ) ¿

( )
1

( 1+ K CO f CO + K CO f CO ) 2 2
2
f +KH O f H
H2 2 2
O
H2
¿

R2=k 2
K CO f CO f H −
2 ( 2 2
f H O f CO
K eq, 2
2

)
( )
1

( 1+ K CO f CO + K CO f CO ) 2 2
2
f +KH O f H
H2 2 2
O
H2

(19 )

( )
3
2
f CH OH f H O
K CO f CO f − H2
3 2

(f )
2 2 3
2
H2 K eq ,3
R3=k 3

( )
1

( 1+ K CO f CO + K CO f CO ) 2 2
2
f +K H O f H
H2 2 2
O
H2

( 20 )

K CH OH CCH OH (1−C H O C CH O CH / ( C CH OH K eq ,4 ) )
2 2 2
3 3 2 3 3 3
R4 =k 4 4
(1+2 √ K CH OH C CH OH + K H O C H O )
3 3 2 2

( 21 )
Table S1. Kinetic, adsorption and equilibrium constants [7], [8], [9], [10].

Kinetic rate equation Units

( )
−109900 [mol/kgcat/s/bar3/2]
k 1=2.69 x 107 exp
RT

( )
−123400 [mol/kgcat/s/bar]
k 2=7.31 x 108 exp
RT

( )
2 −65200 [mol/kgcat/s/bar3/2]
k 3=4.36 x 10 exp
RT

( )
−105000 [mol/kgcat/s]
k 4=1.0278 x 10 10 exp
RT

( )
58100 [bar-1]
K CO =7.99 x 10−7 exp
RT

( )
67400 [bar-1]
K CO =1.02 x 10−7 exp
2
RT

( )
−11 104500 [bar-1/2]
K H O / H =4.13 x 10 exp
2 2
RT

( )
70500 [m3/mol]
K CH OH =7.9 x 10−7 exp
3
RT

( )
41100 [m3/mol]
K H O =0.84 x 10−4 exp
2
RT
5139 [-]
log K eq ,1= −12.621
T
−2073 [-]
log K eq ,2= +2.029
T

K eq ,3=K eq ,1 K eq , 2 [bar-2]

4019 −3 −7 2 6.561 x 10
[-]
4
ln K eq ,4 = +3.707 ln T −2.783 x 10 T + 3.8 x 10 T − 3
−26.6 4
T T

Dimensionless Numbers [1], [2], [11], [12], [13]

 Dimensionless Numbers / Parameters Formulas
Bodenstein Number u¿ L t
Bo =
Dax
Reynold’s Number u¿ ρmix d tube
Re =
μ mix
Schmidt Number μ mix
Sc =
ρmix Dm
Sherwood’s Number Sh = C 1+C 2 ℜ Sc
C 3 C 4

where C 1=2, C 2=0.6, C 3=0.5, C 4=0.66

Mass Transfer Co-efficient Sh
k s=D m
d cat
Prandtl Number μ mix C p , mix
Pr =
λ mix
Nusselt Number 2 1
Nu= (0.5 0.5 3 3
ℜ + 0.2 ℜ ¿ Pr
Nu = 3.66 Fully developed laminar flow
Heat Transfer Co-efficient Nu
h s=λ mix
d cat
Specific surface area At 6
a FS= =
V dt

References:

[1] B. Kreitz, G. D. Wehinger, and T. Turek, “Dynamic simulation of the CO2 methanation in a micro-
structured fixed-bed reactor,” Chem. Eng. Sci., vol. 195, pp. 541–552, Feb. 2019, doi:
10.1016/j.ces.2018.09.053.

[2] S. Guffanti, C. G. Visconti, J. Van Kampen, J. Boon, and G. Groppi, “Reactor modelling and design for
sorption enhanced dimethyl ether synthesis,” Chem. Eng. J., vol. 404, p. 126573, Jan. 2021, doi:
10.1016/j.cej.2020.126573.

[3] H. H. Koybasi and A. K. Avci, “Numerical Analysis of CO 2 -to-DME Conversion in a Membrane

Microchannel Reactor,” Ind. Eng. Chem. Res., vol. 61, no. 30, pp. 10846–10859, Aug. 2022, doi:
10.1021/acs.iecr.2c01764.

[4] “Yaws_chemical_properties_handbook_pdf.pdf.”

[5] D. W. Green and M. Z. Southard, Eds., Perry’s chemical engineers’ handbook, Ninth edition, 85th
anniversary edition. New York: McGraw Hill Education, 2019.

[6] B. J. McBride, M. J. Zehe, and S. Gordon, “NASA Glenn Coefficients for Calculating Thermodynamic
Properties of Individual Species,” 2002.

[7] G. E. H. J. G. H. Graaf, P. J. J. Sijtsema, E. J. Stamhuis, “Chemical equilibria in methanol synthesis,”

Chem. Eng. Sci., vol. 41, no. 11, pp. 2883–2890, 1986.

[8] G. H. Graaf, E. J. Stamhuis, and A. A. C. M. Beenackers, “Kinetics of low-pressure methanol synthesis,”

Chem. Eng. Sci., vol. 43, no. 12, pp. 3185–3195, 1988, doi: 10.1016/0009-2509(88)85127-3.

[9] K. L. Ng, D. Chadwick, and B. A. Toseland, “Kinetics and modelling of dimethyl ether synthesis from
synthesis gas,” Chem. Eng. Sci., vol. 54, no. 15–16, pp. 3587–3592, 1999, doi: 10.1016/S0009-2509(98)00514-4.
[10] W. Z. Lu, L. H. Teng, and W. De Xiao, “Simulation and experiment study of dimethyl ether synthesis
from syngas in a fluidized-bed reactor,” Chem. Eng. Sci., vol. 59, no. 22–23, pp. 5455–5464, 2004, doi:
10.1016/j.ces.2004.07.031.

[11] S. Hosseininejad, A. Afacan, and R. E. Hayes, “Catalytic and kinetic study of methanol dehydration to
dimethyl ether,” Chem. Eng. Res. Des., vol. 90, no. 6, pp. 825–833, Jun. 2012, doi: 10.1016/j.cherd.2011.10.007.

[12] S. Guffanti, C. G. Visconti, and G. Groppi, “Model Analysis of the Role of Kinetics, Adsorption Capacity,
and Heat and Mass Transfer Effects in Sorption Enhanced Dimethyl Ether Synthesis,” Ind. Eng. Chem. Res., vol.
60, no. 18, pp. 6767–6783, May 2021, doi: 10.1021/acs.iecr.1c00521.

[13] J. Lefebvre, S. Bajohr, and T. Kolb, “Modeling of the transient behavior of a slurry bubble column
reactor for CO2 methanation, and comparison with a tube bundle reactor,” Renew. Energy, vol. 151, pp. 118–
136, May 2020, doi: 10.1016/j.renene.2019.11.008.