Electronic supplementary information - Dynamic

simulation of the CO2 methanation in a

micro-structured fixed-bed reactor
Bjarne Kreitza,∗, Gregor D. Wehingera , Thomas Tureka
a
Institute of Chemical and Electrochemical Process Engineering, Clausthal University of
Technology, Leibnizstr. 17, 38678 Clausthal-Zellerfeld, Germany

1. Correlations and Properties

Properties of the cooling medium [1]:

  
Toil
cp,oil = 647.94 + 3.325 · J kg−1 K−1 (1)
K
  
Toil
ρoil = 1308.1 − 0.9492 · kg m−3 (2)
K
  
Toil
λoil = 0.1666 + 0.0001 · W m−1 K−1 (3)
K
 2   !
Toil Toil
µoil = 6 · 10−9 · − 8 · 10−6 · + 0.0028 Pa s (4)
K K

Viscosity of single components [2]:

3  j !
X ϑ
µi = µi,j · ◦ Pa s (5)
j=0
C

The viscosity of the mixture is calculated according to the Wilke approach

[3].

∗
Corresponding author
Email address: kreitz@icvt.tu-clausthal.de (Bjarne Kreitz)

Preprint submitted to Chemical Engineering Science September 24, 2018

 µ0 · 10−5 µ1 · 10−8 µ2 · 10−11 µ3 · 10−15
H2 0.8337 2.202 1.1216 5.1074
CO2 1.3799 4.8847 1.7863 3.4755
H2 O 0.8115 3.9343 0.71973 7.2056
CH4 1.0236 3.2886 1.07925 7.0733

n
X y i · µi
µg = Pn (6)
i=1 j=1 yj · Φi,j

With the parameter Φi,j :

   12   14 2
M
1 + µµji · Mji
Φi,j = h  i 12 (7)
Mi
8· 1+ Mj

Strongly coupled with the viscosity is the thermal conductivity of the gas
mixture. The correlation for the calculation of the thermal conductivities of
the pure components can be found in the work of Elnashaie [4].
3  j !
X Tg
λi = 1.163 · λi,j · W m−1 K−1 (8)
j=0
K

λ0 · 10−2 λ1 · 10−5 λ2 · 10−8 λ3 · 10−12

H2 13.9584 38.5097 −12.5689 47.7818
CO2 1.38695 6.04059 0.914853 −12.7413
H2 O 0.998229 10.0049 −2.96743 23.0937
CH4 0.0324699 29.9243 −32.3017 258.011

The thermal conductivity of the gas mixture is calculated via the Wassil-
jewa approach and the Lindsay-Bromley-Method [4].
n
X yi · λi
λg = Pn (9)
i=1 j=1 yj · Ai,j
 "   34 # 12 2
µi Mj Tg + Si  · Tg + Si,j
Ai,j = 0.25 · 1 + · · (10)
µj Mi Tg + Sj Tg + Si

2
 With:

Si = 1.5 · Tb,i (11)

1
Si,j = Sj,i = FS · (Si · Sj ) 2 (12)

In these equations Si is the Sutherland constant, Tb,i is the boiling tem-

perature of the component and FS is equal to unity for all possible pairs
except CO2 /H2 . In this case the parameter has the value 0.735.
Values for the boiling temperature of CO2 , H2 O, CH4 [4] and H2 [2] are
summarized in the following table. Diffusion volumes of CO2 , H2 O, CH4
are taken from Perry’s [5] and the diffusion volume of methane is calcu-
lated with atomic diffusion volume increments of C= 16.5 cm3 mol−1 and
H= 1.98 cm3 mol−1 .
H2 CO2 H2 O CH4
Tb,i / K 79 194.6 373.15 110.70
νDiff,i / cm3 mol−1 7.07 26.9 12.7 24.42

The heat conduction of the packed bed is calculated with the model of
Zehner-Bauer-Schlünder [6].

  10
1 − εbed 9
B = 1.25 · (13)
εbed
λs
Bs = (14)
λg
B
N =1− (15)
B
  s 
2 B(Bs − 1) Bs B+1 B−1
Bc = ln − − (16)
N N 2 Bs B 2 N
λbed √ √
Bbed = = 1 − 1 − εbed + Bc 1 − εbed (17)
λg

For the calculation of the heat and mass transfer from the gas to the
catalyst surface the correlation from Gnielinski [7] is used.

3
 λg
hGS = N uGS (1 + 1.5(1 − εbed )) (18)
ds
q
N uGS = 2 + N u2GS, lam + N u2GS, turb (19)
N uGS, lam = 0.664P r0.33 Re0.5 (20)
0.037P rRe0.8
N uGS, turb = (21)
1 + 2.443Re−0.1 (P r0.67 − 1)

D
βGS = ShGS (1 + 1.5(1 − εbed )) (22)
ds
q
ShGS = 2 + Sh2GS, lam + Sh2GS, turb (23)
ShGS, lam = 0.664Sc0.33 Re0.5 (24)
0.037ScRe0.8
ShGS, turb = (25)
1 + 2.443Re−0.1 (Sc0.67 − 1)

The overall heat transfer coefficient is calculated with the αwall model [8].

 
hwall ds 5ds
N uwall = = 1.3 + Bbed + 0.19Re0.75 P r0.33 (26)
λg dh
Pe
λeff
r = λbed + λg (27)
KR
 2 !
2 · ds
KR = 7 · 2 − 1 − (28)
dh
u · ds · ρg · cp,g
Pe = (29)
λg

1 1 dh dwall 1
= + eff + + (30)
hov hwall 8λr λwall hoil
The axial dispersion coefficients of heat and mass in a fixed-bed reactor
for gas are calculated with the equations below [8].

4
 Di,bed √
= 1 − 1 − εbed (31)
Di,M
u · ds
P e0 = (32)
Di,bed
√
1 1 − 1 − εbed
= + 0.5 (33)
P emass P e0
u · ds
P emass = (34)
Dax
1 Bbed
= + 0.5 (35)
P eheat Pe
u · ds · cp,g · ρg
P eheat = (36)
λax
The coefficients A and B are required for the pressure drop equation of
Eisfeld and Schnitzlein [9].

2
A=1+   (37)
dh
3· ds
· (1 − εbed )
 2 !2
ds
B= 1.15 · + 0.87 (38)
dh

The following equations are used for the calculation of the convective heat
transfer in the coolant channel in the intermediate flow regime [10]:

5
 Reoil − 2300
γ= (39)
104 − 2300
1
N uL,2300 = 49.371 + (N u2,2300 − 0.7)3 + (N u3,2300 )3 3

(40)
 1
d 3
N u2,2300 = 1.615 2300P roil (41)
L
  16  1
2 d 2
N u3,2300 = 2300P roil (42)
1 + 22P roil L
4

−2
ξ = 1.8 log 10 − 1.5 (43)
"   23 #
(ξ/8)104 P roil d
N uT,104 =  2  1+ (44)
p
1 + 12.7 ξ/8 P roil 3
−1 L

N uoil = (1 − γ)N uL,2300 + γN uT,104 (45)

6
2. Additional Figures

(a) (b)
2.5 5
λg /λss η/ηss
g
λbed /λss
bed
hov /hss 4

relative catalyst efficiency / 1

2 ov
relative properties / 1

3
1.5
steady state

2 steady state
1

1
0.5
0.65 0.7 0.75 0.8 0.85 0.9 0.95
0.65 0.7 0.75 0.8 0.85 0.9 0.95
hydrogen mole fraction / 1
hydrogen mole fraction / 1

Figure 1: (a) Phase plane of the relative heat transfer properties for an amplitude of
∆y = 0.1 and a frequency of f = 0.1 s−1 . The black dot in the center represents the
mean value of the steady-state profile. (b) Relative variation of the catalyst efficiency.
Conditions: Tg0 = 280 ◦C, d = 2 mm, ds = 400 µm, p = 8 bar, GHSV = 3143 h−1 .

(a) (b)
500 1
∆y = 0.05 L-Gas
steady state
∆y = 0.1
∆y = 0.15 0.8
methane mole fraction (dry) / 1

450
gas phase temperature / ◦C

0.6
400

0.4
350

0.2 ∆y = 0.05
∆y = 0.1
300
∆y = 0.15
0
0.65 0.7 0.75 0.8 0.85 0.9 0.95 0.65 0.7 0.75 0.8 0.85 0.9 0.95
hydrogen mole fraction / 1 hydrogen mole fraction / 1

Figure 2: Results for the dynamic simulation of the microstructured fixed-bed reactor. (a)
Phase plane of the maximum temperatures of the gas phase (Tg ) for different amplitudes
and a frequency of f = 0.1 s−1 (blue) and f = 0.05 s−1 (orange) . The black dot in the
center represents the maximum of the steady-state profile. (b) Variation of the methane
outlet concentration for different amplitudes in the phase plane for a frequency of f =
0.1 s−1 . Conditions: Tg0 = 280 ◦C, d = 2 mm, ds = 400 µm, p = 8 bar, GHSV = 3143 h−1 .

7
3. Comparison between Wilke-Bosanquet and Dusty-Gas model
In this simulation study the Wilke-Bosanquet diffusion model was used, as
a compromise between accuracy and complexity. The more accurate Dusty-
Gas model adds a higher degree of numerical complexity to the simulation
and requires a higher effort to solve the problem. To justify our usage of the
simplified diffusion approach, we performed additional calculations to reveal
the differences between both models and to verify our assumption. The fol-
lowing figures show the steady state concentration profile of the components
in the pellet for a temperature of 350 ◦C and a pressure of 8 bar. The prop-
erties of the pellet can be found in the manuscript in Table 1. For details on
the Dusty-Gas model please refer to the work of Solsvik and Jakobsen [11].

(a) (b)
150 150
H2 H2
CO2 CO2
CH4 CH4
cs / mol m−3

cs / mol m−3

100 H2 O 100 H2 O

50 50

0 0
0 0.2 0.4 0.6 0.8 1 0 0.2 0.4 0.6 0.8 1
r r
R
/1 R
/1

Figure 3: Concentration profile in the catalyst pellet calculated with the Wilke-Bosanquet
approach (solid) and the Dusty-Gas model (dotted). Figure (a) is calculated for a bulk
gas phase composition of xH2 = 0.8 and xCO2 = 0.2. Figure (b) is the result for the gas
phase composition at the hot spot with xH2 = 0.5553, xCO2 = 0.1313, xCH4 = 0.1144 and
xH2 O = 0.2288. Conditions: Tg = 350 ◦C, ds = 400 µm, p = 8 bar.

It can be seen that there is only small difference between the Wilke-
Bosanquet approach and the Dusty-Gas model. Therefore, the usage of the
simplified diffusion model seems reasonable. Additionally, the influence of
the convective flow in the dusty-gas model due to the mole change of the
reaction has also been investigated, but this turned out to be not significant
for the assumed pellet.

8
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