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Transcript of static-content.springer.com10.1007... · Web viewproduction from sorbitol over heterogeneous acid...
SUPPLEMENTARY INFORMATION
Isosorbide production from sorbitol over heterogeneous acid catalysts: screening and kinetic study
Gabriel Morales*, Jose Iglesias, Juan A. Melero, Jovita Moreno, Rebeca Sánchez-Vázquez, Ángel Peral, Alberto Cubo
ESCET. Universidad Rey Juan Carlos.
C/ Tulipán s/n. E28933. Móstoles. Madrid. Spain.
* To whom correspondence should be addressed:
Gabriel Morales
Ph. N. +34 914 888 091
e-mail: [email protected]
SI.1
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Sorbitol1,4-SorbitanSorbitan (others)Isosorbide
Exp. Exp. Exp. Exp.
Reaction time (min)
Model. Model. Model. Model.
T=170 oCT=150 oC Exp. Exp. Exp. Exp.
Sorbitol1,4-SorbitanSorbitan (others)Isosorbide
SAC-13T=190 oC
Model. Model. Model. Model.
Exp. Exp. Exp. Exp.
Sorbitol1,4-SorbitanSorbitan (others)Isosorbide
Model. Model. Model. Model.
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ol
Sorbitol1,4-SorbitanSorbitan (others)Isosorbide
Exp. Exp. Exp. Exp.
Reaction time (min)
Model. Model. Model. Model.
Exp. Exp. Exp. Exp.
Sorbitol1,4-SorbitanSorbitan (others)Isosorbide
H-beta-12.5
Model. Model. Model. Model.
Exp. Exp. Exp. Exp.
Sorbitol1,4-SorbitanSorbitan (others)Isosorbide
Model. Model. Model. Model.
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Exp. Exp. Exp. Exp.
mm
ol
Reaction time (min)
Model. Model. Model. Model.
Sorbitol 1,4-SorbitanSorbitan (others)Isosorbide
USY
Sorbitol 1,4-SorbitanSorbitan (others)Isosorbide
Exp. Exp. Exp. Exp.
Model. Model. Model. Model.
Exp. Exp. Exp. Exp.
Model. Model. Model. Model.
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18 Sorbitol (exp.) 1,4-Sorbitan (exp.) Sorbitan (others) (exp.) Isosorbide (exp.)
Sorbitol (exp.) 1,4-Sorbitan (exp.) Sorbitan (others) (exp.) Isosorbide (exp.)
mm
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Reaction time (min)
Sorbitol (exp.) 1,4-Sorbitan (exp.) Sorbitan (others) (exp.) Isosorbide (exp.)
H-ZSM-5
(a)
(b)
(c)
(d)
Figure S1. Kinetic data (experimental and modelled) obtained for SAC-13 (a), zeolite H-beta-12.5 (b), zeolite H-USY (c), and zeolite H-ZSM-5 at different temperatures. Sorbitan (others) include 1,5-sorbitan and 2,5-sorbitan (2-5 anhydro-L-iditol and 2-5 anhydro-D-mannitol). Reaction conditions: sorbitol initial loading
= 3.0 g; sorbitol/catalyst mass ratio = 20/1.
SI.2
I. Summary of kinetic data
I.1. AMBERLYST-70
T (ºC)k1 (kg-1min-1)
k2 (kg-1min-1)
k3 (kg-1min-1)
k4 (kg-1min-1) Kads (mol-1)
150 84.52 33.85 18.44 6.92 1.09E-03170 192.32 94.06 45.62 22.07 2.79E-03190 352.95 292.28 65.78 88.63 1.87E-02
Arrhenius parameter Reaction 1 Reaction 2 Reaction 3 Reaction 4
EA (KJ/mol) 58.28 87.63 52.07 103.58k0 (kg-1min-1) 1.36E+09 2.17E+12 5.36E+07 4.06E+13
0.0021 0.00215 0.0022 0.00225 0.0023 0.00235 0.00240.000
1.000
2.000
3.000
4.000
5.000
6.000
7.000ln k1
1/T (K-1)
ln k
I.2. SBA-15-Pr-SO3H
T (ºC)k1 (kg-1min-1)
k2 (kg-1min-1)
k3 (kg-1min-1)
k4 (kg-1min-1) Kads (mol-1)
150 129.12 4.72 18.15 2.80 3.24E-04170 332.26 25.27 61.32 23.00 5.38E-03190 1107.38 83.27 213.34 151.33 9.95E-03
Arrhenius parameter Reaction 1 Reaction 2 Reaction 3 Reaction 4
EA (KJ/mol) 87.26 117.02 100.23 162.44k0 (kg-1min-1) 7.29E+12 1.41E+15 4.23E+13 3.24E+20
SI.3
0.0021 0.00215 0.0022 0.00225 0.0023 0.00235 0.00240.000
1.000
2.000
3.000
4.000
5.000
6.000
7.000
8.000
ln k1
1/T (K-1)
ln k
I.3. SAC-13
T (ºC)k1 (kg-1min-1)
k2 (kg-1min-1)
k3 (kg-1min-1)
k4 (kg-1min-1) Kads (mol-1)
150 28.42 3.89 6.81 15.68 1.12E-03170 37.71 14.35 10.91 36.21 5.69E-02190 96.15 55.46 31.40 54.74 5.08E-01
Arrhenius parameter Reaction 1 Reaction 2 Reaction 3 Reaction 4
EA (KJ/mol) 49.18 108.02 61.85 51.12k0 (kg-1min-1) 3.01E+07 8.30E+13 2.66E+08 3.41E+07
0.0021 0.00215 0.0022 0.00225 0.0023 0.00235 0.00240.000
0.500
1.000
1.500
2.000
2.500
3.000
3.500
4.000
4.500
5.000
ln k1
1/T (K-1)
ln k
SI.4
I.4. ZEOLITE H-BETA-12.5
T (ºC)k1 (kg-1min-1)
k2 (kg-1min-1)
k3 (kg-1min-1)
k4 (kg-1min-1) Kads (mol-1)
150 23.38 6.16 2.82 --- 4.34E-03170 77.41 29.31 11.15 --- 2.80E-02190 162.64 226.84 21.07 --- 1.42E-01
Arrhenius parameter Reaction 1 Reaction 2 Reaction 3 Reaction 4
EA (KJ/mol) 79.18 146.39 82.30 85.48k0 (kg-1min-1) 1.49E+11 6.65E+18 4.54E+10 1.41E+11
0.0021 0.00215 0.0022 0.00225 0.0023 0.00235 0.00240.000
1.000
2.000
3.000
4.000
5.000
6.000
ln k1
1/T (K-1)
ln k
I.5. ZEOLITE H-BETA-19
T (ºC)k1 (kg-1min-1)
k2 (kg-1min-1)
k3 (kg-1min-1)
k4 (kg-1min-1) Kads (mol-1)
150 31.71 7.08 4.00 --- 6.31E-04170 133.17 32.59 19.93 --- 7.81E-04190 187.90 186.00 28.14 --- 8.22E-04
Arrhenius parameter Reaction 1 Reaction 2 Reaction 3 Reaction 4
EA (KJ/mol) 73.05 132.83 80.15 48.41k0 (kg-1min-1) 3.91E+10 1.69E+17 3.76E+10 1.13E+07
SI.5
0.0021 0.00215 0.0022 0.00225 0.0023 0.00235 0.00240.000
1.000
2.000
3.000
4.000
5.000
6.000
ln k1
1/T (K-1)
ln k
I.6. ZEOLITE H-USY
T (ºC)k1 (kg-1min-1)
k2 (kg-1min-1)
k3 (kg-1min-1)
k4 (kg-1min-1) Kads (mol-1)
150 3.90 2.02 1.22 1.26 8.70E-04170 12.21 2.34 4.84 7.22 2.84E-03190 39.77 4.72 16.80 19.57 5.68E-03
Arrhenius parameter Reaction 1 Reaction 2 Reaction 3 Reaction 4
EA (KJ/mol) 94.47 34.17 106.70 112.19k0 (kg-1min-1) 1.77E+12 3.05E+04 1.84E+13 9.92E+13
0.0021 0.00215 0.0022 0.00225 0.0023 0.00235 0.00240.000
0.500
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ln k1
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SI.6
SI.7
Figure S2. XRD patterns of the commercial zeolites.
Figure S3. Low-angle XRD pattern of SBA-15-Pr-SO3H.
SI.8
0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.00
50100150200250300350400450500
Commercial beta zeolite Hierarchical beta zeolite
P/Po
Adso
rbed
volum
e (cm
3 /g, S
TP)
+100 cm3
/g
Figure S4. Argon adsorption isotherms recorded at 87K for commercial and hierarchical beta zeolites
SI.9
Figure S5. TG (red) and DTG (blue) curves recorded for SBA-15-Pr-SO3H, Amberlyst-70 and zeolite Beta-19, including fresh samples (left); spent samples (middle) and regenerated samples (right). Regeneration
treatment consisted of washing with HCl/EtOH solution for sulfonic catalysts and calcination at 400ºC for the zeolite. Reaction conditions: 150°C, 24h, sorbitol loading = 3.0 g; sorbitol/catalyst mass ratio = 20/1.
SI.10