static-content.springer.com10.1007... · Web viewproduction from sorbitol over heterogeneous acid catalysts: screening and kinetic study Gabriel Morales*, Jose Iglesias, Juan A. Melero,

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]

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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.


SAC-13T=190 oC


Exp. Exp. Exp. Exp.



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Exp. Exp. Exp. Exp.

Reaction time (min)


Exp. Exp. Exp. Exp.


H-beta-12.5


Exp. Exp. Exp. Exp.



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18Sorbitol 1,4-SorbitanSorbitan (others)Isosorbide

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Reaction time (min)


Sorbitol 1,4-SorbitanSorbitan (others)Isosorbide

USY

Sorbitol 1,4-SorbitanSorbitan (others)Isosorbide

Exp. Exp. Exp. Exp.


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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.

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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

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5.000

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7.000ln k1

1/T (K-1)

ln k

I.2. SBA-15-Pr-SO3H


k2 (kg-1min-1)

k3 (kg-1min-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



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0.0021 0.00215 0.0022 0.00225 0.0023 0.00235 0.00240.000

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ln k1

1/T (K-1)

ln k

I.3. SAC-13


k2 (kg-1min-1)

k3 (kg-1min-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



0.0021 0.00215 0.0022 0.00225 0.0023 0.00235 0.00240.000

0.500

1.000

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ln k1

1/T (K-1)

ln k

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I.4. ZEOLITE H-BETA-12.5


k2 (kg-1min-1)

k3 (kg-1min-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



0.0021 0.00215 0.0022 0.00225 0.0023 0.00235 0.00240.000

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ln k1

1/T (K-1)

ln k

I.5. ZEOLITE H-BETA-19


k2 (kg-1min-1)

k3 (kg-1min-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



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0.0021 0.00215 0.0022 0.00225 0.0023 0.00235 0.00240.000

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ln k1

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ln k

I.6. ZEOLITE H-USY


k2 (kg-1min-1)

k3 (kg-1min-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



0.0021 0.00215 0.0022 0.00225 0.0023 0.00235 0.00240.000

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Figure S2. XRD patterns of the commercial zeolites.

Figure S3. Low-angle XRD pattern of SBA-15-Pr-SO3H.

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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

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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.

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static-content.springer.com10.1007... · Web viewproduction from sorbitol over heterogeneous acid catalysts: screening and kinetic study Gabriel Morales*, Jose Iglesias, Juan A. Melero,