On the influence of Si:Al ratio and hierarchical porosity of FAU
zeolites in solid acid catalysed esterification pretreatment of
bio-oil
a Amin Osatiashtiani, b Begoa Purtolas, c Caio C. S. Oliveira, a
Jinesh C. Manayil, a Brunella Barbero, a Mark Isaacs, d Chrysoula
Michailof, d Eleni Heracleous, b Javier Prez-Ramrez, a Adam F. Lee,
a Karen Wilson*
a European Bioenergy Research Institute, Aston University,
Birmingham B4 7ET, UK.
b Institute for Chemical and Bioengineering, Department of
Chemistry and Applied Biosciences, ETH Zurich, Vladimir-Prelog-Weg
1, CH-8093 Zurich, Switzerland.
c Technological Research Institute (IPT), 05508-901, So Paulo,
Brazil.
d Chemical Process & Energy Resources Institute Centre for
Research and Technology-Hellas (CPERI/CERTH) 6th km Harilaou-Thermi
Road, 57001,Thessaloniki, Greece.
* E-mail: [email protected]; Tel: +44 121 204 5456
Electronic Supporting Information
Table S1. Surface elemental analysis of FAU zeolite catalysts by
XPS
Nominal
Si:Al ratio
Concentration / wt%
Concentration / At%
Si:Al atomic ratio
O
Si
Al
O
Si
Al
2.6
46.3
32.1
21.5
59.9
23.7
16.5
1.4
6
48.5
42.4
9.2
62.1
30.9
7.0
4.4
30
47.8
50.4
1.9
61.6
37.0
1.4
25.9
HFAU30
48.8
49.2
2.1
62.5
35.9
1.6
23.0
Figure S1. Schematic of in-situ ATR-IR flow cell.
Figure S2. XRD patterns for FAU zeolites.
Figure S3. Surface atomic concentration of Si and O from
quantification of Si 2p and O 1s XP spectra as a function of Si:Al
ratio in FAU zeolites.
Figure S4. ATR-IR spectra of acetic acid adsorbed over FAU2.6 as
a function of time.
Figure S5. ATR-IR spectra of acetic acid adsorbed over FAU6 as a
function of time.
Figure S6. ATR-IR spectra of acetic acid adsorbed over FAU30 as
a function of time.
Figure S7. ATR-IR spectra of the Methoxy group region during the
adsorption of acetic acid. At 0 min (black line) only methanol is
adsorbed on the catalyst surface. After 30min of acetic acid flow
(red line) the Methoxy peak is more broad and negative because of
the competitive adsorption between the solvent and the probe
molecule.
Figure S8. Esterification of acetic acid with various alcohols
in an alcohol-rich media over FAU zeolites with 2.6 (), 6 (), 30 ()
Si:Al ratio and HFAU zeolite (). (Reaction conditions: 5 mmol
acetic acid, acid:alcohol = 1:5 mol:mol, 10 ml toluene, 100 mg
catalyst, 100 C)
Figure S9. Acetic acid conversion and ester selectivity as a
function of FAU zeolite Si:Al ratio for esterification with a)
benzyl alcohol and b) anisyl alcohol. (Reaction conditions: 5 mmol
acetic acid, acid:alcohol = 1:5 mol:mol, 10 ml toluene, 100 mg
catalyst, 100 C, 3h)
Figure S10. Esterification of acetic acid with methanol (),
anisyl alcohol (), benzyl alcohol (), p-cresol () and n-butanol ()
over FAU30. (Reaction conditions: acid:alcohol = 1 (left), 5
(right), 10 ml toluene, 100 mg catalyst, 100 C)
00.020.040.0611001200130014001500160017001800AbsorbanceWavenumber /
cm-10 min1 min2 min3 min4 min5 min10 min20 min25 min30
minFAU2.6
00.020.040.0611001200130014001500160017001800AbsorbanceWavenumber /
cm-10 min1 min2 min3 min4 min5 min10 min20 min25 min30 minFAU6
00.020.040.0611001200130014001500160017001800AbsorbanceWavenumber /
cm-10 min1 min2 min3 min4 min10 min15 min20 min25 min30
minFAU30
-0.03-0.025-0.02-0.015-0.01-0.0050270029003100AbsorbanceWavenumber
/ cm-10 min30 min
0204060060120180
Acid conversion / %Time / min
p-cresol
0204060060120180
Acid conversion / %Time / min
n-butanol
020406080060120180Acid conversion / %Time / minBenzyl
alcohol
020406080060120180Acid conversion / %Time / minAnisylalcohol
020406080100060120180
Acid conversion / %Time / min
Methanol
0204060802.6630Acid conversion, benzyl acetate selectivity /
%Si:Al ratioSelectivityConversion(a)
0204060802.6630Acid conversion, anisyl acetate selectivity /
%Si:Al ratioSelectivityConversion(b)
020406080100060120180Acid conversion / %Time / minAcid:alcohol
ratio = 1
0510152025060120180
Acid conversion / %Time / min
Acid:alcohol ratio = 5
10203040506070802HFAUFAU30FAU6FAU2.6
0204060800102030At. %Si:Al Atomic Ratio(Si) - O-AlSi - (O) -
Al