ChemCatChem
10.1002/cctc.201801469
FULL PAPER
with methyl glycolate, methyl-2-hydroxyisobutyrate and methyl lactate
were performed in a custom-built plug-flow fixed-bed reactor equipped with
M.D. thanks Research Foundation - Flanders (FWO) for funding
and KU Leuven BOF for his appointment to Research Professor.
E.M., B.F.S and M.D. thank the Industrial Research Fund (IOF,
grant ZKC8139). A patent application was filed for this process.
6
parallel quartz reactors (length 480 mm, inner diameter of 4 mm) that
can be operated one at a time. The quartz reactors were filled with 10-300
mg of catalyst (sieved fraction 250-500 µm), supported by quartz wool. If
less than 300 mg was used, the catalyst bed was diluted with quartz pellets
Keywords: glycolide • bioplastics • transesterification •
(
125-250 µm) in order to get a total catalyst bed weight of 300 mg. Before
sustainable chemistry • supported catalysts
-1
reaction, the catalysts were pretreated for 1 hour (heating rate: 7 °C min )
-1
2
at 300 °C under a N flow of 20 ml min . After this pretreatment, the reactor
[
[
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passively cooled down to the desired reaction temperature. Feed solutions
typically consisted of 95 vol% α-hydroxy ester and 5 vol% o-xylene (non-
interfering internal standard, similar boiling point). The solution was fed to
an evaporation chamber held at 210°C with a Waters 515 HPLC pump
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-
1
(
typically 0.004-0.006 ml min , depending on the used ester), and mixed
-
1
there with a N
2
flow (typically 20 ml min ) yielding a molar composition of
). Changes in
molar composition of the vapor fraction (e.g. higher concentration of
esters) were realized by simultaneously changing the feed mixture and N
[
5]
6]
5
.6/0.2/94.2 of the gas mixture (α-hydroxy ester/o-xylene/N
2
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2
to ensure the same total molar amount of gas was used. The diluted feed
gas was then passed to the reactor (220-300 °C) and over the catalyst bed.
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2
After the reaction, a make-up N -stream (ca. 30 ml min ) was added to
dilute the products prior to analysis. Then, the gas was passed to the on-
line GC for analysis. Transfer lines to and from the reactor tube were
heated at 210 °C. Analysis: Effluent gases were analyzed by an on-line
GC (HP 6890 Series) equipped with an Agilent CP-Sil-24CB capillary
column and FID detector using the following temperature program: 80 °C
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for 3 minutes, heating to 280 °C (20 °C min ) and then isothermal for 1
minute. Product yields were calculated with o-xylene as internal standard,
taking into account response factors for each compound as determined via
calibration curves with commercial standards if available. All data points
were taken after 2 hours on stream. Response factors of components that
are not commercially available (e.g. TMDD or any of the linear dimers)
were estimated based on the response factors of known, similar
compounds such as lactide, glycolide and methanol. Conversion,
selectivity, yield, weight hourly space velocity (WHSV), turnover frequency
8
, 30163-30170.
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(
TOF) and a measure for residence time (weight catalyst over mole
gaseous feed, W/F) were calculated as follows:
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6
147-6176.
ꢗꢘꢙꢚꢛꢃꢘꢜꢃꢝꢞꢟꢃꢠꢘꢡꢢꢚꢣꢤꢚꢥ
Conversion = ꢦꢡꢦꢤꢦꢧꢙꢃꢧꢗꢘꢨꢡꢤꢃꢘꢜꢃꢝꢞꢟ (%)
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Biomacromolecules 2011, 12, 523-532.
ꢗꢘꢙꢚꢛꢃꢘꢜꢃꢩꢣꢘꢥꢨꢠꢤꢃ∗ꢃꢗꢘꢙꢚꢛꢃꢘꢜꢃꢝꢞꢟꢃꢦꢡꢠꢘꢣꢩꢘꢣꢧꢤꢚꢥꢃꢦꢡꢃꢩꢣꢘꢥꢨꢠꢤ
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Synthesis, Structures, Properties, Processing, And Applications, John
Wiley & Sons, Inc., 2010.
Selectivity =
(%)
ꢗꢘꢙꢚꢛꢃꢘꢜꢃꢝꢞꢟꢃꢠꢘꢡꢢꢚꢣꢤꢚꢥ
Yield = conversion x selectivity (%)
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[
22] S. Suzuki, K. Yamane, T. Ono, K. Sunagawa, Patent EP2377858, 2008.
ꢗꢧꢛꢛꢃꢘꢜꢃꢝꢞꢟꢃꢜꢚꢥꢃꢤꢘꢃꢣꢚꢧꢠꢤꢘꢣ
-
1
WHSV =
TOF =
ꢃ(h )
[23] C. A. Thayer, H. E. Bellis, US Patent 5374743, 1994.
ꢠꢧꢤꢧꢙꢪꢛꢤꢃꢗꢧꢛꢛꢃ∗ꢃꢫꢘꢨꢣ
[
24] R. De Clercq, M. Dusselier, E. Makshina, B. F. Sels, Angew. Chem. Int.
ꢗꢘꢙꢚꢛꢃꢘꢜꢃꢝꢞꢟꢃꢠꢘꢡꢢꢚꢣꢤꢚꢥꢃ
Ed. 2018, 57, 3074-3078.
-
1
(h )
ꢗꢘꢙꢚꢛꢃꢘꢜꢃꢬꢦꢃꢘꢡꢃꢠꢧꢤꢧꢙꢪꢛꢤꢃ∗ꢃꢫꢘꢨꢣ
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Oswald, E. Makshina, B. F. Sels, ACS Catal. 2018, 8, 8130-8139.
ꢭꢮꢯꢮꢰꢱꢲꢯꢃꢳꢮꢲꢲ∗ꢴꢵꢶꢷ
-1
[26] M. Cozzolino, M. Di Serio, R. Tesser, E. Santacesaria, Appl. Catal., A
W/F = ꢯꢵꢯꢮꢰꢃꢳꢵꢰꢸꢲꢃꢵꢹꢃꢺꢮꢲ (gcat h mol )
2
007, 325, 256-262.
[
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Poncelet, P. A. Jacobs, P. Grange, B. Delmon), Elsevier, 1991, pp. 627-
636.
Acknowledgements
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R.D.C. acknowledges IWT (Agency for Innovation by Science
and Technology, project number 131404) for financial support.
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[
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