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RSC Advances
out in a house made isothermal stainless steel batch reactor (120 mL) 60
installed in a shaker according to a procedure described elsewhere.46
Notes
The following reaction conditions were applied: temperature 140 °С,
hydrogen pressure 40 bar, initial concentration of D-glucose 1.6 M,
catalyst loading 0.4 g. Samples of the reaction mixture were analysed
via High Pressure Liquid Chromatography (HPLC) complex 65
UltiMate 3000 equipped with the comparison refractometer detector
Waters 410.
of Pharmaceutical Technology, Otto-Schott-Str. 41, D-07745 Jena,
DOI: 10.1039/C4RA14559C
Germany. Fax: +49 3641 949942; Phone: +49 3641 949951; E-mail:
5
bTver Technical University, A.Nikitina str. 22, 170026, Tver, Russia.
Tel./Fax: +7(4822)449317; E-mail: sulman@online.tver.ru
cProcess Chemistry Centre, Åbo Akademi University, Biskopsgatan 8,
20500, Turku/Åbo, Finland. Fax: +359 2215 4479; Phone:+358 2215
4985; E-mail:dmurzin@abo.fi
Continuous Process. Hydrogenation was carried out in a tubular
dBayer Technology Services GmbH, D-51368 Leverkusen, Germany. Fax:
+49-214-30-81118; Phone: +49-214-30-48420; E-mail:
10 mini-fixed-bed reactor setup with an inner volume of 150 mL 70
equipped with a tank containing the solution of D-glucose, tanks with
hydrogen and nitrogen, flowmeter, temperature and pressure
controllers, plate heat-exchanger and thermostat. The catalyst
dClariant (RUS), LLC, Andropov ave. 18/6, 115432, Moscow, Russia. Fax:
+7(495)7972598; Phone: +7(495)7972599; E-mail:
eLaboratory of Chemical Reactor Engineering/Micro Flow Chemistry and
Process Technology, Department of Chemical Engineering and Chemistry,
Eindhoven University of Technology, P.O. Box 513, 5600 MB Eindhoven,
The Netherland; Phone: +40-247 2973; E-mail: v.hessel@tue.nl
15 conditions: D-glucose concentration 0.5 M, temperature 110 oC,
hydrogen pressure 40 bar, glucose solution flow rate 19 mL/min.
Samples of the reaction mixture were analysed as described for the
batch process.
80 sfFraunhofer ICT-IMM Continuous Chemical Engineering Department,
Carl-Zeiss-Str. 18-20, 55129 Mainz, Germany. Fax: +49 6131 990-205;
Phone: +49 6131 990-377; E-Mail: Patrick.Loeb@imm.fraunhofer.de
20 Hydrogenation of D-Glucose using NCNT/Ru.
Batch Process. Hydrogenation of D-glucose over NCNT/Ru was
investigated in a Parr 4561 autoclave (300 mL). The autoclave was
equipped with a gas entrainment impeller, baffles, heating jacket and
a cooling coil, sampling line, pressure, temperature and stirring rate
25 controllers. The D-glucose solution was pre-heated and saturated
with hydrogen in a separate chamber. The catalyst sample was put in
the reactor which was flushed with nitrogen and hydrogen before
† Electronic Supplementary Information (ESI) available: See
85 DOI: 10.1039/b000000x/
References
1.
B. Kusserow, S. Schimpf and P. Claus, Advanced Synthesis &
Catalysis, 2003, 345, 289-299.
heating. When the reactor reached the desired temperature of 120°C 2.
the D-glucose solution was fed to the reactor and the total pressure 90
H.-D. Belitz, W. Grosch and P. Schieberle, Lehrbuch der
Lebensmittelchemie, Springer, Berlin, 2008.
30 was increased to 20 bars of hydrogen. Samples (1-2 mL) were
periodically withdrawn through a 0.5 μm sinter during the
experiments. A 0.1 mol/L 120 mL D-glucose (Fluka, ≥ 98 % purity)
solution was used. The stirring rate was 1000 rpm. The experiments
were carried out between 120 and 180 minutes and the amount of 95
35 catalyst was between 0.1 and 0.2 g.
The concentrations of D-glucose and sorbitol were determined by
HPLC (HITACHI Chromaster HPLC) equipped with a refractive
index detector. A Biorad HPX-87C carbohydrate column was used,
the mobile phase was 1.2 mM CaSO4. The temperature of the column
40 was 70 °C and the flow rate of the mobile phase 0.5 mL/min, the100
detector was at 40 °C. Calibrations were made for D-glucose and
sorbitol.
3.
J. Karolyi, Industrial & Engineering Chemistry Process Design
and Development, 1968, 7, 107-110.
4.
G.
Parmar,
Global
Sorbitol
Market,
_Isosorbide_Propylene_Glycol_Glycerol_and_Other_Downstrea
m_Opportunities_Applications_Toothpaste_Vitamin_C_Sweete
ner_Etc._Size_Share_Growth_Trends_And_Forecast_2012_-
_2018, Accessed 10, 2013.
5.
6.
H. Schiweck, A. Bär, R. Vogel, E. Schwarz, M. Kunz, C.
Dusautois, A. Clement, C. Lefranc, B. Lüssem, M. Moser and S.
Peters, in Ullmann's Encyclopedia of Industrial Chemistry,
Wiley-VCH Verlag GmbH & Co. KGaA, 2000.
P. Gallezot, N. Nicolaus, G. Fleche, P. Fuertes and A. Perrard,
Journal of Catalysis, 1998, 180, 51–55.
Continuous Process. Continuous hydrogenation of D-glucose over
NCNT/Ru was investigated in a continuously operating fixed bed
45 reactor set-up having six reactors in parallel, operated in co-current105 7.
trickle flow. The inner diameter of the reactor tubes was 12.5 mm
and the length of the electrically heated part was 12 cm. K-type
thermocouples were used to control the temperature. Knauer
Smartline 100 pumps were used to feed the D-glucose solution
T. Turek and C. Eisenbeis, Abschlussbericht zum Projekt
„Hydrierung
von
D-Glucose
Institut
zu
D-Sorbitol
an
Monolithkatalysatoren“,
für
Chemische
Verfahrenstechnik,
TU
Clausthal;
Max-Buchner-
Forschungsstiftung, Clausthal-Zellerfeld, 2009.
110 8.
P. Anastas and J. Warner, Green Chemistry: Theory and Practice,
Oxford University Press, 1998.
50 (Fluka, > 98%). The reaction conditions used for the continuous set-
up are the following: temperature 130 °C, glucose solution flow rate
2.0 mL/min, hydrogen flow rate 50 mL/min at a pressure of 20 bar.
The glucose concentration was 0.2 mol/L and the amount of catalyst
was 0.05-0.50 g. The particle size of the catalysts used in the
9.
D. Ott, D. Kralisch, I. Denčic, Y. Laribi, P. D. Perrichon, V.
Hessel, C. Berguerand, L. Kiwi-Minsker and P. Loeb,
ChemSusChem, doi: 10.1002/cssc.201402313.
55 continuous reactors were between 125 and 250 µm. Samples were115 10.
periodically withdrawn from the reactors and analysed with HPLC
as described in the previous section.
I. Denčić, D. Ott, D. Kralisch, T. Noël, J. Meuldijk, M. de Croon,
V. Hessel, Y. Laribi and P. Perrichon, Organic Process Research
& Development, doi: 10.1021/op5000573.
Further synthesis conditions for both, batch and continuous
11.
German Patent, DE 000003936757 A1, 1989.
hydrogenation are summarized in Tables 1 and 2.
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