Chemie

Ingenieur Hydrogenation 513

Technik

Communication

New Catalysts for the Hydrogenation of Glucose

to Sorbitol
Reinhard Geyer1, Peter Kraak2, Axel Pachulski1,* and Rainer Schödel3
DOI: 10.1002/cite.201100108

Nickel catalysts supported on ZrO2, TiO2 and ZrO2/TiO2 mixtures performed more active, selective and stable than Ni/SiO2
catalysts in the hydrogenation of glucose to sorbitol. This was shown by catalytic testing as well as by determination of Ni
crystallite size before and after the test. The reason for the better performance was assumed to be metal-support interaction
in the Ni/ZrO2, Ni/TiO2 and Ni/ZrO2/TiO2 catalysts.
Keywords: Catalyst, Glucose, Hydrogenation, Nickel, Sorbitol
Received: June 17, 2011; revised: October 20, 2011; accepted: January 03, 2012

1 Problem 2 Experimental

Numerous literature exist about the hydrogenation of glu-
cose to sorbitol on supported Ru catalysts [1 – 4]. The large-
scale production of sugar alcohols is carried out mainly by
catalytic hydrogenation of mono- and polysaccharides in a
suspension process using Raney-type nickel catalysts [5 – 7].
Furthermore, fixed bed processes in the presence of Ni cata-
lysts are known for the production of sorbitol from glucose
[8]. Both technical processes have advantages and disadvan-
tages. The suspension process is characterized in particular
by a good use of the catalyst and good temperature control.
A disadvantage is the high effort for the removal and recy-
cling as well as the abrasive properties of the Raney-type
nickel catalysts.
The advantages of the fixed bed process are the higher
space-time yield and the absence of the expensive separation
of the catalyst. The predominantly used Ni/SiO2 catalysts
show high activity and selectivity. The downside is the aging
of the catalyst, which is mainly caused by leaching of the
carrier and the associated metal sintering. A replacement of
the supported nickel catalysts by pressed Raney-type nickel
catalysts is expensive.
It was therefore the task of the present work to search for
new and more stable supported nickel catalysts. First it was
focused on the development of catalysts applied in suspen-
sion process and that is the reason why also the catalytic
testing took place in suspension phase.
– in a hydrogen flow (3 L h–1) at 180 °C for 1 h. After the
1
Dr. Reinhard Geyer, Dr. Axel Pachulski (Axel.Pachulski@cri-
criterion.com), KataLeuna GmbH Catalysts, Am Haupttor,
Gebäude 8322, 06237 Leuna, Germany; 2Dr. Peter Kraak,
Faradaystraße 55, 04159 Leipzig, Germany; 3Dr. Rainer Schö-
del, Falladastraße 19, 06179 Teutschenthal, Germany.
Ni/SiO2, Ni/ZrO2, Ni/TiO2, Ni/ZrO2/TiO2 and Ni/MgO/
SiO2/Al2O3 catalysts were prepared by precipitation. The
resulting precipitates were washed on filter presses until a
Na content < 0.1 wt-% was reached and dried for 24 h at
110 °C. 60 mL of the dried filter cake were calcined under a
flow of 120 L h–1 of air at 450 °C for 6 h after a heating ramp
of 5 °C min–1. Afterwards the product was pressed into loose
tablets and activated by reduction. The reduction was per-
formed in a flow of hydrogen (space velocity 2000 v vh–1) at
400 °C with rate of 5 °C h–1 followed by a 4 h hold. After the
reduction the catalysts were cooled to ambient temperature
in a nitrogen flow and stabilized in a 60 L h–1 nitrogen flow
containing oxygen (oxygen content 0.1 vol.-% up to 2 vol.-%)
at temperatures from 50 up to 60 °C for 12 h. The thus pre-
pared catalysts were crushed to a particle fraction < 63 lm
before further testing.
The nickel content was determined on the unreduced sam-
ple by using different XRF (X-ray fluorescence) calibration
curves for Ni/ZrO2, Ni/SiO2, Ni/ZrO2/TiO2 and Ni/ZrO2/
SiO2 catalysts. For each catalyst component calibration sam-
ples were prepared in a wide concentration range. The sam-
ples were treated in air at 800 °C for 2 h, crushed to a particle
size of 10 lm and then pressed into pills, which were trans-
ferred into the XRF device SRS 303 from Siemens.
The reduced and passivated catalyst was characterized by
determination of the nickel metal content and the nickel
surface area. Prior to measurement of the nickel metal con-
tent 100 mg of the reduced, passivated catalyst were reduced
reduction the catalyst was purged with nitrogen (2 L h–1) at
350 °C for 1 h to desorb hydrogen. Afterwards the sample
was cooled down in a flow of nitrogen (2 L h–1) from 350 °C
to room temperature within 0.5 h. Then 20 cm3 of hydro-

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514 A. Pachulski et al.

chloric acid (18 wt-%) were transferred into the reactor with- –ln(1 – x) vs. time, where x is the conversion of glucose
in 1 min. The reaction mixture was heated to 80 °C for 0.5 h within 1 h,
and then cooled down to 20 °C. The thus formed hydrogen – sorbitol yield in % after 4 h,
was measured volumetrically at 20 °C. The nickel content – overall rate in terms of lmol sorbitol produced per g Ni
was calculated from the volume of hydrogen corresponding metal and time based on number of moles sorbitol pro-
with the reaction equation of the reaction of metallic Ni with duced after 4 h,
hydrochloric acid. – specific rate in terms of turnover frequencies (TOF) calcu-
The nickel surface area of the catalysts was evaluated from lated by division of the overall rate by the chemisorbed
the pulse CO chemisorption. Prior to the chemisorption 1
CO value in lmol CO gNimetal .
measurement the passivated catalyst was reduced in a The stability of the metal dispersion under reaction condi-
hydrogen flow of 3 L h–1 at 180 °C for 1 h followed by cooling tions was investigated with selected catalysts by a treatment
down to 0 °C. The CO chemisorption was measured at 0 °C in the reaction mixture over a period of 100 h (standard test)
by introducing pulses of CO (volume: 0.335 cm3) into the and then the average nickel crystallite size was determined
flow of hydrogen (2 L h–1). The pulses were continued until after filtration and covering by an oil layer by using the XRD
no further uptake of CO was measured. The chemisorption 7 from Richard Seifert & Co Freiberger Präzisionsmechanik
was done in TPD/R/O 1100 from Thermo Fisher Scientific GmbH.
including thermal conductivity detectors. The nickel metal The scattering curve sections were recorded perpendicu-
surface was calculated from the CO uptake under the larly to the (111) lattice plane from the broadening of the in-
assumption that a single nickel surface atom chemisorbs terference line under the following conditions:
one CO molecule and one nickel atom occupies 0.0645 nm2. – data generator: 40 mA at 30 kV
Based on the number of CO molecules chemisorbed the – radiation: Cu-Ka
following dispersion data were calculated: Ni surface area – filter: Ni
1
in m2 gcat1 , Ni surface area in m2 gNimetal , CO chemisorbed – angle range: 2h = 41° – 49°, in steps of Dh = 0.05°
1
in lmol CO gNimetal and dispersion D in % according to – counting time: 20 s
D = 100 Ns/NT. In this context Ns is number of nickel surface The analysis of the liquid reaction products was carried
atoms in lmol CO chemisorbed and NT is total number of out by a HPLC device from Agilent quipped with the separa-
nickel metal atoms. The nickel crystallite size (c. s.) was de- tion column AminexR HPX-87C, 300 × 7.8 mm from Bio-
termined by Ni c. s. = 5/(SNiqNi) wherein Sin is the Ni metal Rad.
surface area in m2g–1 and qNi is the metal density in g m–3.
The catalytic test was performed in the autoclave 9801 e
Limbo from Büchi. The passivated catalysts were added to 3 Results
the glucose solution, heated to reaction temperature
under a hydrogen pressure of 0.5 MPa without stirring and The dispersion data, the nickel and nickel metal contents of
then tested under the following conditions (standard condi- the catalysts are given in Tab. 1. The different dispersion
tions): data show that the nickel catalysts based on ZrO2 or TiO2
– reaction temperature T: 120 °C supports have a significantly lower nickel metal dispersion
– reaction pressure p: 12 MPa than the Ni/SiO2 and Ni/MgO/Al2O3/SiO2 catalyst.
– catalyst concentration ccat: 1.5 wt-%
– stirring rate: 2500 min–1
Table 1. Composition and dispersion data of the studied catalysts (s. a.: surface area).
– reaction mixture: 100 g glucose
+ 100 g water Catalyst NiO content Nimetal CO chem. D [%] Ni s. a. Ni s. a.
– reaction time t: 4 h [wt-%] content 1
[lmol CO gNimetal ] [m2 gcat1 ] [m2 gNi1 ]
The gas flow controller Büchi [wt-%]
press BHPC 400 was used as a
Ni/SiO2 78.5 48 1355 7.9 33.6 70.0
pressure regulator and measur-
ing device of the hydrogen con- Ni/MgO/Al2O3/SiO2 55.5 42 1793 10.5 31.4 74.8
sumption. With this arrangement Ni/ZrO2 78.3 51.2 829 4.9 20.5 40.0
the hydrogen consumption could
Ni/TiO2/ZrO2 79.4 44.5 790 4.6 19.8 44.5
be measured under a constant re- (9.9 % TiO2
action pressure. 9.9 % ZrO2)
As measure for the catalytic
Ni/TiO2 60.3 39.9 948 5.6 15.2 38.1
performance of the catalysts dif-
(37.6 % TiO2
ferent activity indicators were 0.1 % Na2O)
used:
Ni/ZrO2/SiO2 78.4 51.7 927 5.4 22.9 44.3
– pseudo-first order rate constant
(2.3 % SiO2)
k obtained from plots of

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 Chemie
Ingenieur Hydrogenation 515
Technik

The results of catalytic measurements are demonstrated

in Figs. 1 – 4 and Tab. 2. A series of experiments were per-
formed on the Ni/ZrO2/SiO2 catalyst to estimate the influ-
ences of stirring rate, reaction temperature and pressure as
well as catalyst concentration on the rate constant. As
shown in Fig. 1 the rate constant increases up to a stirring
rate of 1800 min–1 and remains almost constant at higher
stirring rates. Because of this result all catalytic tests in the
autoclave were carried out with a stirring rate of 2500 min–1.

Figure 3. Influence of the reaction temperature on initial rate

constant k (reaction conditions: p = 2 MPa, t = 1 h, ccat = 1.5 wt-%,
50 wt-% aqueous glucose solution and stirrer speed = 2500 min–1).

The reaction pressure was varied between 6 and 16 MPa

to determine its influence on the catalyst activity. Fig. 4
illustrates the influence of reaction pressure on the hydroge-
nation rate constant k. As expected, k increases with increas-
ing reaction pressure.

Figure 1. Rate constant k versus stirrer speed for Ni/ZrO2/SiO2

(reaction conditions: T = 120 °C, p = 12 MPa, T = 1 h, ccat = 1.5 wt-%,
50 wt-% aqueous glucose solution).

The influence of the catalyst load m on the initial rate con-

stant k was measured by running different experiments
with catalyst concentrations from 0.74 up to 2.91 wt-%. The
experimental results were plotted as 1/k vs. 1/m as shown in
Fig. 2. The graph is linear with zero intercept. This result
suggests that the external gas-liquid mass transfer is negligi-
ble for the given experimental conditions [9, 10]. These data
show furthermore that poisoning phenomena can be Figure 4. Influence of the reaction pressure p on initial rate con-
stant k (reaction conditions: T = 120 °C, t = 1 h, ccat = 1.5 wt-%,
excluded. 50 wt-% aqueous glucose solution and stirrer speed = 2500 min–1).

The catalysts described in Tab. 1 were tested in the hydro-

genation of glucose under standard conditions. The rate
constants, sorbitol yields, the specific rates and TOF are
given in Tab. 2. A comparison of the rate constants shows
that the supported Ni/ZrO2, Ni/TiO2 and Ni/ZrO2/TiO2
catalysts have higher initial hydrogenation activities
than the Ni/SiO2 catalysts. In addition these catalysts have
higher sorbitol selectivities as seen by sorbitol yields. The
Ni/MgO/Al2O3/SiO2 catalyst shows the highest initial hy-
Figure 2. Influence of catalyst loading on initial rate constant k
(T = 120 °C, p = 12 MPa, t = 1 h, 50 wt-% aqueous glucose solution
drogenation activity (k). However, this high activity is con-
and stirrer speed = 2500 min–1).

Table 2. Catalytic characteristics of the studied catalysts.

The effect of reaction temperature
Catalyst Sorbitol yield [%] k [min–1] Overall activity Specific activity
on the rate constant was investigated [lmol sorbitol gNi1 s 1 ] TOF [10–3 s–1]
in the range of 105 to 133 °C. The re-
sult is shown in Fig. 3. An apparent Ni/SiO2 92.4 5.6 24.73 18.2
activation energy of 72.3 kJ mol–1 was Ni/MgO/Al2O3/SiO2 83.9 10.3 25.66 14.3
calculated by using the Arrhenius re-
lationship. In comparison to that Ni/ZrO2 93.2 6.1 23.37 28.2
Brahme and Doraiswamy [11] deter- Ni/TiO2/ZrO2 96.7 7.8 27.93 35.3
mined an activation energy of
Ni/TiO2 97.5 6.9 35.88 44.8
62.7 kJ mol–1 for the glucose hydroge-
Ni/ZrO2/SiO2 97.8 8.5 24.55 26.5
nation on Raney-type nickel catalysts.

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516
nected with a low selectivity because a lot of the by-product
mannitol (8.1 %) was detected.
The comparison of the overall activities related to sorbitol
produced per nickel metal content and second shows that
only the TiO2 containing catalysts has a better catalytic per-
formance than the Ni/SiO2 catalyst. In case of the specific
activities the ZrO2 and TiO2 containing catalysts have signif-
icant higher TOFs (26.5 – 44.8 · 10–3) than the Ni/SiO2 cata-
lyst (18.2 · 10–3). Schimpf et al. [12] found a TOF of 14 · 10–3
on a commercial Ni/SiO2 catalyst with about 70 wt-% Ni at
120 °C, 120 bar and 20 wt-% aqueous glucose solution. Sur-
prisingly the TiO2 containing catalysts show the highest spe-
cific rates.
It is worth to note that there is no correlation between the
metal dispersion and specific hydrogenation activity of the
different catalyst systems. Probably the hydrogenation activ-
ity of the catalysts is determined by dispersion and a metal-
support interaction. Further investigations are necessary to
prove this hypothesis.
A further advantage of the Ni/ZrO2 catalysts is the higher
stability during hydrogenation. Tab. 3 summarizes the Ni
crystallite sizes of the Ni/ZrO2 and Ni/SiO2 catalysts before
and after a 100 h treatment under reaction conditions. This
table shows also the crystallite sizes of the fresh catalysts cal-
culated from the CO chemisorption values. The Ni crystal-
lite sizes measured by XRD are smaller than the crystallite
sizes calculated from the results of chemisorption methods.
This result is expected because the XRD measurements as a
volume averaged method are also recording dislocations in
the crystal structure that are not registered by chemisorp-
tion, which is a surface area averaged measurement.
Table 3. Stability of the metal dispersity (c. s.: crystallite size).
Catalyst Average Ni c. s. [nm]
before hydrogenation after hydrogenation
CO chem. XRD
Ni/ZrO2 13.9 5.4 7.6
Ni/SiO2 8.0 4.2 9.6
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A. Pachulski et al.
It is obvious that the catalyst based on the ZrO2 support
has a higher stability of the metal dispersion than the Ni/SiO2
catalyst which can be explained by a reduced leaching of the
ZrO2 support.
4 Conclusions
In summary it can be concluded that compared to the Ni/
SiO2 catalyst Ni-supported catalysts based on ZrO2, TiO2
and ZrO2/TiO2 mixtures have under the selected conditions
of the glucose hydrogenation to sorbitol:
– an enhanced hydrogenation activity,
– a better selectivity and
– a higher stability of metal dispersion.
References
[1] P. Gallezot, N. Nicolaus, G. Flèche, P. Fuertes, A. Perrard,
J. Catal. 1998, 180, 51. DOI: 10.1006/jcat.1998.2261
[2] B. W. Hoffer, E. Crezee, P. R. M. Mooijman, A. D. van Lange-
veld, F. Kapteijn, J. A. Moulijn, Catal. Today 2003, 79 – 80, 35.
DOI: 10.1016/S0920-5861(03)00040-3
[3] B. Kusserow, S. Schimpf, P. Claus, Adv. Synth. Catal. 2003, 345
(1 – 2), 289. DOI: 10.1002/adsc.200390024
[4] K. van Gorp, E. Boerman, C. V. Cavenaghi, P. H. Berben, Cat-
al. Today 1999, 52, 349. DOI: 10.1016/S0920-5861(99)00087-5
[5] P. Gallezot, P. J. Cerino, B. Blanc, G. Fleche, P. Fuertes, J. Cat-
al. 1994, 146, 93. DOI: 10.1016/0021-9517(94)90012-4
[6] B. J. Arena, Appl. Catal., A 1992, 87 (1), 219. DOI: 10.1016/
0926-860X(92)80057-J
[7] R. Albert, A. Strätz, G. Vollheim, Chem. Ing. Tech. 1980, 52 (7),
582. DOI: 10.1002/cite.330520708
[8] V. Tukac, Collect. Czech. Chem. Commun. 1997, 62 (9), 1423.
[9] G. W. Roberts, in Catalysis in Organic Synthesis (Eds: P.N.
Rylander, H. Greenfield), Academic Press, New York 1976.
[10] H. Hichri, A. Accary, J. Andrieu, Chem. Eng. Process. 1991, 30
(3), 133. DOI: 10.1016/0255-2701(91)85002-6
[11] P. H. Brahme, L. K. Doraiswamy, Ind. Eng. Chem. Process Des.
Dev. 1976, 15 (1), 130. DOI: 10.1021/i260057a22
[12] S. Schimpf, C. Louis, P. Claus, Appl. Catal., A 2007, 318, 45.
DOI: 10.1016/j.apcata.2006.10.034
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