Journal of Chemical Technology and Biotechnology J Chem Technol Biotechnol 79:403–406 (online: 2004)

DOI: 10.1002/jctb.1001

Preparation of sorbitol from D-glucose

hydrogenation in gas–liquid–solid three-phase
flow airlift loop reactor
Jian-Ping Wen,∗ Chang-Lin Wang and Yan-Xin Liu
School of Chemical Engineering and Technology, Tianjin University, Tianjin 300072, People’s Republic of China

Abstract: A new process for D-glucose hydrogenation in 50 wt% aqueous solution, into sorbitol in a
1.5 m3 gas–liquid–solid three-phase flow airlift loop reactor (ALR) over Raney Nickel catalysts has been
developed. Five main factors affecting the reaction time and molar yield to sorbitol, including reaction
temperature (TR ), reaction pressure (PR ), pH, hydrogen gas flowrate (Qg ) and content of active hydrogen,
were investigated and optimized. The average reaction time and molar yield were 70 min and 98.6%
under the optimum operating conditions, respectively. The efficiencies of preparation of sorbitol between
the gas–liquid–solid three-phase flow ALR and stirred tank reactor (STR) under the same operating
conditions were compared.
 2004 Society of Chemical Industry

Keywords: D-glucose; hydrogenation; sorbitol; gas–liquid–solid three-phase flow airlift loop reactor

INTRODUCTION ALR could give more efficient production of sorbitol

Sorbitol is an important material that has been widely
used in many fields such as, amongst others, the
pharmaceutical, food, tooth-paste, cosmetics, and
chemical industries. Furthermore, sorbitol is the main
material for the preparation of vitamin C.
There are two methods of synthesizing sorbitol:
catalytic hydrogenation1 and electro-synthesis.2,3 Of
these, catalytic hydrogenation using a stirred tank
reactor or fixed bed reactor is most widely used
in commercial production, using D-glucose in 50
wt% aqueous solution or in 70 wt% aqueous
solution as reactant and ruthenium,4,5 nickel,6,7
cobalt8 or hydrogen storage alloys9 – 11 as catalysts
under high reaction temperature and high reaction
pressure. Also, at these conditions, reaction materials
are easily caramelized, thereby adversely affecting
the reaction efficiency of D-glucose hydrogenation.
Nothing is known, however, about the process of
direct hydrogenation of D-glucose to yield sorbitol in a
gas–liquid–solid three-phase flow ALR, characterized
by a well defined flow pattern, better dispersing
effects, relatively low power consumption and a
higher mass transfer coefficient.12 – 14 The aims of the
present study were to develop the gas–liquid–solid
three-phase flow ALR and to devise the optimum
operating conditions for the preparation of sorbitol
from D-glucose hydrogenation. A comparison of the
efficiencies of ALR and STR was carried out to
demonstrate that a gas–liquid–solid three-phase flow
under the same operating conditions.
EXPERIMENTAL
Principle of synthesis
Sorbitol was obtained by the catalytic hydrogenation
of D-glucose. In this reaction D-glucose was used as
starting material, hydrogen gas as reductant and Raney
Nickel as catalyst. The synthetic route is outlined in
Fig 1.
Experimental setup
The experimental setup used to prepare sorbitol is
schematically shown in Fig 2. One 2.785 m high draft
tube of 0.42 m inside diameter was fixed concentrically
inside the main 3.0 m high reactor tube of 0.6 m
inside diameter. The height and the diameter of the
expanding section were 0.8 m and 1.2 m, respectively.
Correspondingly, the work volume of the reactor
was 1.5 m3 . A concentric jet nozzle of 0.02 m inside
diameter was located in the bottom part of the riser.
Hydrogen gas in the storage tank flowed through
the buffer tank and was jetted into the reactor by
the air compressor’s pressurization. The hydrogen gas
flowrate was controlled by a calibrated rotameter.
The extra hydrogen gas was reintroduced into the
buffer tank for recycling. The reaction temperature
was adjusted by a temperature controller system.

∗ Correspondence to: Jian-Ping Wen, School of Chemical Engineering and Technology, Tianjin University, Tianjin 300072, People’s
Republic of China
E-mail: jpwen@tju.edu.cn
(Received 30 June 2003; revised version received 17 November 2003; accepted 5 December 2003)

 2004 Society of Chemical Industry. J Chem Technol Biotechnol 0268–2575/2004/$30.00 403

J-P Wen, C-L Wang, Y-X Liu
Figure 1. Structural formula and synthetic route of sorbitol.
P 8
2
7
6 T
2
2 100.2%, 1.24%, 1.23%, 0.9999, respectively. The
3
5
1 2
4 10
9 product
Figure 2. Experimental setup: 1—stock tank of H2 ; 2—stopvalve;
3—buffer tank; 4—air compressor; 5—gas flowmeter; 6—ALR;
7—temperature detector; 8—pressure detector; 9—decompressed
filtration unit; 10—temperature controller system.
Materials
Glucose with specific rotation 53.20 was prepared as a
50 wt% aqueous solution, in which the concentration
of chloride ion was controlled at less than 300 ppm.
Hydrogen gas was obtained through methanol-
splitting decomposition and its purity was greater
than 99%. FNL20 Nickel–aluminum–molybdenum
alloy powder (grain size: 0.1–0.35 mm, nickel content:
>80%) was purchased from Jinzhou Catalyst Factory
and used as catalyst.
Synthesis process
The preparation of sorbitol was performed as
follows: in the ALR, 1.5 m3 50 wt% D-glucose
solution and 37.5 kg nickel catalysts were added
and mixed thoroughly by continuously feeding
hydrogen gas. The reaction pressure and the reaction
temperature were then increased to the required
pressure and temperature. The concentration of
Table 1. HPLC conditions
Column temperature 90 ◦ C
Mobile phase Vacetonitrile /Vwater 60/40
Flowrate 0.5 cm3 min−1
404
D-glucose was determined by high performance
liquid chromatography (HPLC). The hydrogenating
reaction stopped when the concentration of D-glucose
decreased to less than 0.5%. Then the reaction
pressure was reduced to the atmospheric pressure
and the reaction temperature was cooled to room
temperature. Later, the reaction mixture was filtered
under reduced pressure in order to get rid of the
solid catalysts: a solution of the product, sorbitol, was
obtained. The concentration of sorbitol and mannitol
were determined by HPLC.
Detecting method
The specific rotation of glucose and pH of the reaction
mixture were detected by polarimeter (WXG-4,
China) and acidimeter (PHS-3C, China), respectively.
The quantity of sorbitol and mannitol were detected
by HPLC (Waters 510, USA) with a UR detector
(Waters 486). The detecting conditions of HPLC are
listed in Table 1.
The results of HPLC showed that the retention
time, average recovery, standard deviation, variation
coefficient and linear correlation were 15.5 min,
major byproduct is mannitol and its retention time
was 14.5 min.
RESULTS AND DISCUSSION
Effect of reaction temperature (TR )
The effect of TR on reaction time and molar yield is
shown in Fig 3. The reaction time decreased gradually
with TR but the molar yield of sorbitol was insensitive
to TR when TR was less than 140 ◦ C and decreased
evidently when TR was greater than 140 ◦ C. This
result may be explained by the increase in reaction
temperature increasing the reaction rate and thereby
shortening the reaction time, on the other hand, the
further increase in the reaction temperature caused
the reaction material to caramelize, resulting in an
increase in the molar yield of byproduct. So, 140 ◦ C
was selected as the optimum reaction temperature.
Effect of reaction pressure (PR )
Figure 4 shows the effect of PR on the reaction
time and molar yield of sorbitol. The reaction time
decreased with the increase in the reaction pressure
but the molar yield of sorbitol increased. An increase
in the reaction pressure would enhance the solubility
of hydrogen gas in the solution and thus increase
the reaction rate. The optimum PR for the shortest
reaction time and the highest molar yield of sorbitol
was 7 MPa atmosphere pressure.
Analytical column YWG-C18 , 10 µm 30 × 0.4 cm
Detecting wavelength 240 nm
Injection volume 20 mm3
J Chem Technol Biotechnol 79:403–406 (online: 2004)

, reaction time
, molar yield
Figure 3. Effect of reaction temperature on reaction time and molar
yield of sorbitol (PR = 6 MPa; active hydrogen = 290 cm3 g−1 ;
pH = 4; Qg = 4.5 m3 h−1 ).
, reaction time
, molar yield
Figure 4. Effect of reaction pressure on reaction time and molar yield
of sorbitol (TR = 130 ◦ C; active hydrogen = 290 cm3 g−1 ; pH = 4;
Qg = 4.5 m3 h−1 ).
Effect of active hydrogen
As observed from Fig 5, the increase of active
hydrogen contained in unit mass of nickel catalysts
can accelerate D-glucose hydrogenation but not alter
the reaction equilibrium. The optimum content of
active hydrogen was 310 cm3 g−1 .
Effect of pH
The typical results of the reaction time and molar
yield of sorbitol as a function of pH are illustrated in
Fig 6. The reaction time decreased with increase in
pH but the molar yield of mannitol increased more
remarkably. This may be attributed to the fact that the
increase in the pH can increase the amount of negative
charge in the active regions of catalysts and enhance
the ability of catalysts to donate electrons, resulting
in increased reaction rate. An increase in pH can also
bring about result in isomeric change of D-glucose into
mannitol. The optimum pH of the reaction solution
was 4.2 for the molar yield of mannitol less than 1.0%.
J Chem Technol Biotechnol 79:403–406 (online: 2004)
Preparation of sorbitol from D-glucose hydrogenation
, reaction time
, molar yield
Figure 5. Effect of active hydrogen on reaction time and molar yield
of sorbitol (TR = 130 ◦ C; PR = 6 MPa; pH = 4; Qg = 4.5 m3 h−1 ).
, reaction time
, molar yield
Figure 6. Effect of pH on reaction time and molar yield of mannitol
(TR = 130 ◦ C; PR = 6 MPa; active hydrogen = 290 cm3 g−1 ;
Qg = 4.5 m3 h−1 ).
Effect of hydrogen gas flowrate (Qg )
As seen from Fig 7, the reaction time decreased
with increasing in the hydrogen gas flowrates. This
was mainly attributed to the fact that the increasing
gas flowrates brings about the uniform distribution
of nickel catalysts as the solid phase, the increase
of the gas holdup and the decrease of the bubble
diameter. These variations increased the gas–solid and
liquid–solid interfacial area and the overall gas–liquid
and liquid–solid volumetric mass transfer coefficient,
thus changing the hydrogen gas kinetic regime and
producing an increase in the reaction rate with
fixed selectivity. However, when Qg was greater than
4.0 m3 h−1 , both the reaction time and molar yield
of sorbitol were insensitive to further increases in
the Qg , leading to excessive power consumption. The
optimum hydrogen gas flowrate was 4.0 m3 h−1 .
Stability observation under the optimum
operating conditions
The experiment was carried out at TR = 140 ◦ C,
PR = 7 MPa, active hydrogen = 310 cm3 g−1 , pH =
405
J-P Wen, C-L Wang, Y-X Liu

decreased 34.9% in the ALR relative to those in the

STR under the same operating conditions, ie TR =
140 ◦ C, PR = 7 MPa, active hydrogen = 310 cm3 g−1 ,
pH = 4.2, Qg = 4.0 m3 h−1 . These results may be due
to the higher liquid–solid and gas–liquid mass transfer
coefficients in the ALR.

CONCLUSIONS
A new process for the production of sorbitol by
D-glucose hydrogenation in gas–liquid–solid three-
phase flow ALR has been considered. The optimum
operating conditions are as follows: TR is 140 ◦ C, PR is
, reaction time 7 MPa, active hydrogen is 310 cm3 g−1 , pH is 4.2, Qg is
, molar yield 4.0 m3 h−1 . Under the optimum operating conditions,
the average reaction time and the average molar
Figure 7. Effect of air lift flowrate on reaction time and molar yield of yield of sorbitol are 70 min and 98.6%, respectively.
sorbitol (TR = 130 ◦ C; PR = 6 MPa; active hydrogen = 290 cm3 g−1 ; The gas–liquid–solid three-phase flow ALR has a
pH = 4).
better reaction time and molar yield of sorbitol
compared with the stirred tank reactor under the same
4.2, Qg = 4.0 m3 h−1 . As can be seen from Fig 8, operating conditions.
under the above optimum operating conditions the
average reaction time and the average molar yield of
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