Russian Journal of Applied Chemistry, Vol. 77, No. 1, 2004, pp. 26 !29.

Translated from Zhurnal Prikladnoi Khimii, Vol. 77, No. 1,

2004, pp. 28!31.
Original Russian Text Copyright + 2004 by Vyglazov.

PHYSICOCHEMICAL STUDIES
ÍÍÍÍÍÍÍÍÍÍÍÍÍÍÍÍÍÍÍÍÍÍÍÍ ÍÍÍÍÍÍÍÍÍÍÍÍÍÍÍÍÍÍÍÍÍÍÍÍ
OF SYSTEMS AND PROCESSES

Kinetic Characteristics of Xylitol Crystallization

from Aqueous-Ethanolic Solutions
V. V. Vyglazov
St. Petersburg State Forestry Engineering Academy, St. Petersburg, Russia
Received July 10, 2003

-
Abstract The kinetics of xylitol crystallization from aqueous-ethanolic solutions as a function of the initial
solution supersaturation, solvent composition, and temperature was studied. The effect of solvent composition
on the rate of the xylitol bulk crystallization was considered.

Among sugar substitutes, an important role belongs
to pentahydric aliphatic polyol, xylitol, prepared by
reductive transformation of D-xylose [1]. Inclusion of
xylitol in the list of food additives (E 967) [2] and
confirmation of its anticarious properties extended ap-
plications of this polyol. The main branches of xylitol
use are food production, perfumery, pharmaceutics,
and chemistry.
The technology of food xylitol production consists
of the following main stages: hydrolysis of hemicel-
lulose polysaccharides of pentosan-containing plant
raw materials (birch wood, cotton husk, corn cob
shanks); pentosan hydrolyzate preparation for hydro-
genation; hydrogenation of xylose solution; purifica-
tion and concentration of xylitol solution; and xylitol
crystallization. Crystallization is an important stage
of xylitol production, since in many respects it deter-
mines the yield and quality of the target product.
The possibilities of increasing the xylitol yield and
quality by optimization of the known technology of
xylitol crystallization from concentrated aqueous solu-
tions are practically exhausted.
The method of xylitol separation including pre-
liminary crystallization from supersaturated aqueous
solution and subsequent crystallization in the ethanol3
water mixture is more efficient [3]. The optimum
mode of xylitol crystallization can be determined from
the data on the process statics and kinetics. Previous-
ly, on the basis of the solubility data, we developed
a model of the statics of xylitol crystallization from
aqueous-ethanolic solutions [4]. In this work, we
studied the kinetics of polyol crystallization.
EXPERIMENTAL
The xylitol crystallization from aqueous-ethanolic
solutions was studied as a function of the degree of
solution supersaturation (characterized by supersatura-
tion coefficient S), solvent composition, and tempera-
ture at a constant stirring rate of 100 rpm. Xylitol
crystallization was studied under the isothermal condi-
tions at 5, 25, and 40oC. The compositions of water3
ethanol mixtures were taken with regard to probable
values of the liquid-to-solid ratio M [i.e., the ratio of
95.3% ethanol weight to the weight of dry substances
of the crystallizate (massecuite)]. It was 60 390 vol %
(or 53.9387.5 wt %) with respect to ethanol, which
corresponds to the 0.10 < M < 0.50 range used in in-
dustrial xylitol crystallization. The initial supersatura-
tion was reached by heating. The degree of super-
saturation was selected with regard to polyol solubil-
ity [4] by the formula S = cin/cs, where S is super-
saturation coefficient and cin and cs are the xylitol ini-
tial concentration and solubility (g per 100 g of the
solvent), respectively.
Food xylitol used [TU (Technical Specifications)
64-10-04 389] was preliminarily recrystallized and
dried to the moisture content of 0.03%. The xylitol
purity determined by GLC [5] was 99.9%, mp of crys-
tals 93.5394.0oC. The solvent was prepared by mixing
of ethanol (rectificate) with distilled water at 20oC.
The refractive indices of water3ethanol mixtures pre-
pared agree with data of [6]. Xylitol crystallization
was performed in a three-necked flask equipped with
a stirrer and thermometer. The temperature was con-
trolled with 0.1oC accuracy.
Crystallization was monitored through a change in
the refractive index of a liquid phase sample. Pre-
liminarily, the nTD3cet calibration plots were built for
each ethanol concentration and temperature. A linear
dependence nTD3cet was observed for the concentration
range corresponding to supersaturated metastable state
of the solution. This is characteristic also for other

1070-4272/04/7701-0026 C 2004 MAIK [Nauka/Interperiodica]

 KINETIC CHARACTERISTICS OF XYLITOL CRYSTALLIZATION 27

substances [7]. The error in determination of xylitol

concentration in aqueous-ethanolic solution by the (a)
refractive index was 0.05 g per 100 g of the solvent,
which corresponds to the interval from + 0.25 (in 60%
ethanol) to +2 rel% (in 90% ethanol) at 5oC.
The crystalline products obtained were examined
microscopically to estimate the granulometric com-
position. Linear dimensions of a large number of par-
ticles (> 60) were measured under a microscope
equipped with a special scale. Each crystal was meas-
ured along two mutually perpendicular directions, and
the average value L was taken as its linear size. Micro-
scopic analysis allowed determination of the size
distribution of particles in the fraction (%) [8]. t, min
(b)
The data on xylitol crystallization under various
conditions in the form of typical kinetic curves are
shown in Fig. 1. The xylitol solubility cs at fixed
temperature and solution composition is shown by a
dashed line. The analysis of the kinetic curves showed
that the increase in the ethanol concentration cet in
the intercrystallite liquor of the xylitol suspension
accelerates xylitol separation into the solid phase. For
example, at 25oC, xylitol crystallization proceeds
by a factor of 11 faster in 90% than in 60% ethanol
(Table 1). The time of decrease in the degree of solu-
tion supersaturation from 1.86 to 1.10 was taken as
the time of xylitol crystallization. t, min
The initial period of xylitol crystallization is satis- Fig. 1. Kinetics of xylitol crystallization in aqueous3
ethanolic solutions at 5oC. (S) Degree of supersaturation
factorily described by the equation [9]
and (c) xylitol concentration (g per 100 g of the solvent).
Initial c: (a) (1) 55.0 and (2) 50.2; (b) (1) 5.0 and (2) 4.6.
J = KN cnin, (1) cet (vol %): (a) 60 and (b) 90.

where J is the nucleation rate; KN, nucleation rate structure. Extrapolation of the linear dependences
constant; cin, initial xylitol concentration (g per 100 g described by Eq. (2) to the range of greater super-
of solvent); and n, nucleation order. saturation, where tind = 1, allows evaluation of maxi-
When the crystallization has an induction period, mum supersaturations Slim characterizing the upper
Eq. (1) transforms into Eq. (2): boundary of metastability and determination of the
region of stability of xylitol solutions as a whole. In
log tind = Kind 3 nlog (cin/cs), (2)
Table 1. Duration of xylitol crystallization t from aqueous-
where tind is the induction period (min); Kind, induc- ethanolic solutions*
tion period constant; and cs, xylitol solubility (g per
ÄÄÄÄÄÄÄÄÄÂÄÄÄÄÄÄÄÄÄÄÄÄÄÄÄÄÄÄÄÄÄÄÄÄÄÄÄÄÄÄ
³ t, min, at indicated temperature, oC
100 g of solvent). cet, vol % ÃÄÄÄÄÄÄÄÄÄÂÄÄÄÄÄÄÄÄÄÄÂÄÄÄÄÄÄÄÄÄ
The slope of the linear dependence of log tind on ³ 5 ³ 25 ³ 40
log (cin /cs) is equal to the nucleation reaction order n; ÄÄÄÄÄÄÄÄÄÅÄÄÄÄÄÄÄÄÄÅÄÄÄÄÄÄÄÄÄÄÅÄÄÄÄÄÄÄÄÄ
the latter changes for xylitol from n = 7 at cet = 60 ³ 285 ³ 345 ³ 930
60 vol % and 5oC to n = 30 at cet = 90 vol % and 70 ³ 110 ³ 122 ³ 380
40oC. 80 ³ 70 ³ 80 ³ 117
90 ³ 25 ³ 32 ³ 85
The rate of xylitol nucleation increases with in- ÄÄÄÄÄÄÄÄÄÁÄÄÄÄÄÄÄÄÄÁÄÄÄÄÄÄÄÄÄÄÁÄÄÄÄÄÄÄÄÄ
creasing temperature and cet, especially at M > 0.3, * cet is the ethanol concentration in water3ethanol mixture;
which is connected with changes in the mixed solvent the same for Table 2.

RUSSIAN JOURNAL OF APPLIED CHEMISTRY Vol. 77 No. 1 2004

28 VYGLAZOV

Table 2. Fractional composition of xylitol crystals at various crystallization temperatures

ÄÄÄÄÄÄÄÄÄÄÄÂÄÄÄÄÄÄÄÄÄÄÄÄÄÄÄÄÄÄÄÄÄÄÄÄÄÄÄÄÄÄÄÄÄÄÄÄÄÄÄÄÄÄÄÄÄÄÄÄÄÄÄÄÄÄÄÄÄÄÄÄÄÄÄÄÄÄÄÄÄÄÄÄ
³ Content, %, of crystals of indicated size, mm
ÃÄÄÄÄÄÄÄÄÄÄÄÂÄÄÄÄÄÄÄÄÄÄÄÂÄÄÄÄÄÄÄÄÄÄÄÄÂÄÄÄÄÄÄÄÄÄÄÄÄÂÄÄÄÄÄÄÄÄÄÄÄÂÄÄÄÄÄÄÄÄÄÄ
cet, vol % ³ >0.15 ³ <0.15 ³ >0.15 ³ <0.15 ³ >0.15 ³ <0.15
ÃÄÄÄÄÄÄÄÄÄÄÄÁÄÄÄÄÄÄÄÄÄÄÄÅÄÄÄÄÄÄÄÄÄÄÄÄÁÄÄÄÄÄÄÄÄÄÄÄÄÅÄÄÄÄÄÄÄÄÄÄÄÁÄÄÄÄÄÄÄÄÄÄ
³ 5o C ³ 25oC ³ 40oC
ÄÄÄÄÄÄÄÄÄÄÄÅÄÄÄÄÄÄÄÄÄÄÄÂÄÄÄÄÄÄÄÄÄÄÄÅÄÄÄÄÄÄÄÄÄÄÄÄÂÄÄÄÄÄÄÄÄÄÄÄÄÅÄÄÄÄÄÄÄÄÄÄÄÂÄÄÄÄÄÄÄÄÄÄ
60 ³ 82 ³ 18 ³ 58 ³ 42 ³ 54 ³ 46
70 ³ 66 ³ 34 ³ 50 ³ 50 ³ 41 ³ 49
80 ³ 40 ³ 60 ³ 42 ³ 58 ³ 18 ³ 82
90 ³ 0 ³ 100 ³ 0 ³ 100 ³ 5 ³ 95
ÄÄÄÄÄÄÄÄÄÄÄÁÄÄÄÄÄÄÄÄÄÄÄÁÄÄÄÄÄÄÄÄÄÄÄÁÄÄÄÄÄÄÄÄÄÄÄÄÁÄÄÄÄÄÄÄÄÄÄÄÄÁÄÄÄÄÄÄÄÄÄÄÄÁÄÄÄÄÄÄÄÄÄÄ
60% ethanol, Slim changes from 2.99 at 5oC to 2.12 tion from aqueous-ethanolic solutions is confirmed by
at 40oC, and in 90% ethanol, from 2.40 at 5oC to 1.86 the linear dependence of log (c /cs) on the crystalliza-
at 40oC. The decrease in the width of the metastable tion time Dt (Fig. 2).
zone with increasing cet satisfactorily agrees with the The first order of the crystallization reaction under
theory connecting a decrease in Slim with decreasing isothermal conditions shows that the xylitol crystalli-
solvent permittivity (eH O = 82.1 and eC H OH = 25.0 zation rate is limited by the rate of diffusion of polyol
2 2 5
at 20oC [11]). molecules to the surface of growing crystals.
The second stage of bulk xylitol crystallization It was found that, as the ethanol concentration in
from aqueous-ethanolic solutions involves direct for- the mixed solvent is increased, e.g., from 80 to
mation of crystalline precipitates. At fairly high solu- 90 vol %, the xylitol crystallization rate increases by a
tion supersaturation, when the rate of back dissolution factor of approximately 3 (K1 increases from 1.7 0
from the surface of growing crystals can be neglected 1033 to 4.9 0 1033 min31). For cet = 80 390 vol %, the
and the surface area after attaining the maximal rate linear dependence of log (c /cs) on Dt keeps at S 1.13
of the process changes insignificantly, the expres- 1.3, and for cet = 60 370 vol %, at S = 1.231.5.
sion derived from the chemical kinetics equation for
heterogeneous reactions [9] These S values characterize the width of the first
zone of metastability in the xylitol3ethanol3water
Dt = A ! B log (c/cs), (3) phase diagram. In this region of supersaturation,
already existing crystals grow without formation of
is valid. Here Dt = t 3 tind, A = (1/K1) log (cin /cs), B = new crystallization centers, which is very important
1/K1, t is the total time of observation (min), and for the technology of xylitol crystallization.
K1, the rate constant of xylitol crystal growth (min31). A microscopic estimation of the fractional com-
The applicability of Eq. (3) to xylitol crystalliza- position of xylitol crystals prepared in kinetic experi-
ments showed that the crystal size substantially
log (c/cs) depends of cet and T (Table 2). At cet < 80 vol %,
larger crystals are formed.
Under industrial conditions, massecuite crystals
should be capable of further growth in the ethanolic
solution characterized by supersaturations correspond-
ing to the first metastable zone.
To prevent the secondary nucleation, ethanol
should be introduced into the crystallizing system
gradually. To obtain larger crystals, the cet value in
the intercrystalline liquor should not exceed 80 vol %
Dt, min (Table 2).
Fig. 2. Logarithm of the degree of supersaturation of xylitol
aqueous-ethanolic solutions c /cs as a function of crystal- CONCLUSIONS
lization time Dt at various temperatures. cet (vol %): (1,
2) 60, (3) 70, and (4, 5) 80. Temperature (oC): (1, 5) 25 (1) A study of xylitol crystallization as a function
and (2! 4) 5. of the degree of the initial solution supersaturation,

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 KINETIC CHARACTERISTICS OF XYLITOL CRYSTALLIZATION 29

solvent composition, and temperature revealed the
main kinetic characteristics of this process: maximal
supersaturation of solutions in the form of the first
and second metastability boundaries, induction period,
nucleation reaction order, and the rate constant of
xylitol crystal growth.
(2) The data obtained were used to choose the
optimum mode of xylitol crystallization on the labora-
tory and semicommercial scale and were taken into
consideration when designing the crystallization
apparatus.
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