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Thermal degradation kinetics of sucrose, glucose and

fructose in sugarcane must for bioethanol production

Article in Journal of Food Process Engineering · September 2006

DOI: 10.1111/j.1745-4530.2006.00080.x

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 THERMAL DEGRADATION KINETICS OF SUCROSE,
GLUCOSE AND FRUCTOSE IN SUGARCANE MUST FOR
BIOETHANOL PRODUCTION

J. NOLASCO JUNIOR1 and P.R. DE MASSAGUER

Universidade de Campinas-UNICAMP
Faculdade de Engenharia de Alimentos (FEA)/Departamento
de Ciência de Alimentos
Rua Monteiro Lobato, 80, Campinas, São Paulo,
Brasil C.P. 6121 – CEP 13083-862

Accepted for Publication May 30, 2006

ABSTRACT

Thermal degradation of sugars contained in sugarcane must (21.5°Brix,

pH 6.14) was evaluated at temperatures of 110, 120, 130 and 140C, using
the thermal-death-time tube method, determining remaining sugars by high-
pressure liquid chromatography. The study analyzed thermal degradation
kinetics of both the total reducing sugars (TRS) and glucose and fructose
individually.
All curves of remaining sugars presented strong nonlinearity, with initial
shoulder and final tail adjusted by an extended logistic model that was adapted
for two species for TRS, and a simple logistic model for the monosaccharides.
It was shown that rate constants are influenced by temperature according
to two irreconcilable methods: the Arrhenius and the Bigelow methods.
Obtained activation energies for fructose and glucose were quite coincident,
140.37 and 140.23 kJ/mol, respectively. Thermal resistance parameters were
21.59 and 21.61C, respectively. Comparison of the rate constants revealed
that fructose degraded approximately 9–10 times faster than glucose.

INTRODUCTION

Bioethanol is produced in Brazil by fermentation of sugars in sugarcane

must. Because bioethanol and sugar plants are typically integrated, the must is
composed of cane juice and molasses as by-products of the sugar production
process.

1
Corresponding author. J. Nolasco, Jr., R 13 de maio, 1727, 13419-270, Piracicaba, São Paulo, Brasil.
TEL: 27+55-021-19-34225966; EMAIL: Jonas.nolasco@terra.com.br

Journal of Food Process Engineering 29 (2006) 462–477. All Rights Reserved.

462 © 2006, The Author(s)
Journal compilation © 2006, Blackwell Publishing
 THERMAL DEGRADATION KINETICS OF SUGARS IN SUGARCANE MUST 463

Because of its physicochemical characteristics, sugarcane must sustain a

diversified microbiota, and contamination is predominantly formed by gram-
positive Lactobacillus sp. and Bacillus sp. Among the latter, the heat-resistant
sporeformer Bacillus stearothermophilus has been reported to form up to 6.9%
of the contaminant microflora (Gallo and Canhos 1991; Klaushofer et al.
1998). In the fermentation process, the contaminants not only compete with
yeast for substrate, but also give rise to undesirable yeast flocculation. Con-
tamination is frequently blamed for high-level losses found in the ethanol
production section, up to 1.5–5.0% drop in fermentation yield (Yokoya and
Oliva-Neto 1991; Oliveira-Freguglia and Horii 1998; Stroppa et al. 1998;
Trombini et al. 1988; Alcarde and Yokoya 2003).
Control strategies of such contaminants in the fermentation process have
been concentrated on the use of antibiotic products, such as penicillin, monensin
and virginiamycin, or commercial formulas containing two or more of these
products. Antibiotics have also been used worldwide in animals, both to treat
infections and as growth promoters. Intensive and extensive use of antibiotics
have been pointed out as one of the most important dangers resulting in the
development of antibiotic-resistant bacteria that can be harmful to humans
because of the transfer of antibiotic resistance to human pathogens. It has been
shown, e.g., that the increase in consumption of antibiotics by animals has been
accompanied by a similar rise in the number of antibiotic-resistant strains of
human pathogens. Europe and mainly Nordic countries have banned or severely
restricted the intensive use of those antimicrobials, but in Brazil, it remains as
the most important strategy to control contaminants in alcoholic fermentation.
(Lima et al. 1999; Thal and Zervos 1999; Stroppa et al. 2000; Oliva-Neto and
Yokoya 2001; van den Bogaard et al. 2002).
The decision to design an optimal thermal process for inactivation of
sugarcane must contaminants requires a prior knowledge of thermal death
kinetics of target microorganisms as well as knowledge of thermal degradation
kinetics of the main nutrients to be preserved: sucrose and its thermal hydroly-
sis products glucose and fructose, all related to conditions of °Brix and pH.
The existence of at least two organic functions (C=O and C–OH) gives
these sugars several options of chemical heat-induced transformations, also
in view of reactivity differences of the various hydroxyl groups in the
same molecule. Alkaline degradation, degradation in acid medium with
hydroxymethylfurtural (HMF) as the main degradation product, Maillard reac-
tions with Strecker degradation and caramelization are some of these heat-
induced degradation reactions (Bobbio and Bobbio 1992). According to Bohn
et al. (1998), in conditions such as low sugar concentration, neutral or slightly
acidic pH, the Maillard reaction and alkaline degradation may be neglected.
This is the case for extraction and juice clarification processes for sugar and
alcohol production in Brazil.
464 J. NOLASCO JUNIOR and P.R. DE MASSAGUER

In any thermal degradation reaction, sucrose invariably hydrolyzes first to

the thermolabile hexoses glucose and fructose, fructose being more thermo-
labile than glucose (Kelly and Brown 1978). The same authors have mentioned
several studies involving buffered solutions of glucose in a wide range of
concentration (1–40%), pH (1–7) and temperature (40–190C). For these con-
ditions, activation energy (Ea) for glucose thermal degradation varied from
123.5 to 138.2 kJ/mol. For fructose thermal degradation, Kelly and Brown
(1978) reported activation energies from 92.9 to 96.3 kJ/mol and stated that
HMF production through fructose degradation was approximately 12 times
larger than the one obtained with glucose degradation. In their literature
review, Kelly and Brown (1978) reported works with buffered solutions of
sucrose, pH 5.6, from 0.2 to 2.0 M at 100C, in which hexose decomposition
showed consecutive reaction behavior. For the 0.2-M sucrose solution, fruc-
tose reached the maximum concentration after 127 h with a decomposition
constant of 7.5 ¥ 10-3 h-1, while glucose reached the maximum concentration
after 237 h with a decomposition constant of 1.77 ¥ 10-3 h-1.
No reports have been found in the literature on kinetic parameters for
sugar thermal degradation in sugarcane must.
The objective of this research is to assess the kinetic parameters for
thermal degradation of sugars contained in sugarcane must, based on both the
thermolabile hexoses glucose and fructose individually, and on total reducing
sugars (TRS). Those data are necessary for the design of an optimal thermal
treatment to inactivate the contaminant bacteria from sugarcane must while
satisfying sugar content retention.

MATERIALS AND METHODS

Kinetic Assay
Thermal degradation kinetics of the sugars sucrose, glucose and
fructose contained in sugarcane must was carried out by the closed
thermal-death-time (TDT) tube method according to Stumbo (1973).
Heating temperatures for the kinetic assays were 110, 120, 130 and 140C.
TDT tubes (6-mm TDT tube internal diameter ¥ 8-mm TDT tube external
diameter ¥ 100-mm length) were filled up with 2 mL of sugarcane must,
sealed in an oxygen gas flame and submerged completely in a circulating
thermostatic oil bath (Polystat PolyScience model G12105-20, Cole-Palmer,
Vernon Hills, IL) precision 0.1C, which was adjusted to the designed treat-
ment temperatures. The TDT tubes were taken out at specific time intervals
relative to each temperature. All programmed thermal treatments were per-
formed in duplicate, each treatment with a thermal lag of 3 min.
 THERMAL DEGRADATION KINETICS OF SUGARS IN SUGARCANE MUST 465

TDT Tube Thermal Lag Evaluation

The thermal lag for each temperature was determined with a TDT tube
holding 2 mL of sugarcane must and with a flexible type T thermocouple,
duplex Omega TT-36 wire (Omega, Bridgeport, NJ), located at the geometric
center of the tube and measured in minutes to reach the treatment temperature.

Sugarcane Must Preparation

The sugarcane must at 21.5°Brix was made up of 15% (v/v) of 13.2°Brix
juice retrieved from filters used to recover sugar from sludge in the juice
clarification process, 22% (v/v) of final molasses at 60°Brix and the remaining
63% (v/v) of sugarcane juice from the second tandem of the crusher extraction
at 10°Brix. The sugarcane must was clarified for sludge removal according to
current practice in industrial juice clarification processes in Brazilian mills, and
was maintained cool at 0C in a cold camera (Reveco, Brazil), until the accom-
plishment of the kinetic trials. The cold camera used was of proper manufacture,
made of masonry with a thermal cover, climatized and kept at 0C for storage
of sugarcane seeds. The clarification process was carried out by addition of
phosphoric acid (0.25 mL/L of sugarcane must), liming at a lime concentration
of 10 specific density of solutions, °Be, to pH 6.4, followed by heating to boiling
at atmospheric pressure and dosage of anionic polymeric compound (4 mL/L of
sugarcane must). Solids were finally sedimented at a temperature slightly below
the boiling temperature, in a clarification kit composed of four graded test tubes
of 1 L each, which were fitted with incandescent lamps with light-intensity
regulators to control the internal temperature of the kit. After clarification, the
resulting sugarcane must was at 21.5°Brix and pH 6.14.All °Brix measurements
were carried out in a digital refractometer (Leica model 10480, serial number
122523, Leica Microsystem Inc., New York). All pH measurements were
carried out with a Micronal pH meter (model B375, Micronal, SP, Brazil).

Method for Sugar (Sucrose, Glucose and Fructose) Analysis

Remaining sugar contents in sugarcane must, after each thermal treatment,
were measured by high-pressure liquid chromatography (HPLC). Samples
were filtered through a cellulose acetate/nitrate membrane of 0.45-m pore size.
The HPLC was equipped with a precolumn Shodex KS-801 (6-mm
diameter ¥ 50-mm length; Shodex, Kawasaki, Japan), a main column Shodex
KS-801 (8-mm diameter ¥ 300-mm length) and an index refraction detector. A
solution of NaOH of 0.0005 N was used as mobile phase (0.4 L/min).
Complementary thermal treatment times were accomplished at 120C
(48, 96, 144, 168, 192 and 240 h) and at 140C (2.0, 2.25 and 2.5 h) measuring
the remaining sugarcane must sugar contents by HPLC with CarboPac Pa-1
466 J. NOLASCO JUNIOR and P.R. DE MASSAGUER

column (Dionex Corp., Sunnyvale, CA), detector of pulsed ammeter amperom-

etry and sodium hydroxide solution of 150 mM as mobile phase (1.0 mL/min).

Mathematical Models for Thermal Degradation Kinetic Data

Glucose and fructose thermal degradation kinetics were studied through
the remaining sugar fraction at time t (S) after each thermal treatment time and
were modeled through the simple logistic model and null thermal lag, t = 0,
Eq. (1a), which was obtained by replacing t = 0 in the general logistic model,
Eq. (1b).

2
S= (1a)
(1 + ekt )

S=
(1 + e− kτ )
(1b)
(1 + ek (t −τ ) )
TRS thermal degradation kinetics were studied through S after each
thermal treatment time and were modeled through the extended logistic model
for two species, Eq. (2). In this equation, the parameter a reflects the fraction
of species 1; k, specific thermal degradation rate constants; and t, the thermal
lags. TRS content was calculated by Eq. (3) through sucrose, glucose and
fructose contents measured after each thermal treatment time.

⎧ α [(1 + e− k1τ1 )] ⎫ ⎧ (1 − α ) [(1 + e− k2τ 2 )] ⎫

S=⎨ ⎬+⎨ ⎬ (2)
⎩ (1 + e 1 1 ) ⎭ ⎩ [1 + e 2 2 ] ⎭
k (t −τ ) k (t −τ )

X (t ) sucrose ⎞
X (t )TRS = ⎛ + X (t )glucose + X (t )fructose (3)
⎝ 0.95 ⎠

Kinetic parameters were obtained by nonlinear regression through the

software Statistica 6.0 (Statsoft, Tulsa, OK).

Effect of Temperature on Thermal Degradation Rate Constants

The temperature influence on rate constants was assessed through both
the Arrhenius and the Bigelow methods.
In the Arrhenius method, the logarithm of the thermal rate constant was
plotted against the reciprocal of the absolute temperature. The slope index of
the semilogarithmic curve represented the Ea. In the Bigelow method, the
 THERMAL DEGRADATION KINETICS OF SUGARS IN SUGARCANE MUST 467

logarithm of decimal reduction time parameter at constant temperature (D)

was plotted against the temperature, with the negative reciprocal of the semi-
logarithmic curve representing the thermal resistance parameter (z).
Pruitt and Kamau (1993) suggested that better D estimates for curves
adjusted by logistic models were obtained using the estimated k parameters
from the logistic models to calculate the time when S = 0.1, which by definition
is the D. Substituting t = D and solving for D, Eq. (1b) results for each species:

D1 = τ 1 +
[ ln (9 + 10 × e− k τ )]
1 1

(4a)
k1

D2 = τ 2 +
[ ln (9 + 10 × e− k τ )]
2 2

(4b)
k2

The Ea from the Arrhenius method was converted to z through

Ramaswamy et al. (1989) (using Tmin = 383.15 K and Tmax = 413.15 K, the
minimum and maximum trial temperatures, respectively) and compared with
the z obtained directly from the Bigelow method.

RESULTS AND DISCUSSION

Sugar thermal degradation kinetics in sugarcane must were studied by

measuring both the remaining glucose and fructose hexose contents and the
remaining TRS contents after several thermal treatments.
Logistic models were chosen for fitting well to the kinetics that show
initial thermal lag and final tailing. Pruitt and Kamau (1993) proposed the use
of simple logistic models for a unique population of bacteria and extended it
to systems involving destruction of two populations of bacteria whose survi-
vors’ curves show thermal lag, and where simple exponential models give poor
adjustment. The same models, Eqs. (1a) and (2), were used here to describe
glucose, fructose and TRS thermal degradation kinetics. In Eq. (2), the sub-
scripts 1 and 2 refer to fructose and glucose, respectively.
Thermal degradation kinetics based on the hexoses glucose and fructose
were retrieved from the moment of maximum concentration of those chemical
components. At this moment, sucrose concentration had approached zero,
because all sucrose in the sugarcane must was hydrolyzed to glucose and
fructose. This happened after the following times of thermal treatments: 36.0 h
at 110C, 12.0 h at 120C, 6.0 h at 130C and 2.5 h at 140C. These treatment
times for each temperature were used as zero values in the model, because in
this study the interest was in hexose thermal degradation and not in hexose
468 J. NOLASCO JUNIOR and P.R. DE MASSAGUER

T = 110C T = 120C
Remaining glucose (x/x0)

Remaining glucose (x/x0)

Corrected time (h) Corrected time (h)

T = 130C T = 140C
Remaining glucose (x/x0)

Remaining glucose (x/x0)

Corrected time (h) Corrected time (h)

FIG. 1. GLUCOSE THERMAL DEGRADATION IN SUGARCANE MUST (pH 6.14, 21.5°BRIX)

Experimental plots and adjusted remaining glucose curves at constant temperature treatments
from the simple logistic model (Eq. 1a) with thermal lag, t, equal to zero, adopting as initial
point the time at maximum concentration. The plotted points are means of two measurements.
X, sucrose, glucose, fructose or total reducing sugar (TRS) content in time t; X0, sucrose, glucose,
fructose or TRS content when t = 0.

formation, which is predominant in the beginning of thermal treatments.

Remaining glucose and fructose curves (Figs. 1 and 2) during thermal treat-
ments were well fitted by Eq. (1a) and specific thermal degradation rate
constants for glucose and fructose, kglucose and kfructose, respectively, could be
obtained (Table 1).
Remaining TRS curves during thermal treatments showed similar behav-
ior as two chemical components that differ in their sensitivity to heat and
therefore degrade at different rates k1 and k2 (see Fig. 3 and Table 2). TRS
represents the total amount of sugar available for fermentation and is a useful
measure for ethanol plants. From Eq. (3), TRS represents the sum of potential
reducing sugars to be produced from sucrose hydrolysis plus the glucose and
fructose contents. As the only products from sucrose hydrolysis are glucose
and fructose, and from the obtained a values representing the ratio between the
 THERMAL DEGRADATION KINETICS OF SUGARS IN SUGARCANE MUST 469

T = 110C T = 120C
Remaining fructose (x/x0)

Remaining fructose (x/x0)

Corrected time (h) Corrected time (h)

T = 130C T = 140C
Remaining fructose (x/x0)

Remaining fructose (x/x0)

Corrected time (h) Corrected time (h)

FIG. 2. FRUCTOSE THERMAL DEGRADATION IN SUGARCANE MUST

(pH 6.14, 21.5°BRIX)
Experimental plots and adjusted remaining fructose curves at constant temperature treatments from
the simple logistic model (Eq. 1a) with thermal lag, t, equal to zero, adopting as initial point the
time at maximum concentration. The plotted points are means of two measurements.
X, sucrose, glucose, fructose or total reducing sugar content in time t; X0, sucrose, glucose, fructose
or TRS content when t = 0.

TABLE 1.
ESTIMATED KINETIC PARAMETERS FOR THE LOGISTIC MODEL (EQ. 1a) FOR
THERMAL DEGRADATION OF GLUCOSE AND FRUCTOSE IN SUGARCANE MUST
(pH 6.14, 21.5°BRIX) WITH CONFIDENCE INTERVAL ⬎99%

T (C) kglucose (h-1) r 2* s† F‡ kfructose (h-1) r 2* s† F‡

110 0.002540 0.98 0.000639 364 0.012465 0.95 0.006012 150

120 0.005527 0.96 0.001743 116 0.046901 0.98 0.003043 237
130 0.021492 0.96 0.001957 159 0.109236 0.97 0.005445 167
140 0.054924 0.94 0.002876 118 0.243502 0.96 0.005572 183

* regression coefficient.
† SD.
‡ regression statistical F-test.
T, temperature; kglucose, specific thermal degradation rate constant for glucose; kfructose, specific thermal
degradation rate constant for fructose.
470 Remaining TRS (x/x0) J. NOLASCO JUNIOR and P.R. DE MASSAGUER

Remaining TRS (x/x0)

T = 110C T = 120C

Time (h) Time (h)

T = 140C
Remaining TRS (x/x0)

Remaining TRS (x/x0)

T = 140C

Time (h) Time (h)

FIG. 3. TOTAL REDUCING SUGAR (TRS) THERMAL DEGRADATION IN SUGARCANE

MUST (pH 6.14, 21.5°BRIX)
Experimental plots and adjusted remaining TRS curves at constant temperature treatments, from the
extended logistic model for two species (Eq. 2). The plotted points are means of two measurements.
X, sucrose, glucose, fructose or total reducing sugar (TRS) content in time t; X0, sucrose, glucose,
fructose or TRS content when t = 0.

TABLE 2.
ESTIMATED KINETIC PARAMETERS FOR THE EXTENDED LOGISTIC MODEL (EQ. 2)
FOR THERMAL DEGRADATION OF TOTAL REDUCING SUGARS IN SUGARCANE MUST
(pH 6.14, 21.5°BRIX) WITH CONFIDENCE INTERVAL ⬎99%

T (C) a k1 (h-1) t1 (h) k2 (h-1) t2 (h) r 2* s† F‡

110 0.52 1.58E-2 0.10 1.96 ¥ 10-3 0.11 0.994 0.000505 3219
120 0.55 5.53E-2 12.61 4.39 ¥ 10-3 0.07 0.999 0.000154 6809
130 0.49 2.27E-1 7.74 1.75 ¥ 10-2 0.12 0.999 0.000106 7289
140 0.58 3.41E-1 1.20 4.33 ¥ 10-2 7.80 0.998 0.000168 8173

* regression coefficient.
† SD.
‡ regression statistical F-test.
T, temperature; a, population fraction that degrades with thermal degradation rate; t, thermal lag
parameter of the logistic model; k1 and k2, specific thermal degradation rate constants.
 THERMAL DEGRADATION KINETICS OF SUGARS IN SUGARCANE MUST 471

kfructose (1/h)

kfructose (1/h)
kfructose = 0.65 × k1(TRS)

kglucose = 1.26 × k2(TRS)

k1(TRS) (h–1) k2(TRS) (h–1)

FIG. 4. LINEAR REGRESSION BETWEEN RATE CONSTANTS (k1 AND k2) FROM
REMAINING TOTAL REDUCING SUGAR (TRS) THERMAL DEGRADATION MODEL
AND SPECIFIC THERMAL DEGRADATION RATE CONSTANTS FOR FRUCTOSE (kfructose)
AND GLUCOSE (kglucose) THERMAL DEGRADATION MODELS
(A) k1 versus kfructose (R2 = 0.97, s = 0.00068, F = 42, P = 0.022). (B) k2 versus kglucose (R2 = 0.99,
s = 1.35E-07, F = 12780, P = 7.8 ¥ 10-5).

two hexoses (0.49–0.58), it can be stated that sucrose thermal hydrolysis was
practically equimolecular regarding the formation on the hexoses for all tem-
peratures studied.
It could be assumed that the chemical components 1 and 2 from Eq. (2)
refer to fructose and glucose, respectively, because the value of the correlation
coefficient obtained from linear regression of the respective rate constants is
high (Fig. 4). Both rate constants k1 and k2, from the TRS thermal degradation
kinetics study, comprise sucrose hydrolysis, which is the main process at
the beginning of sugar thermal degradation. According to Nolasco Junior and
De Massaguer (2005), sucrose hydrolysis rate constants have magnitudes, on
the average, that are 12 times larger than fructose thermal degradation rate
constants and 70 times larger than glucose thermal degradation rate constants
that were obtained in this study.
Activation energies (Ea1 and Ea2) for TRS thermal degradation (Fig. 5)
were 140.37 and 140.23 kJ/mol, respectively, and represent the Ea values for
fructose and glucose thermal degradation, respectively. Those Ea values were
converted to Bigelow z, according to the equation of Ramaswamy et al. (1989),
in the temperature range of 110–140C, yielding z1 = 21.59C and z2 = 21.61C.
k1 and k2 for TRS thermal degradation were also converted to decimal
reduction parameters (D1 and D2) (Table 3) by Eqs. (4a) and (4b), to assess z
according to the Bigelow method (Fig. 6). Thermal resistance parameters z1
and z2, so calculated, were 22.56 and 21.95C, respectively, and differed 4.3
and 1.6%, respectively, from z calculated from the interconversion equation
between the two methods as proposed by Ramaswamy et al. (1989). From
Figs. 5 and 6, it can be seen that the two irreconcilable methods in terms of
temperature dependence of rate constants were fitted with a high correlation
472 J. NOLASCO JUNIOR and P.R. DE MASSAGUER

–0.5 –3.0

–1.5 –4.0
Ln (k1)

Ln (k2)
–2.5 –5.0

–3.5 slope = –16.8839 × 103 –6.0 slope = –16.8666 × 103

Ea/R = 16.8839 × 103 Ea/R = 16.8666 × 103
–4.5 –7.0

(1/T)×103 (K–1) (1/T)×103 (K–1)

FIG. 5. ARRHENIUS PLOT FOR TOTAL REDUCING SUGAR THERMAL DEGRADATION

REACTION IN SUGARCANE MUST (pH 6.14, 21.5°BRIX)
(A) Specie 1 (R2 = 0.966, s = 0.1014, F = 56.1, P = 0.017). (B) Specie 2 (R2 = 0.988, s = 0.0331,
F = 171.64, P = 0.0058).
k1 and k2, specific thermal degradation rate constants; T, temperature; Ea, activation energy;
R, gas general constant.

TABLE 3.
DECIMAL REDUCTION TIME PARAMETERS, D1 AND D2,
CALCULATED FROM TOTAL REDUCING SUGAR (TRS)
RATE CONSTANTS, k1 AND k2

T (C) D1 (h)* D2 (h)†

110 186.2352 1502.473

120 60.31221 670.7055
130 18.20951 168.6089
140 9.250705 72.07694

* Calculated by Eq. (4a).

† Calculated by Eq. (4b).
T, temperature.

coefficient and gave z1 and z2 quite good agreement, but when the kinetics of
destruction are not of first-order kinetics, the determination of heat resistance
through calculation of the D becomes meaningless (Abraham et al. 1990).
D (Table 3), however, were quite different, showing clearly that compo-
nent 1 (fructose) was degraded, on average, nine times faster than component
2 (glucose). Based on k, component 1 (fructose) was degraded, on average, 10
times faster than component 2 (glucose).
Ea values for glucose and fructose thermal degradation were similar,
maybe because of their chemical isomeric characteristics. Kelly and Brown
(1978), however, reported distinct Ea values for both hexoses: 123.5–138.2 kJ/
mol for glucose and 92.9–96.3 kJ/mol for fructose. On the other hand, rate
constant values obtained here revealed that fructose degraded approximately
 THERMAL DEGRADATION KINETICS OF SUGARS IN SUGARCANE MUST 473

Log (D1)

Log (D2)
slope = –0.044318C–1 slope = –0.045567C–1
z = 22.56C z2 = 21.95C

T(C) T(C)

FIG. 6. BIGELOW THERMAL-DEATH-TIME PLOT FOR TOTAL REDUCING SUGAR

THERMAL DEGRADATION REACTION IN SUGARCANE MUST (pH 6.14, 21.5°BRIX)
(A) Species 1 (R2 = 0.987, s = 0.006423, F = 152.89, P = 0.0065). (B) Species 2 (R2 = 0.989,
s = 0.005803, F = 178.91, P = 0.0055).
z, thermal resistance parameter.

9–10 times faster than glucose. A similar conclusion was drawn by Kelly and
Brown (1978), who reported that fructose decomposes around 10 times faster
than glucose. The fast decomposition of fructose with respect to glucose is
presumably due to the higher enolization rate of fructose (De Bruijn et al.
1986). The enolization rate difference observed in the fructose and glucose
molecules is due to differences in the reactivity of the fructose carbonil group
(C-2) with respect to the glucose carbonil group (C-1), because of the positions
of the neighboring hydroxyl groups.

CONCLUSIONS

As far as sugar chemical compounds in sugarcane must are concerned, it

can be roughly stated that sucrose expressed as reducing sugar represents 93%
by weight of the TRS, and glucose and fructose together represent 7% by
weight of the TRS. During sugar thermal degradation in sugarcane must, two
degradation reactions take place concomitantly: the sucrose hydrolysis to the
thermolabile hexoses glucose and fructose, and the degradations of these two
hexoses each one at its own velocity. The overall degradation process was
monitored here by the remaining TRS after the thermal treatments.
Only after all sucrose was hydrolyzed and hexoses reached their
maximum contents was it possible to study glucose and fructose thermal
degradation kinetics individually by monitoring their concentration decline
with treatment time.
Thermal degradation kinetic studies based on TRS are very meaningful
for ethanol production because TRS comprise the overall sugar content avail-
474 J. NOLASCO JUNIOR and P.R. DE MASSAGUER

able for fermentation. This sugar concentration decay can be monitored from
the beginning of the thermal treatment.
As for sugarcane must conditions used in this research, pH was essen-
tially as found in current sugarcane must preparation practice; however, °Brix
can vary according to sugar mill strategies of ethanol and sugar production. We
opted for 21.5°Brix because higher sugar concentrations in sugarcane must
result in fermented wines with higher alcoholic contents and more efficient
fermentations. However, it should be interesting to evaluate these kinetics by
varying the sugarcane must °Brix from 10 to 25°Brix.
The thermal degradation kinetics from this work, in conjunction with
the appropriate sucrose thermal hydrolysis kinetics (Nolasco Junior and De
Massaguer 2005), can be used to properly design cane juice clarifiers for
milling units, preventing both the sucrose hydrolysis and hexose degrada-
tion. Furthermore, in conjunction with appropriate thermal resistance, kinetic
data of sugarcane must contaminants can be used to properly design a
thermal process to inactivate contaminants with optimal sugar content reten-
tion, contributing to the worldwide effort to ban intensive industrial use of
antibiotics. Contaminant control in ethanolic fermentation processes could
be based on temperature, a physical agent, instead of the current control
practice based on antibiotics.

NOMENCLATURE

(1 - a) sugar fraction degrading at specific thermal degradation rate

k = k2
1,2 indexes to specify sugar species 1 and 2
D decimal reduction time parameter at constant temperature (h)
D1 decimal reduction parameter of sugar fraction 1 (h)
D2 decimal reduction parameter of spore fraction 2 (h)
DE thermal-death-time (TDT) tube external diameter (mm)
Di TDT tube internal diameter (mm)
Ea activation energy, (kJ/mol)
k specific thermal degradation rate constant (h-1)
kfrutose specific thermal degradation rate constant for fructose (h-1)
kglucose specific thermal degradation rate constant for glucose (h-1)
°Be specific density of solutions. In the sugar and alcohol industry, it
is used to express concentration of lime solutions (1°Be = 2 g of
dry substance/100 mL of solution)
°Brix soluble solid concentration (%m/m)
R gas general constant = 8.314 ¥ 10-3 kJ/molK
S(X/X0): remaining sugar fraction at time t
 THERMAL DEGRADATION KINETICS OF SUGARS IN SUGARCANE MUST 475

t sugarcane must thermal treatment time at each temperature (h)

TDT thermal death time
TRS total reducing sugars
X sucrose, glucose, fructose or TRS content (%m/m) in time t
X0 sucrose, glucose, fructose or TRS content (%m/m) when t = 0
z thermal resistance parameter to reduce D value at 10% of its
initial value (temperature units)
a population fraction that degrades with thermal degradation rate
k = k1
s SD
t thermal lag parameter of the logistic model (h)

ACKNOWLEDGMENT

The authors wish to thank Copersucar Technology Center for the finan-
cial support of this project.

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