Industrial Crops & Products 128 (2019) 338–345

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Industrial Crops & Products

journal homepage: www.elsevier.com/locate/indcrop

Removal of hexenuronic acid to reduce AOX formation in hot chlorine T

dioxide bleaching of bagasse pulp
⁎ ⁎
Haichuan Zhanga,b, Shuangxi Niea,b, , Chengrong Qina,b, Shuangfei Wanga,b,
a
College of Light Industry and Food Engineering, Guangxi University, Nanning, 530004, PR China
b
Guangxi Key Laboratory of Clean Pulp & Papermaking and Pollution Control, Nanning, 530004, PR China

A R T I C LE I N FO A B S T R A C T

Keywords: In this study, the effects of the hemicellulose-linked hexenuronic acid (HexA) on the kappa number, brightness
Bagasse pulp reversion and effluent properties under the hot chlorine dioxide bleaching (D-hot) stage were investigated.
Hexenuronic acid Moreover, the effects of the chlorine dioxide content on the residual HexA of bagasse pulp in D0 and D-hot stage
Hot-chlorine dioxide bleaching was evaluated. HexA was determined by UV–vis, and the absorbable organic halogen (AOX), chemical oxygen
AOX
demand (COD) and total organic carbon (TOC) in the bleached effluent were analyzed by using the AOX ana-
Brightness reversion
lyzer, COD analyzer and TOC analyzer, respectively. The results showed that the amount of chlorine dioxide
could be reduced by D-hot pretreatment. The kappa number and brightness reversion of the bleached pulp
obviously improved. Compared to the control, the AOX content decreased dramatically with an increase in
temperature. However, the COD and TOC increased significantly. A kinetic model considering the removal of
hexenuronic acid and its degradation was proposed. Degradation reactions of hexenuronic acid are first-order
with respect to their content, and the pH influences the degradation of hexenuronic acid. The activation energy
is 2.23 kJ/mol when the pH is 3.2, indicating that the degradation of hexenuronic acid is very rapid under these
conditions.

1. Introduction
For glucuronoxylan-containing raw materials, such as bagasse in
alkaline pulping, hydroxide ions react with 4-O-Meglucuronic acid
groups of the hemicellulose side chain to form hexenuronic acids
(HexA) (Chakar et al., 1999; Jonathan et al., 2017; Nie et al., 2018a).
The formation rate of HexA depends on some operating variables of the
kraft process, including the cooking time, cooking temperature and the
active alkali amount. The lignin-hexenuronic acid-xylan complexes are
formed during the kraft pulping processes (Cadena et al., 2011; Fan
et al., 2017; Song et al., 2016; Yao et al., 2015).
Recently, a novel method based on the use of UV–vis spectrometry
has been determined to be a simple, convenient and powerful approach
for quantitatively analyzing the degradation products from the HexA
moiety as furan derivatives (Chai et al., 1999). The identification of
acidic degradation products of HexA is attributed to early research by
Teleman et al (Teleman et al., 1996). Additional acid reactions with
HexA result in the formation of furan 2-carboxylic acid and 5-for-
mylfuran-2-carboxylic acid, which were found to be approximately
90% and 10% (Fig. 1), respectively (Brogdon, 2009). The resulting
hydrolyzate is analyzed at the UV–vis wavelength of 245 nm from the
absorption of furan 2-carboxylic acid and 290 nm from the absorption
of 5-formylfuran-2-carboxylic acid. Nevertheless, there are also re-
searchers that have used the UV–vis spectrometry method to measure
the furan derivatives from HexA at wavelengths of 245 nm and 285 nm
(Vuorinen et al., 1996). Chai et al. reported a simple and rapid spec-
troscopic method to quantify the content of HexA in chemical pulps
(Chai et al., 1999). The method is based on the highly selective hy-
drolysis of HexA in a mercuric chloride-sodium acetate solution. By
using a dual-wavelength spectroscopic determined from the furan de-
rivatives contents by further degradation of HexA, the spectral inter-
ference from the leached lignin in the resulting solution can be elimi-
nated.
The interest in research on HexA in chemical pulps lies in the fact
that HexA can negatively affect subsequent pulp bleaching, as well as
the properties of bleached pulps (Nie et al., 2013). It is well known that
HexA present in unbleached pulp also consumes a portion of the
bleaching reagents, such as chlorine dioxide, peroxy acids and ozone,
resulting in higher bleaching costs and environmental pollution (Lin
et al., 2018). A fraction of the chlorine dioxide used in bleaching is
converted to hypochloric acid. HexA not only reacts with chlorine di-
oxide but also with its intermediates, such as hypochloric acid and

⁎
Corresponding authors at: College of Light Industry and Food Engineering, Guangxi University, Nanning, 530004, PR China.
E-mail addresses: nieshuangxi@gxu.edu.cn (S. Nie), wangsf@gxu.edu.cn (S. Wang).

https://doi.org/10.1016/j.indcrop.2018.11.025
Received 20 June 2018; Received in revised form 6 November 2018; Accepted 12 November 2018
Available online 20 November 2018
0926-6690/ © 2018 Elsevier B.V. All rights reserved.
H. Zhang et al.
Fig. 1. Acid degradation products of the HexA group. Most are some type of furan derivatives.
chlorine (Lehtimaa, 2010; Tarvo, 2010), thereby influencing the
bleachability and the formation of AOX (Cadena et al., 2011; Costa and
Colodette, 2007; Pei et al., 2016). Some studies have shown that AOX
formation is highly reliant on the amount of residual HexA in the pulp
(Björklund et al., 2002; Costa and Colodette, 2002). Unstable AOX is
derived from HexA in the effluent (Björklund et al., 2004) and OX
produced in the chlorine dioxide bleaching stage is derived from the
reaction of chlorine with HexA (Costa and Colodette, 2007). Tarvo et al.
found that the formation of AOX results from the decomposition of OX
in the chlorine dioxide bleaching of kraft pulp with the passage of time
(Tarvo, 2010). However, these OX derived from HexA are easily de-
chlorinated under a neutral pH and an appropriate temperature (Eiras
et al., 2009). Moreover, 2-furoic acid and other degradation products of
HexA are formed and consume chlorine dioxide during chlorine dioxide
bleaching. As a result, 2-furoic acid forms chlorinated products, which
can be detected as AOX (Karim et al., 2011).
HexA groups suffer from both electrophilic and nucleophilic attacks,
which has a negative effect on the brightness stability (Andrew et al.,
2013; Karim et al., 2011). HexA can modify the optical properties of
bleached pulps by decreasing the brightness and increasing the
brightness reversion. A recent study (Rosenau et al., 2017; Zwirchmayr
et al., 2017) has shown that the HexA-derived chromophores have a
pronounced effect on the brightness development of chemical pulps
during bleaching. Therefore, the HexA must be selectivity degraded
prior to delignification or bleaching by hydrolysis with mild acids
(Chakar et al., 1999) or enzymes (Cadena et al., 2011; Martinsampedro
et al., 2015; Nie et al., 2018b). Some researchers have reported that
96% of HexA is eliminated after the hot acid stage (Andrew et al., 2013)
and only 13.6 ∼ 26.0% is removed after enzyme pretreatment (Nie
et al., 2015). Removing HexA helps save bleaching chemicals, reduces
the amount of AOX and improves the selectivity of the bleaching
(Chakar et al., 1999). The hydrolysis rate of HexA is known to increase
with an increasing temperature and decreasing pH. The difficulties with
the complete removal of residual HexA could be related to lignin-hex-
enuronic acid-xylan complexes. Although chlorine dioxide has a good
selectivity in delignification, AOX will still be generated in conventional
chlorine dioxide bleaching (Yao et al., 2017). Meanwhile, HOCl can
oxidize pulp cellulose when the contents of residual HexA groups are
Table 1
Characteristics of bagasse pulp before and after bleaching.a
Samples Brightness (%ISO) Brightness reversion (%ISO)
Unbleached pulp 43.24 ——
D0-bleached pulp 50.02 1.95
D-hot bleached pulp 54.07 0.38
a
Chlorine dioxide dosage is 2.5%.
339
Industrial Crops & Products 128 (2019) 338–345
very low, which may result in degradation of the cellulose (Zhou, 2011;
Zhou et al., 2008). Hot chlorine dioxide bleaching (D-hot) technology
has been applied for the removal of HexA and AOX reduction. Com-
pared with conventional chlorine dioxide bleaching, D-hot technologies
not only can avoid the tedious treatment of the D0 and the easy break of
the bonds between HexA and hemicellulose but also a higher deligni-
fication selectivity (Zhang et al., 2017).
The main objective of this study is, through the impact of residual
HexA on the kappa number, brightness reversion of bleached bagasse
pulp, and bleached effluent properties, to investigate the relationship
between the structural changes and degradation kinetic parameters of
HexA (activation energy, pre-exponential factor, and order of reaction)
in D-hot. This is crucial for a better understanding of the HexA de-
gradation process in D-hot. Meanwhile, the objective of this study is to
provide a theoretical foundation for the degradation of HexA during D-
hot of bagasse pulps.
2. Material and methods
2.1. Chemicals and raw materials
Unbleached bagasse pulp and an aqueous solution of chlorine di-
oxide was obtained from a Chinese kraft pulp mill. The concentration of
chlorine dioxide, expressed as active chlorine, was measured before the
experiment by iodometric titration. The chlorine dioxide solution was
stored in a brown bottle and the concentration of available chlorine was
17.4 ∼ 21.2 g/L. All other chemicals used in this study were purchased
from Sigma-Aldrich, and all chemicals were analytical grade (Zhang
et al., 2018c). The kappa number, HexA content, viscosity, brightness,
and brightness stability of the bagasse pulp before and after bleaching
were investigated as listed in Table 1.
2.2. Chlorine dioxide bleaching
The chlorine dioxide bleaching experiments were conducted in
closed plastic bags and put into an electric-heated thermostatic water
bath. Standard industrial bleaching parameters were used: D0, 60 ℃; D-
hot, 95 ℃. All stages were carried out performed at a 10% pulp
Kappa number Viscosity (ml/g) HexA content (μmol/g)
8.7 1095 16.5
4.1 1063 7.44
3.1 1003 4.48
H. Zhang et al.
consistency, a chlorine dioxide amount of 1% ∼ 4%, and a pH of 2.6 ∼
3.8 for 25 ∼ 125 min. Pulp was kneaded every 15 min during the
bleaching. The pulps were washed with distilled water and filtered to
collect the filtrate after bleaching. The bleached pulp was placed in a
lab with a constant temperature and constant humidity for 24 h and
then subjected to characterization.
The brightness of the bagasse pulp was determined according to the
TAPPI standard (T 560 om-05), the kappa number of the pulp was
determined based on the TAPPI standard (T 236 om-99) and the visc-
osity of the pulp was determined based on the TAPPI standard (T230
om-04). The brightness reversion was obtained according to ISO 5630-3
(80℃, 65% R.H. for 24 h).
2.3. Analysis of degradation products by UV–vis spectroscopy and
calculation of HexA content
Several methods for quantitatively analyzing HexA in pulps have
been reported (Zhu, 2014), such as the VTT method, KTH method and
TAPPI T 282 om-13 Test Method. However, the VTT method is quite
time consuming, mainly because of a longtime enzymatic hydrolysis of
HexA in pulp, and the KTH method and TAPPI T 282 om-13 Test
Method employ several hazardous chemicals, such as mercuric acetate
and mercury chloride. Here, we use the method in which a pulp sample
is hydrolyzed with a 3.5 pH buffer solution of formic acid/sodium
formate at 110 ℃ for one hour in a nitrogen atmosphere (Fig. S1). The
resulting hydrolysate is analyzed by UV–vis spectroscopy and the
amount of HexA is determined from the absorption of the furan deri-
vatives, i.e., the degradation products of HexA. The UV–vis absorption
of 2-furoic acid at 245 nm is the main signal peak of the acid hydrolysis
products from HexA. The HexA content was determined using Eq. (1).
A245
CHexA =
8.7 × m
where CHexA is the HexA content in the pulp (μmol/g), A245 is the ab-
sorbance value of 2-furoic acid determined at 245 nm, 8.7 is absorption
coefficient, and m is the pulp dry weight (g).
2.4. Analytical methods of effluent
AOX measurements were employed by a Multi X 2500 halide ana-
lyzer (Jena, Germany). The content of AOX was calculated through the
micro coulomb titration method. For the basic method and process,
refer to our previous studies (Nie et al., 2014a; Zhang et al., 2018a).
The chemical oxygen demand (COD) was evaluated according to stan-
dard methodology EPA 00340. Total organic carbon (TOC) analyses
were performed in a TOC-VCPH Shimadzu analyzer.
2.5. Determination of the kinetic parameters during the degradation of
HexA in D-
The determination of the kinetic parameters of HexA was based on
the modified form hot.of the Arrhenius equation that was used for de-
termining the kinetic parameters of biomass from a spectroscopy ana-
lysis technique (Yang et al., 2014).
The global kinetics of the degradation reaction can be expressed as
follows:
dXi
= ki X m
dt
The Arrhenius equation can be written as
Eai
ki = A∙e− RT
A can be written as
A = [H+]n ∙Ai
Substituting the value of ki in equation 2 and taking the Natural
Industrial Crops & Products 128 (2019) 338–345
logarithm (ln) on both sides
dXi E
ln = ln Ai − ⎛ ai ⎞ + n. ln [H+] + m∙lnX
dt ⎝ RT ⎠ (5)
X can be written as
X = Xi0 − Xi (6)
Eq. (5) can be converted to
d E
ln Xi = ln Ai − ⎛ ai ⎞ + n. ln [H+] + m∙ln (Xi0 − Xi )
dt ⎝ RT ⎠ (7)
Eq. (7) is in the form of
y = B + Cx + Dz + Ef (8)
where y, x, z, f, B, C, D and E in Eq. (8) are defined as follows:
d
y = ln dXi ; x = 1/RT; z = ln [H+]; f = ln (Xi0 − Xi ) ; B = ln Ai; C =
t
-Eai; D = n; E = m. X, t, ki, n, m, A, Eai, R, T, Xi0, and Xi in equations
2 − 7 are defined as follows: X is the content of HexA undergoing re-
action (μmol/g), t is the residence time (s), ki is the degradation rate
(min−1), n is the order of the reaction for [H+], m is the order of the
reaction for the HexA content, A is the pre-exponential factor (min−1),
Eai is the activation energy of the degradation reaction (kJ. mol−1), R is
the universal gas constant (kJ. mol−1 K−1), T is the absolute tempera-
ture (K), Xi0 is the initial content of HexA residue in unbleached bagasse
pulp (μmol/g), and Xi is the content of the HexA residue at time t
(μmol/g).
The constants B, C, D, and E in Eq. (8), which denote ln A, − E, n,
and m, respectively, were estimated by a multilinear regression of the
experimental data using the LINEST function in Microsoft Excel.
3. Results and discussion
(1)
3.1. Impact of HexA on AOX, Kappa number and brightness reversion
The effect of the chlorine dioxide amount on the residual HexA was
studied by varying the active chlorine charge in the range 1.0% ∼
4.0%. The main results are composed in Fig. 2a. Under the D0 and D-hot
conditions of bleaching, the final residual HexA depended on the
chlorine dioxide amount. The residual HexA content in D-hot bleached
pulps was much less than the control pulps. Chlorine dioxide demand
can be decreased by 20% ∼ 33% to remove the same HexA. The re-
sidual HexA of the pulp obtained was 3.85 μmol/g for D0 and
1.97 μmol/g for D-hot when the amount of chlorine dioxide was 4%.
However, more chlorine dioxide had only a relatively minor additional
effect on HexA removal. This is caused by the degradation of HexA
during D-hot, which breaks the bonds of the lignin-HexA-Xylan com-
plexes, increasing the degradation of HexA and thereby decreasing the
consumption of chlorine dioxide in D-hot. Meanwhile, the residual
lignin of bagasse pulp was also removed by D-hot. With regard to
bleaching, HexA does not react with chlorine dioxide, but does react
with its intermediates such as hypochloric acid and chlorine (Lehtimaa,
2010; Tarvo, 2010), thereby influencing the bleachability and enhan-
cing the consumption of chlorine dioxide.
Fig. 2b shows the relationship between the HexA content and the
kappa number during chlorine dioxide bleaching of bagasse kraft pulp.
The results show that the kappa number of bagasse pulp increases with
an increase in the HexA content, which is in agreement with a previous
study by Shin et al (Shin et al., 2004). They reported that a higher
(2)
residual HexA contributed to the kappa number more than the residual
extractives in pulps. In fact, permanganate reacts with HexA under
acidic conditions prevailing in the standard kappa number measure-
(3)
ment (Li and Gellerstedt, 1997). HexA can contribute anywhere from
13% to 26% to the kappa number of bagasse kraft pulps and is more
important in bleachable hardwood pulps. In the present work, a larger
(4)
data set corroborates previous studies, indicating that there was a
correlation between the residual HexA removal and the total kappa
340
H. Zhang et al.
Fig. 2. Impact of residual HexA on AOX, kappa number and brightness reversion.
Table 2
Parameters of fitting for HexA and AOX.
Correlation of HexA (μmol. g−1) vs. AOX (mg.L−1)
Stages Slope Intercept R2
D0 2.43 ± 0.13 49.72 ± 0.52 0.8231
D-hot 3.66 ± 0.59 36.82 ± 2.32 0.7261
Different T 1.41 ± 0.16 20.43 ± 0.64 0.9834
number reduction with chlorine dioxide bleaching for bagasse pulps.
The kappa number of the pulp decreased by 1 unit on average when
5.6% of HexA was removed.
The impact of HexA removal during bleaching on the brightness
stability is significant (Andrew et al., 2013; Cadena et al., 2010;
Sevastyanova et al., 2006). The comparison of the influence of residual
HexA on brightness reversion for two kinds of bleached pulp is de-
monstrated in Fig. 2b. It was shows that the pulp brightness reversion
was affected through the severity of D-hot. The pulp brightness rever-
sion was increased as the severity of residual HexA was enhanced.
When the sample was bleached at 60 ℃ for 60 min and 95℃ for 60 min,
the residual HexA content was 10.5 mmol/kg and 7.7 mmol/kg, re-
spectively. As the residual HexA decreased, the reversion number de-
creased from 4.2%ISO to 0.7%ISO at the same chlorine dioxide amount.
When the bagasse pulp was bleached with the same chlorine dioxide
charge, the residual HexA content was reduced with the bleaching
temperature. For example, the HexA content decreased from 59% (60
℃) to 44% (95 ℃) at a 2.5% chlorine dioxide charge because more
bonds of lignin-HexA-Xylan complexes (Cadena et al., 2011) were
broken by a higher temperature environment. The improvement in the
brightness reversion can be explained by the reducing chromophores
(Eiras et al., 2008) during the removal of HexA or lignin-HexA-xylan
complexes by D-hot. The conjugated double bond from HexA is re-
sponsible for a significant portion of the chromophores of bagasse kraft
pulp (Rosenau et al., 2017; Zwirchmayr et al., 2017). These unsaturated
bonds are the main binding sites of metal ions (Sevastyanova et al.,
2006). Selectively removing HexA cannot only improve the brightness
341
Industrial Crops & Products 128 (2019) 338–345
stability of the pulp but also reduce the metal ion content in the
bleached pulp (Ragauskas, 2000). As the temperature of the bleaching
increases, hemicellulose is more depolymerized, solubilized, and par-
tially degraded, which increases the removal of HexA. Therefore, the
brightness reversion of D-hot bleached pulp was less than that of the
control pulp.
Temperature usually plays a critical role in chlorine dioxide
bleaching. D-hot has been proven to be an effective method of reducing
the AOX content in the ECF bleaching sequence (Kumar et al., 2007;
Ventorim, 2005; Zhang et al., 2018a). Fig. 2c shows the AOX formation
and residual HexA during bleaching of the model in the D0 stage and D-
hot stage. The detailed fitting parameters of the model are summarized
in Table 2. The correlation coefficient R2 = 0.7261, 0.8231, and 0.9834
for D-hot, D0 and a different temperature, respectively. This result in-
dicates that a certain correlation exists between the AOX content and
the residual HexA for all pulps of D0 and D-hot, regardless of the
temperature in the range of 70℃ ∼ 95℃. The correlation coefficient of
different bleaching temperatures is much higher than that of D0 and D-
hot. This result demonstrates that the formation of AOX and the de-
gradation of HexA are mostly ascribed to rising the reaction tempera-
ture. Interestingly, similar results were achieved for the AOX con-
tribution of residual HexA in chlorine dioxide bleaching of ECF short
sequences (Björklund et al., 2004; Nie et al., 2015). HexA reacts with
hypochloric acid and chlorine produces AOX (Cadena et al., 2011). As
expected, the AOX content drops after the D-hot treatment is sig-
nificantly more than that after the D0 stage. Such results are due to the
D-hot treatment of bagasse kraft pulps, resulting in a significant de-
gradation of residual HexA.
3.2. Impact of AOX on COD and TOC
To study the impact of the residual HexA on effluent quality, both
bleaching effluents were analyzed. Fig. 3a shows the relationship be-
tween AOX and COD at the D0 and D-hot stages. It can be observed that
the COD value is enhanced, while the AOX content is increased by
bleaching in the D0 or D-hot stage. The detailed fitting parameters of
H. Zhang et al.
Fig. 3. Impact of AOX on COD and TOC in the D0 and D-hot stages.
Table 3
Parameters of fitting for COD and AOX.
Correlation of COD (mg.L−1) vs. AOX (mg.L−1)
Stages Slope Intercept
D0 0.17 ± 0.006 11.24 ± 1.40
D-hot 0.19 ± 0.0003 10.02 ± 0.81
Table 4
Parameters of fitting for TOC and AOX.
Correlation of TOC (mg.L−1) vs. AOX (mg.L−1)
Stages Slope Intercept
D0 0.025 ± 0.005 16.92 ± 1.97
D-hot 0.014 ± 0.008 13.26 ± 4.04
the model are summarized in Table 3. The correlation coefficient of
COD vs. AOX in D0 stage effluent (R2 = 0.9943) is much higher than
that of the D-hot stage effluent (R2 = 0.9757). This indicates that the
COD of the D0 stage effluent is mostly ascribed to the AOX. Similar
trends were observed in the relationship between the AOX content and
TOC in Fig. 3b. The detailed fitting parameters of the model are sum-
marized in Table 4. There is a general belief that D-hot treatment re-
duces the AOX increases the COD and TOC of the bleaching effluents.
These results are well in agreement with other references (Ventorim,
2005). In our case, the AOX was reduced by approximately 50% with
the same consumption of chlorine dioxide. It has been reported that a
major portion of the residual HexA could be gradually degraded to
organic low molecular compounds, such as furfural, 2 (5 H)-furanone,
2-furancarboxylic acid, 3- furancarboxylic acid, 3-methyl-2,5-fur-
andione and 2-methyl-furan (Zhang et al., 2018b), which increases the
COD and TOC (Costa and Colodette, 2007; Ventorim, 2005). On the
other hand, there is a contribution to the COD and TOC from the AOX
groups in the D0 or D-hot stage effluents.
3.3. Degradation of HexA in bagasse fibers during D-hot
A typical HexA removal versus reaction time profile for the D-hot
stage is shown in Fig. 4a. The removal of HexA is increased with an
increasing reaction time. As the reaction continues, the rate of HexA
removal reaches an asymptotic level. In addition, the bleaching time is
too long, resulting in the degradation of cellulose (Karim et al., 2011)
and a reduction in the yield of bleached pulp.
According to the yield changes of the HexA residue, it was de-
termined that the chemical reactions that occurred during HexA de-
gradation at a higher temperature were more sensitive than at the
temperature between 60 and 70 ℃, as shown in Fig. 4b. The relation-
ship between the rate constants and reaction temperature can be es-
tablished with the Arrhenius equation. Considering the effect of the
Industrial Crops & Products 128 (2019) 338–345
concentration of hydrogen ions (Girisuta et al., 2013; Maloney et al.,
1985), the rate constants can be expressed by equations (3) and (4). To
estimate the kinetic parameters in the kinetic model proposed in this
paper, equations (2) – (8) were solved using the multilinear regression
R2 of the experimental data on each degradation conditions. The calcu-
0.9757 lated kinetic parameters of HexA are shown in Table 5. The energy of
0.9943
activation was determined to be 77.93 kJ /mol for pH = 2.6, 2.23 kJ/
mol for pH = 3.2 and 39.31 kJ/mol for pH = 3.8. This should be
compared to the energy of activation for the bulk degradation of HexA,
which was previously reported to be 117 kJ /mol for hardwood pulp
(Bouchard, 2006) and 50 ∼ 60 kJ /mol for softwood pulp (Bergnor-
Gidnert et al., 1998). It seems as though part of the HexA content of
R2 bagasse pulp is stable during the degradation and is independent of
0.68 temperature, whereas another part dissolves together with the lignin,
0.92 degrading to a certain extent depending on the temperature.
The degradation of HexA is closely related to the pH during D-hot.
The degradation rate of HexA is relatively high when the pH of the
bleaching system ranges from 2.6 to 3.8. As showed in Fig. 4c, the pH
has different effects on the degradation of HexA under different tem-
perature conditions. With the change of pH from 2.6 to 3.8, the de-
gradation of HexA first increased and then decreased. At pH 2.6, the
degradation rate of HexA was 67.65%. A low pH will hamper the high
temperature D-hot process and produce more hypochlorite due to the
invalid decomposition of chlorine dioxide (Svenson et al., 2002), which
produces more AOX. At pH 3.2, the degradation of HexA reached the
maximum (up to 68.45%), because the pH was very close to the acid
hydrolysis constant of HexA (Vuorinen et al., 1999). When the pH was
3.8, the degradation amount of HexA decreased. In fact, the pH of the
bleaching system at the initial stage is 3 to 4. The pH of the bleaching
system decreases as the amount of organic acid increases and as the
bleaching time increases.
Chemical reaction kinetics are often used to study the reaction
mechanism of some chemical reactive substances (Nie et al., 2014a(a);
Nie et al., 2014b(b)). At present, many researchers focus on predicting
the concentration of degradation products through established kinetic
models (Vallejos et al., 2015; Yang et al., 2014). The kinetic model for
HexA generation and degradation during pulping processes has been
studied (Bahuguna and Shukla; Danielsson et al., 2007; Simão et al.,
2005).
In most cases, almost 90% of the HexA present in the pulp is de-
graded by acid into furan derivatives. The compound absorbs strongly
in the UV–vis spectra of 2-furoic, as shown in Fig. S2. The amount of
HexA is determined from the absorption of 2-furoic at 245 nm.
Based on previous research results (Zhang et al., 2018a, b), a de-
gradation pathway for HexA in D-hot is proposed as showed and shown
in Fig. 5. In the appropriate conditions, HexA converts into (1) 2- furoic
and (2) 5- formyl -2- furoic acid (Sevastyanova et al., 2006; Teleman
et al., 1996). At the same time, hypochlorous acid is produced during
the reaction of ClO2 with residual lignin (Lehtimaa, 2010; McKague,
1995; Zawadzki et al., 2000). Therefore, the AOX (3) ∼ (6) is produced
342
H. Zhang et al. Industrial Crops & Products 128 (2019) 338–345

Fig. 4. Impact of reaction time, temperature and pH on HexA removal.

Table 5
Kinetic statistical parameters of HexA degradation in temperature and pH range
of D-hot stage.
T (K) pH ki (10−3. min-1) A (min−1) Ea(kJ/mol) R2

80 2.6 0.76 0.74 77.93 ± 4.1 0.68

85 0.88 0.86 0.94
90 1.56 1.52 0.81
95 2.09 2.09 0.89
80 3.2 1.96 1.96 2.23 ± 0.17 0.99
85 2.34 2.34 0.65
90 1.66 1.66 0.94
95 2.28 2.25 0.96
80 3.8 1.41 1.39 39.31 ± 1.9 0.97
85 2.20 2.17 0.96
90 2.03 2.00 0.94
95 2.65 2.62 0.99

during the reaction of hypochlorous acid with residual HexA(Lehtimaa,

2010; Zhang et al., 2018a).
The pre-exponential factors in this study were 0.74 ∼ 2.09 min−1
for pH = 2.6, 1.96 ∼ 2.25 min−1 for pH = 3.2 and 1.39 ∼ 2.62 min−1
for pH = 3.8. They were much higher than reported by Bahuguna et al.,
where the pre-exponential factors were 27.6 min−1 below pulping
(Bahuguna and Shukla, 2010). The HexA degradation orders de-
termined in this study were 1 for HexA and 0.09 ∼ 0.34 for the H+
concentration. The results illustrated that the degradation reactions in
D-hot were heterogeneous. However, most of the studies assumed first-
order reactions for their investigation of the HexA degradation kinetics
in D-hot (Clavijo et al., 2012). Jiang et al. reported that the kinetic
orders for HexA was separated into two pseudo-first-order during the
acid hydrolysis process (Bouchard, 2006).
Based on the abovementioned kinetic model and the experimental
results, it can be observed that the HexA degradation is incomplete in
the D-hot stage. These results are in agreement with those of studies by
Fatehi et al (Fatehi et al., 2009), who reported that the degradation of
Fig. 5. Degradation pathway of HexA during hot chlorine dioxide bleaching.
HexA can be observed in two stages: easy degradation and hard de-
gradation. At present, part of the refractory HexA still constitutes
21.55% of the total.
The values of n and m can be determined by linear regression,
n = 0.34 for 80 ℃, 0.35 for 85 ℃, 0.10 for 90 ℃ and 0.09 for 95 ℃. The
value of m was 1.
The corresponding parameters are determined when the reaction
temperature is changed, and the concentration of hydrogen ions is held
constant. From these, we can determine the Ea and A of HexA de-
gradation as 2.23 ∼ 77.93 kJ/mol and 0.74 ∼ 2.62, respectively. The
activation energy is expected to be very low when the pH is 3.2, in-
dicating that the degradation of HexA is very rapid under this condi-
tion.

343
H. Zhang et al.
4. Conclusions
A D-hot pretreatment was found to be the most beneficial for re-
sidual HexA removal. The thus improved kappa number and brightness
reversion of bleached bagasse pulp and the AOX was reduced. This also
simultaneously saves more chlorine dioxide than the traditional D0
stage. In contrast, the value of COD and TOC in the D-hot stage was-
tewater was very high. The reason for the COD and TOC increase was
ascribed to the degradation of HexA. The degradation behavior of HexA
was evaluated in the temperature range from 80 to 95 ℃. The lowest
yield of the HexA residue was obtained at 95 ℃ and showed an increase
at lower temperatures. The activation energy (Ea), pre-exponential
factor (A), and reaction order (m) of HexA was 2.23 ∼ 77.93 kJ/mol,
0.74 ∼ 2.62 and 1, respectively. The degradation pathway of HexA at
the D-hot stage was proposed as follows: (1) HexA converts into (1) 2-
furoic and (2) 5- formyl -2- furoic acid, (2) the hypochlorous acid reacts
with residual HexA format AOX (3) ∼ (6).
Acknowledgements
The project was supported by the National Natural Science
Foundation of China (31760192), the Guangxi Natural Science
Foundation of China (2016GXNSFBA380234) and the Scientific
Research Foundation of Guangxi University (Grant No.XGZ160166).
Appendix A. Supplementary data
Supplementary material related to this article can be found, in the
online version, at doi:https://doi.org/10.1016/j.indcrop.2018.11.025.
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