Journal of Bioresources and Bioproducts 7 (2022) 180–189

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Journal of Bioresources and Bioproducts

journal homepage: http://www.keaipublishing.com/en/journals/journal-of-
bioresources-and-bioproducts/

Evaluating process of auto-hydrolysis prior to kraft pulping on

production of chemical pulp for end used paper-grade products
Wenchao Jia a,b, Miaofang Zhou a,b, Chenfeng Yang a,b, He Zhang a,b, Meihong Niu a,b,
Haiqiang Shi a,b,∗
a
Liaoning Key Laboratory of Lignocellulose Chemistry and Biomaterials, College of Light Industry and Chemical Engineering, Dalian Polytechnic
University, Dalian 116034, China
b
Liaoning Collaborative Innovation Center for Lignocellulosic Biorefinery, College of Light Industry and Chemical Engineering, Dalian Polytechnic
University, Dalian 116034, China

a r t i c l e i n f o a b s t r a c t

Keywords: The objective of this work is to systematically evaluate the performance of the hydrolysis-based
Auto-hydrolysis kraft pulping process and associated pulp and black liquor characteristics. Acacia wood chips were
Kraft pulping auto-hydrolyzed under various severities, then the hydrolyzed wood chips were kraft pulping. The
Pulping performance
results indicated that the yield of pulp significantly dropped with intensifying the auto-hydrolysis
Fiber morphology
severity. Meanwhile, the removal rate of pentosan reached 98.6% in the screened pulp at the P-
Black liquor
factor of 1 000. The fiber length, fines and fiber crimp of the screened pulp were not affected by the
auto-hydrolysis treatment. Auto-hydrolyzed pulps deteriorated fibrillation and beating response
of the pulp in a refining process. However, fiber length and fines changed obviously after beating
treatment. After auto-hydrolysis, the tensile index of the paper matrices decreased, some particle
substances were found on the surface of the pulp fiber, and the solid and organic content of the
black liquor were improved.

1. Introduction

With increasing attention to the environment, especially the greenhouse effect and the diminishing supply of fossil fuels, the
incentives for creating alternate and renewable energy sources are high (Duarte et al., 2011; Wang et al., 2020). Lignocellulosic
biomass is a principal source of cellulosic fibers used in pulp and paper manufacture. The lignocellulosic biomass to be pulped
usually includes 15%–30% lignin, 20%–30% hemicellulose, 40%–50% cellulose, and 2%–5% extractives (Hamaguchi et al., 2013).
In recent years, biomass refining technologies to produce other value-added products than traditional pulp and paper have been
studied significantly. Among them, the technology of Integrated Forest Biorefinery (IFBR) is the most representative (Heiningen,
2007). This concept combines the technical characteristics of chemical pulping and biomass refining to make more rational use of
cellulose, hemicellulose, and lignin in pulping materials. To produce hemicelluloses, a pretreatment prior to chemical pulping has
been proposed in a so-called hydrolysis process. This pretreatment section is important as it facilitates the production of hemicelluloses
in the chemical pulping industry. In this process, the hemicellulose is extracted as polysaccharides or monosaccharides, and dissolved
in hydrolysis liquor, which contains mainly pentose and hexose components (Vázquez et al., 2005; Xu et al., 2007; Bian et al., 2010).
The obtained xylose is processed to form a series of high value-added products, such as ethanol and xylitol (Qureshi et al., 2006;

∗
Corresponding author.
E-mail address: shihq@dlpu.edu.cn (H. Shi).

https://doi.org/10.1016/j.jobab.2022.05.002
Received 5 February 2022; Received in revised form 6 March 2022; Accepted 19 March 2022
Available online 16 May 2022
2369-9698/© 2022 Published by Nanjing Forestry University. This is an open access article under the CC BY-NC-ND license
(http://creativecommons.org/licenses/by-nc-nd/4.0/)
W. Jia, M. Zhou, C. Yang et al. Journal of Bioresources and Bioproducts 7 (2022) 180–189

Canilha et al., 2008; Huang et al., 2010). Hemicellulosic sugars can also be utilized as basic components for biodegradable materials
or other petroleum-based chemicals and products (Jeffries and Jin, 2004; Thomas et al., 2004).
Several methods, including steam treatment, organic solvent, alkali, and dilute acid have been used to remove a fraction of hemi-
cellulose from lignocellulosic biomass prior to chemical pulping (Parajó et al., 1997; Palm and Zacchi, 2003; Beukes and Pletschke,
2011; de Oliveira Santos et al., 2018). These treating processes are either prohibitively expensive, produce difficult-to-manage hy-
drolysates, or necessitate the use of high-pressure and expensive equipment. Hydrothermal extraction is also a suitable technology to
separate hemicellulose and does not require any chemicals (Liu et al., 2015a; Shen et al., 2021). During the auto-hydrolysis extraction
process, the hydronium ions generated by self-ionization of water react with the acetyl groups of hemicellulose side chains and then
produce acetic acid, which plays a role of catalyst to further facilitate the removal of the acetyl groups and thus form additional acetic
acid (Gütsch et al., 2012; Li et al., 2014). Meanwhile, a significant proportion of hemicellulose can be degraded and solubilized as an
oligosaccharide (Yoon and Heiningen, 2008). The hydrothermal extraction pretreatment can be advantageous for various causes: the
pre-hydrolysate liquor includes a significant amount of dissolved hemicellulose, the crucial part of cellulose is only a little degraded,
additional chemical costs can be lowered, and using water as liquid media is more environmentally friendly (Hamaguchi et al.,
2013).
Therefore, combining hydrothermal extraction with the pulping process to convert hemicellulose into chemicals and fuel might
be cost-effective for pulp mills (Lu et al., 2012). Chen et al. (2010) found that the auto-hydrolysis of wood chips could result in
the degradation of a significant amount of hemicellulose, with minor lignin and cellulose dissolution. Removing such an amount of
hemicellulose from the wood chips through the auto-hydrolysis process would increase the porosity of fiber cell walls and also expose
additional free hydroxyl groups on cellulose, enhancing the following alkali impregnation effectiveness during the pulping process
(Jiang et al., 2016). In this process, more hemicellulose removal would leave a purer cellulosic product and thus higher viscosity
of the generated pulp, which can be achieved under mild extraction conditions. Conversely, cellulose could be damaged, and pulp
viscosity might drop under severe extraction conditions (Lu et al., 2012). With decreased swelling of hemicellulose-extracted pulps,
the interfiber contact during beating decreases, deteriorating external fibrillation and hence beating response (Walton et al., 2010;
Hamaguchi et al., 2013). In this respect, a previous publication (Yoon and Heiningen, 2008) reported considerably increased PFI
type pulp beater revolutions for hydrolyzed pulps to obtain a given freeness. Also, reducing hemicellulose from pulp will generate
a detrimental effect on various pulp characteristics, such as bursting strength, compression strength, tensile stiffness, and tensile
strength, while having a little effect on elongation and a modest increase in tearing strength of pulp (Helmerius et al., 2010). Other
characteristics of the pulps, Zero-span wet tensile strength, Scott bond energy and Z-directional strength appear to be unaltered
by hemicellulose percentage (Hamaguchi et al., 2013). In addition, some studies have found that auto-hydrolysis kraft pulping has
additional disadvantages, for example, the generation of viscous deposits on the hydrolyzed wood chip surface (Gehmayr et al.,
2011; Martin-Sampedro et al., 2014; Zheng et al., 2021). These precipitates mainly contain lignin that polymerizes with carbohydrate
derivatives or with itself to form particles on the wood chip surface (Jia et al., 2022). Changes in lignin reactivity during hydrolysis
may impair the efficiency of subsequent cooking operations. After intense hydrolysis, the deposited lignin likely leads to delayed
delignification in pulping and bleaching (Leschinsky et al., 2008).
So far, the effectiveness of the integrated biorefinery based on the hydrolysis-kraft process, pulping performance, final pulp and
black liquor properties have not been thoroughly evaluated. In this study, to understand the effect of hydrolysis intensity on yield and
characteristics of the final pulp achieved from hydrolysis-kraft pulping, acacia wood chips were hydrolyzed under varied severities,
which was followed by kraft pulping under identical cooking conditions.

2. Materials and methods

2.1. Materials

The quick-growing Indonesian acacia wood chips with a similar size of 3 cm × 2 cm × 2 mm were supplied by Shandong Asia Symbol
Pulp & Paper Co., China. The wood chips were air-dried and kept in ziplock bags for subsequent usage. Chemical studies revealed
that these wood chips comprised of 21.33% pentosan (GB/T 2677.9—1994), 73.23% holocellulose (GB/T 2677.10—1995), 23.93%
Klason lignin (GB/T 2677.8—1994), 2.17% acid-soluble lignin (GB/T 10,337—1989), 0.39% ash (GB/T 742—2018), and 4.02%
benzene-ethanol extractive (GB/T 2677.7—1994). Xylose (chromatographic grade) was supplied by Sigma-Aldrich, Shanghai. Other
chemicals (analytical grade) were purchased from Sinopharm Chemical Reagent Co., China.

2.2. Auto-hydrolysis process

The Autohydrolysis process for extracting hemicelluloses was carried out in an electric heating digester with four of 2 L stainless
steel vessels (ZQS1-E, Xianyang Tongda, China). The follows were the auto-hydrolysis conditions: 250 g of oven-dried wood chips,
the solid-to-liquid ratio of 0.25, 170 °C of specified temperature and kept for the desired time from 0 to about 90 min at the specified
temperature. The heating rate curve followed a linear equation with R2 = 0.967 (Fig. 1). When the auto-hydrolysis extraction was
finished, the cooking vessels were withdrawn from the heat source and cooled. The solid residues and auto-hydrolysate (AHL) were
isolated through a Büchner funnel. The unwashed solid residues were air-dried and then subjected to a kraft pulping process.
The objective of this study is to illustrate the potential utilization of auto-hydrolysis-kraft chemical pulp for paper-grade products.
The P-factor of the auto-hydrolysis process is typically employed to assess the combined effect of time and temperature (i.e., strength

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200

150

y=2.1481x+50.888

T (℃)
100 R2=0.967

50

0
0 10 20 30 40 50 60
t (min)

Fig. 1. Temperature profile as a function of heating time.

Table 1
Auto-hydrolysis conditions corresponding to P-factor and residual wood chip
recovery.

Temperature ( °C) Time (min) P-factor Residual wood chip recovery (%)

170 2.9 120 89.53

170 11.0 200 86.41
170 31.3 400 83.76
170 51.6 600 82.45
170 72.0 800 79.85
170 92.3 1 000 77.78

or severity) (Shi et al., 2019b). The formula for calculating the P-factor (Pf ) is as follows:
15, 106,
𝑃f = ∫0𝑡 𝑉𝑇 ∕𝑉373K = ∫0𝑡 exp(40.48 − )dt (1)
𝑇
where T is the Kelvin temperature (K), t is the reaction time (min), VT is the reaction rate at a certain temperature (mol/(L•s)); V373K
is the reaction rate at 100 °C (mol/(L•s)). Auto-hydrolysis conditions corresponding to the P-factor and the recovery of residual wood
chips are listed in Table 1. The P-factor of the raw wood chip group was 0.

2.3. Kraft pulping

In this study, kraft pulping was carried out using the identical device as the auto-hydrolysis extraction process. The follows were
the kraft pulping conditions: 150 g of raw material or 150 g of raw material after auto-hydrolysis extraction (unwashed), 600 g of
water, 22.5 g of active alkali (AA, calculated as Na2 O), and 30% sulfidity, 165 °C of specified temperature and kept for 150 min. The
black liquor and pulps were isolated by hand twisting in a cotton bag after cooking. To determine the unscreened pulp yield, the pulps
were cleaned completely with deionized water and packed in ziplock bags to balance moisture. Then, the pulps were disintegrated
using a fiber disintegrator for 2 min with a consistency of 0.4%. The disintegrated pulps were screened through a laboratory plate
screener to measure the screened pulp and screened rejects yield. The screened pulps were packed in ziplock bags for the subsequent
treatment.

2.4. Composition and properties of screened pulp

The viscosity and Kappa number of the screened pulps were determined in accordance with GB/T 1548—1989 and GB/T
1546—1989, respectively. The pentosan, klason lignin, acid-soluble lignin, and benzene-ethanol extractive content of the screened
pulps were determined in accordance with GB/T 2677.8—1994, GB/T 747—1989, GB/T 10,337—1989, and GB/T 10,741—1989,
respectively.

2.5. Beating pulp

Firstly, 30 g of oven-dried screened pulp was taken and the interwoven fibers or bundles were dissociated into individual fibers
by mechanical spalling through a standard fiber dissociator. Then, the dissociated pulp was refined through the stainless PFI refiner
(Mark V1, Norway) to obtain refined pulp by adjusting revolutions of beating to 5 000. After Beating, take part of the refined pulp
to determine the degree of beating, the remaining refined pulp were packed in ziplock bags for subsequent treatment.

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60
(a) 15 (b)
55 Unscreened pulp Pentosan
Screened pulp Lignin
12
50 Benzene-alcohol extractive

Content (%)
Yield (%)

45 9

40 6

35
3

30
0
25 0 200 400 600 800 1000
0 200 400 600 800 1000
P-factor P-factor

1100 105 110

(c) (d)
28 Kappa number 100
1000 102

Hemicellulose loss rate (%)

Pulp viscosity

Lignin removal rate (%)

90

Pulp viscosity (mPa·s)

24
900
Kappa number

80
99

20 800 70

96
60
700
16 Hemicellulose - relative to the original wood chips
50
Hemicellulose - relative to auto-hydrolyzed wood chips
93
600 Lignin - relative to the original wood chips
40
12 Lignin - relative to auto-hydrolyzed wood chips

500 90 30
0 200 400 600 800 1000 0 200 400 600 800 1000

P-factor P-factor

Fig. 2. Pulping performance of auto-hydrolyzed acacia chips. (a) Yield of unscreened and screened pulp; (b) Composition of screened pulp; (c)
Kappa number and viscosity; (d) Removal rate of pentosan and lignin.

2.6. Fiber length and fiber morphology

Fiber length analysis of each screened pulps and refined pulps sample was analyzed by Kajaani FS 300. Weighing the amount of
screened pulps or refined pulps and placing them in a 100 mL beaker, the pulps were disintegrated at 25 °C water for 48 h under
stirring and then diluted to achieve samples with a quite low consistency of 0.01%. The 30–50 mL of fiber suspension was placed in
a testing cup for testing and the number of fibers detected each second is above 20 with a total number of around 10 000.
Fiber morphology of each screened pulps and refined pulps sample was analyzed by optical microscope (DM2700M, Leica). The
0.1 g of the pulp was diluted to a concentration of about 0.1% with deionized water. The 3–4 drops of the suspension were pipetted
onto a glass slide. After covering with a coverslip, excess liquid was removed with filter paper. Fiber morphology was then observed
by adjusting the microscope magnification.

2.7. Pulp handsheets preparation and testing

A manual hand-sheet-making machine (ASM-32N2F, China) was used to prepare the screened pulp handsheets and refined pulp
handsheets. The basis weight of handsheets was fixed at 60 g/m2 . The tear index and tensile index of handsheets were measured
based on GB/T 455.1—1989 and GB/T 453—1989, respectively.

2.8. Analysis of black liquor

The solid content, organic matter content and residual alkali of the black liquor were determined according to previous publications
(Shi et al., 2019a; 2019b). The lignin content of the black liquor was determined in accordance with GB/T 747—1989.

3. Results and discussion

3.1. Kraft pulping performance of auto-hydrolyzed wood chips

The pulping performance of auto-hydrolyzed acacia chips was analyzed after kraft pulping. As shown in Fig. 2a, the unscreened
and screened pulp yields of the auto-hydrolyzed kraft pulp dropped with the increase of the auto-hydrolysis strength. When the

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P-factor was increased from 0 to 1 000, the yields of unscreened pulp and screened pulp dropped from 54.79% and 51.64% of the
control group to 37.06% and 34.17%, respectively. During the auto-hydrolysis process, the acetyl groups on the hardwood xylan side
chains could react with hydronium ions to form acetic acid (Villaverde et al., 2009; Liu et al., 2015b). The long-chain hemicellulose
was further broken to form oligosaccharides and monosaccharides. As the acid dissolves and forms, the pH of the auto-hydrolyzed
liquid decreases, causing the hemicellulose glycan to further dissolve. Meanwhile, a part of the degradation of lignin and cellulose
was also present during the auto-hydrolysis process (Hou et al., 2014). The yield of auto-hydrolyzed wood chips dropped as auto-
hydrolysis strength increased. As a result, the pulp yield decreased. It was worth noting that when the P-factor < 200, the unscreened
and screened pulp yield decreased rapidly. This phenomenon was explained by our previous publication (Shi et al., 2019a). In the
early phase (P-factor < 200) of auto-hydrolysis, the yield of the process dropped sharply to about 86%, and a fast loss in the weight
of holocellulose was noticed.
The contents of pentosan, lignin, and benzene-ethanol extractive in the screened pulp are shown in Fig. 2b. When P-factor <
400, the pentosan content in pulp dropped rapidly from 14.44% to 2.99%. Then, it slowly dropped to 0.86% at the P-factor of 1
000. With the auto-hydrolysis strength increased, the hemicellulose content in wood chips decreased. Meanwhile, the hemicellulose
also underwent alkaline hydrolysis during the kraft pulping process. In an earlier study (Shi et al., 2019a), we found that the auto-
hydrolyzed wood chips had a rapid decline in pentosan content (P-factor < 400), which was in accordance with the pentosan content
trend shown in Fig. 2b. In addition, as shown in Fig. 2b, when P-factor < 600, the content of lignin in pulp decreased, and the content
of benzene-ethanol extractive increased. When P-factor > 600, the lignin content in pulp increased, and the content of benzene-ethanol
extractive decreased.
We tested the viscosity and Kappa number of the screened pulp, and the results were shown in Fig. 2c. It can be seen from Fig. 2c
that the viscosity increased in the early phase (P-factor < 120) of auto-hydrolysis, and then it decreased as the P-factor increased. This is
because, in the early phase of auto-hydrolysis, part of the hemicellulose with short-chain was dissolved in hydrolysate, the percentage
of cellulose with long-chain in pulp improved, resulting in a rise in viscosity. As auto-hydrolysis severity is further enhanced, cellulose
can be degraded, the proportion of short chains increases, and the viscosity decreases (Ko et al., 2015). The Kappa number of the
screened pulp was also shown in Fig. 2c, and the results were different from other literature. The results from previous study (Lu
et al., 2012) showed that structural alteration led to an improved reactivity of wood chips after hydrothermal extraction, and Kappa
number dropped with enhancing extraction temperature and time. Mendes et al. (2009) found when eucalyptus chips were undergone
hydrothermal pretreatment with a P-factor of 375, and the Kappa number was reduced by 40%.
However, in this study, we found that the Kappa number of auto-hydrolyzed woodchip pulp increased when P-factor < 200,
which may be because the proportion of lignin in the wood chips improved after auto-hydrolysis, increasing the difficulty of lignin
removal. At 200 < P-factor < 800, the Kappa number reduced from 25.62 to 19.67. This was attributed to the decomposition of auto-
hydrolyzed wood chips and the increase of pore volume, which improved the alkali impregnation effect and deepened the severity
of delignification. At this phase, the amount of lignin in the screened pulp was dropped. The Kappa number increased from 19.67 to
23.57 when P-factor increased from 800 to 1 000. This might be due to the deposition of lignin on wood chip surface during the late
phase of auto-hydrolysis (Villaverde et al., 2009), which affected the delignification process and increased the lignin content in the
screened pulp.
As illustrated from Fig. 2d, the severity of delignification in the pulping process is generally deepened by the auto-hydrolysis kraft
pulping process, and the removal rate of the pentosan was 94.3%–98.6% at the P-factor of 400–1 000, which had the potential to
produce advanced dissolving pulp.

3.2. Fiber morphology of pulps and physical strength of paper matrix

The screened pulp was beaten at 5 000 r/min, and the fiber morphology and the physical strength of the paper matrix before and
after the beating were tested. First, we measured the beating degree of the refined pulp, and the outcome was depicted in Fig. 3a.
When P-factor was changed from 0 to 400, the beating degree was reduced from 27.2 to 23.4. The interfiber contact during beating
was reduced as the swelling of hemicellulose-extracted pulps decreased, deteriorating external fibrillation and hence beating response
(Hamaguchi et al., 2013). For hydrolyzed pulps, a previous study (Yoon and Heiningen, 2008) reported considerably improved PFI
revolutions to achieve a given freeness. When the P-factor was increased from 400 to 1 000, the beating degree increased from 23.4
to 31.1.
Fig. 3b showed the content of fine fiber and fiber curl in the screened pulp and refined pulp. We can find that the percentage of
fines and fiber crimps in the control group and the auto-hydrolyzed screened pulp did not change much. However, it is interesting
to notice that the fine fiber content in the refined pulp rapidly increased from 5.80% at the P-factor of 400 to 16.82% at the P-factor
of 1 000. This may be one of the reasons for the increase in the beating degree after the P-factor > 400. The percentage of fiber curl
after beating had also increased, which might be considered a weakness of the auto-hydrolysis kraft pulping.
As illustrated in Fig. 3c, the mean length of the screened pulps was in the range of 0.57–0.63 mm, and the length-weighted mean
length was in the range of 0.67–0.72 mm. From this point alone, it could be considered that the auto-hydrolysis intensity had no
obvious effect on the kraft pulp fiber length (Duarte et al., 2011). However, we could see a significant change in fiber length by
analysis of the refined pulp. The mean length and length-weighted mean length dropped from 0.63 mm and 0.72 mm in the control
group to 0.44 mm and 0.53 mm in the P-factor of 1 000, respectively. Under the same beating speed, the fiber length changes greatly
before and after beating, and the reason may need further exploration.
Fig. 3d showed the relationship between the tear strength and tensile strength of handsheets before and after beating. The tensile
index of the handsheets made with screened pulp and refined pulp was linearly decreased from 57.63 and 83.12 N·m/g of the control

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25
34 (a) Fine(l)-the screened pulp (b)
Fiber curl-the screened pulp
Beating degree Fine(l)-the refined pulp
32 20
Fiber curl-the refined pulp
Beating degree (°SR)

30

Content (%)
15
28

26 10

24
5
22

20 0
0 200 400 600 800 1000 0 200 400 600 800 1000

P-factor P-factor

0.80 25 90
L(N)-the screened pulp (c) Tear index of the refined pulp
0.75
L(l)-the screened pulp (d)
Tear index of the screened pulp 80
L(N)-the refined pulp
Tensile index of the refined pulp
L(l)-the refined pulp 20
0.70 Tensile index of the screened pulp 70
Tear index (mN·m2/g)

Tensile index (N·m/g)

0.65 60
15
L (mm)

0.60 50

0.55 10
40

0.50 30
5
0.45 20

0.40 0 10
0 200 400 600 800 1000 0 200 400 600 800 1000
P-factor P-factor

Fig. 3. Fiber morphology of pulps and physical strength of handsheets. (a) Beating degree under different P-factors; (b) Content of fine fiber and
fiber curl; (c) Mean length and length-weighted mean length of fiber; (d) Tear strength and tensile strength of handsheets.

sample to 30.21 and 43.21 N·m/g of the pre-extracted sample in the P-factor of 200, respectively (about 48% decline). The decline of
tensile strength at this phase might be attributed to the lignin content of the pulp (a larger Kappa number in Fig. 2c), which impaired
the expansion and flexibility of the fibers, affecting the tensile strength significantly. Furthermore, according to the previous study,
the decline of tensile strength might be attributed to hemicellulose extraction, therefore reducing the bond between the fibers of pulp
handsheets. At the same time, we can find that when the P-factor < 400, the tensile strength of the handsheets after beating increased
by 18.98%–30.67%. Taking measures, such as beating, could compensate for the decline in the physical strength characteristics of
paper produced by the lack of hemicellulose. It was discovered by observing the changing trend of the tear index of screened pulp that
auto-hydrolysis had an unremarkable effect on the tear index of the paper matrix, and the tear index increased after beating. Tearing
resistance is considered to affect by the strength and number of the fiber-to-fiber bonds, the fiber length, and the overall amount of
fibers involved in the sheet breaking (Yoon and Heiningen, 2008). Other than a very high degree of bonding, in which improved fiber
length could diminish the tear strength, it was commonly believed that the tear strength boosted with an enhancement in the fiber
length (Shi et al., 2019a). In this study, the fiber length decreased significantly after beating, but the tear index increased, which may
have some highly bonded fibers. Although fiber length significantly affects paper strength, other factors must be considered in some
cases when assessing paper strength.
The microscope was used to observe the screened pulp and refined pulp, and the results were shown in Fig. 4a. The surface of
unhydrolyzed wood screened pulp fiber was smooth, and the fiber surface was externally fibrillated after beating. When the pulps at
the P-factor of 200, 600 and 1 000 were observed, we found that the auto-hydrolyzed pulp fiber partially broke, and the fiber became
soft after beating. However, unlike unhydrolyzed pulp, some of the particles and spherical substances were present on the surface
of the auto-hydrolyzed pulp fibers. Through further observation in Fig. 4b, it is noted that these substances might be lignin-like
substances produced during the auto-hydrolysis process, which remained on the fiber surface after the pulping. When the P-factor
< 600, the lignin-like substance was dissolved in the benzene-ethanol solution, and the content of the benzene-ethanol extractive in
the screened pulp was increased. When the P-factor > 600, the structure of lignin-like changed, no longer soluble in benzene-ethanol
solution, the content of benzene-ethanol extractive in the screened pulp decreased, and the lignin content increased. The lignin-like
substances on the surface of the auto-hydrolysis-kraft pulping pulp might have a negative impact on subsequent paper properties.

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Fig. 4. Microscopic observation of pulps. (a) Screened pulp and refined pulp under different P-factors; (b) Particles and spherical substances existed
on surface of pulp fiber.

3.3. Component analysis of black liquor

Black liquor analysis is an essential analytical item for alkaline cooking. The residual alkali content in black liquor is a significant
indicator for the alkali recovery of the papermaking progress. The residual alkali content in black liquor reflects the amount of
alkali consumed for the delignification of the wood chips in the cooking process and reflects the cooking consequence. As shown in
Fig. 5a, when P-factor < 400, the amount of residual alkali rapidly decreased from 3.08 g/L of the control group to 2.32 g/L; when
400 < P-factor < 600, the amount of residual alkali increased from 2.32 to 2.55 g/L; while P factor > 600, the amount of residual
alkali tended to be stable in the range of 2.55–2.57 g/L. The rapid decline in the amount of residual alkali had the following reasons:
the auto-hydrolyzed wood chips elevated the porosity of the fiber cell wall, promoting the delignification process, and increasing the
alkali consumed; a part of the hydrolysate was retained in the auto-hydrolyzed wood chips, which could also use up some alkali in the
cooking liquor (Boucher et al., 2014). When P-factor > 400, more lignin substances were deposited on the wood chip surface, which
affected the infiltration of cooking liquor and increased the amount of residual alkali. When P-factor > 600, the amount of residual
alkali became stable. This might be due to the close mass of the remaining wood chips at the later stage of hydrolysis. In addition, in
this experiment, the same amount of cooking liquor was used for kraft pulping. The alkali consumption of the delignification process
is very close, leading to the amount of residual alkali in black liquor tending to be stable. In addition, the pH trend of black liquor is
substantially consistent with the tendency of the residual alkali amount.
The components of black liquor include organic substances (lignin and carbohydrate degradation products) and inorganic sub-
stances (alkali, sulfides, etc.). The solid content, lignin content, organic matter content, and inorganic matter content in black liquor

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13.0 180 2.0

3.4 (a) (b)
Residual alkalinity 12.8 160
3.2 Black liquor pH 1.8
Relative viscosity
Residual alkalinity (g·L-1)

12.6 140 Organic matter

Relative viscosity
Content (g·L-1)
3.0 Inorganic matter
12.4 Solid content 1.6
120
2.8 Lignin content

pH
12.2
100
2.6 1.4
12.0
80
2.4
1.2
11.8
60
2.2
11.6
40 1.0
2.0 0 200 400 600 800 1000
0 200 400 600 800 1000
P-factor
P-factor

Fig. 5. Component of black liquor. (a) Residual alkali content and pH value; (b) Solid content, organic matter content, inorganic matter content
and lignin content.

were tested in this experiment, and the results are shown in Fig. 5b. Firstly, we found that the solid content and organic matter con-
tent in the pre-hydrolyzed black liquor improved from 145.03 and 81.6 g/L to 162.49–165.48 g/L and 95.85–98.12 g/L, respectively,
when compared with the control group. The solid content increased by 11.93%–14.11%, the organic matter content increased by
17.45%–20.25%, and the inorganic content in the black liquor did not change much. By auto-hydrolysis, the wood chips removed
more organic matter in the subsequent kraft pulping process. Secondly, it can be found that the lignin content of black liquor increased
slowly in the early phase (P-factor < 400). While P-factor > 400, the lignin content in black liquor was lowered due to a decline
in the wood chip yield after pre-hydrolysis rather than the weakening of the delignification process (Li et al., 2007). In general,
organic matter in black liquor refers to lignin and carbohydrate degradation products. By observing the lignin content and organic
matter content of black liquor, we could intuitively find that the value of organic matter content (excluding lignin of black liquor)
increased obviously after auto-hydrolysis treatment. As the auto-hydrolysis intensity increased, the value of the organic matter con-
tent (excluding lignin) further increased. It indicated that the auto-hydrolysis of the wood chips promoted the dissolution of cellulose
and hemicellulose in the following kraft pulping course, leading to a decline in pulp yield (Fig. 2d). In a previous study (Shi et al.,
2019a), when P-factor > 400, the hemicellulose content in wood chips did not change much, but it could be illustrated from Fig.
5b that the content of carbohydrate degradation products (organic content minus lignin content) continued to increase, which was
due to the dissolution and degradation of cellulose. Auto-hydrolysis-kraft pulping needs to consider the problems associated with
more carbohydrate degradation and dissolution. The results of Fig. 5b also showed the relative viscosity of the black liquor. As the
severity of auto-hydrolysis is deepened, the viscosity of the black liquor gradually decreased. There are many factors affecting the
viscosity of black liquor, such as pulping materials and methods, black liquor concentration, etc. In this experiment, the trend in the
viscosity of black liquor was opposite to that of its solid content, which was unexpected. The reason might be that as the severity
of auto-hydrolysis was deepened, the content of hemicellulose in wood chips was significantly reduced and part of the cellulose was
degraded, the hemicellulose content in the subsequent pulping black liquor decreased and the cellulose molecular weight became
smaller (Hamaguchi et al., 2013; Jia et al., 2022).

4. Conclusions

This work systematically evaluated the performance of the hydrolysis-based kraft pulping process and associated pulp and black
liquor characteristics. Acacia wood chips were first auto-hydrolyzed under various severities and then kraft pulping. As the intensity
of auto-hydrolysis increased to P-factor of 1 000, the yield of screened pulp and unscreened pulp dropped from 51.64% and 54.79%
for the control group to 34.17% and 37.06%, respectively. Meanwhile, the removal rate of the pentosan was 98.6% which had made
pulp with high purity suitable for dissolving pulp production. In addition, the viscosity of the screened pulp increased in the early
phase of auto-hydrolysis and then dropped as the P-factor increased. Auto-hydrolyzed pulps deteriorated external fibrillation and led
to a beating response. The autohydrolysis intensity had no significant effect on the fiber length, fines and fiber curls of screened pulp.
After beating, however, the fiber length was significantly reduced, and the fine content was markedly increased. The tensile index
of the screened and refined pulp handsheets was linearly reduced from 57.63 and 83.12 N·m/g of the control sample to 30.21 and
43.21 N•m/g of the pre-extracted sample with a P-factor of 200, and auto-hydrolysis had little effect on the tear index of handsheets.
After pre-hydrolysis, some particles and spherical substances existed on the surface of pulp fiber, and the organic matter content and
solid content in black liquor were improved. Despite the fact that the hydrolysis-based kraft pulping process can produce chemical
pulp with a high cellulose content, the utilization of hemicellulose in the hydrolyzate remains an urgent problem to be solved, and
solving this problem will improve the development prospects for chemical pulp production.

Conflict of Interest

There are no conflicts to declare.

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W. Jia, M. Zhou, C. Yang et al. Journal of Bioresources and Bioproducts 7 (2022) 180–189

Acknowledgments

This study was financially supported by Natural Science Foundation of China (No. 31971608), Natural Science Foundation of
Liaoning Province (No. 2019-ZD-0125), Liaoning Baiqianwan Talents Program (No. 2019) and Innovative Talents in Liaoning Uni-
versities and Colleges (No. 2020).

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