Applied Biochemistry and Biotechnology (2022) 194:4946–4958

https://doi.org/10.1007/s12010-022-03985-7

ORIGINAL ARTICLE

Biorefinery Cascade Processing for Converting Corncob

to Xylooligosaccharides and Glucose by Maleic Acid
Pretreatment

Zhina Lian1 · Qibo Zhang1 · Yong Xu1 · Xin Zhou1 · Kankan Jiang2

Accepted: 27 May 2022 / Published online: 8 June 2022

© The Author(s), under exclusive licence to Springer Science+Business Media, LLC, part of Springer Nature 2022

Abstract
Corncob as an abundant and low-cost waste resource has received increasing atten-
tion to produce value-added chemicals, it is rich in xylan and regarded as the most
preferable feedstock for preparing high value added xylooligosaccharides. The use of
xylooligosaccharides as core products can cut costs and improve the economic effi-
ciency in biorefinery. In this study, maleic acid, as a non-toxic and edible acidic cat-
alyst, was employed to pretreat corncob and produce xylooligosaccharides. Firstly,
the response surface methodology experimental procedure was employed to maxi-
mize the yield of the xylooligosaccharides; a yield of 52.9% (w/v) was achieved with
0.5% maleic acid (w/v) at 155 °C for 26 min. In addition, maleic acid pretreatment
was also beneficial to enhance the enzymatic hydrolysis efficiency, resulting in an
enzymatic glucose yield of 85.4% (w/v) with a total of 10% solids loading. Finally,
a total of 160 g of xylooligosaccharides and 275 g glucose could be produced from
1000 g corncob starting from the maleic acid pretreatment. Overall, a cascade pro-
cessing for converting corncob to xylooligosaccharides and glucose by sequential
maleic acid pretreatment and enzymatic hydrolysis was successfully designed for the
corncob wastes utilization.

Keywords Corncob · Xylooligosaccharides · Maleic acid · Enzymatic hydrolysis · Glucose

Zhina Lian and Qibo Zhang contributed equally to this work.

* Xin Zhou
[email protected]
1
Jiangsu Co‑Innovation Center of Efficient Processing and Utilization of Forest Resources,
College of Chemical Engineering, Nanjing Forestry University, 210037 Nanjing,
People’s Republic of China
2
School of Basic Medical Sciences and Forensic Medicine, Hangzhou Medical College,
310053 Hangzhou, People’s Republic of China

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Introduction

Biorefinery technologies provide routes to utilize lignocellulosic biomass, especially in the

agricultural and forestry waste processing industries, for producing energy, bio-chemicals,
and bio-fuels [1–3]. Corncob, as the byproduct of corn processing, is a suitable candidate
for biorefinery because it is inexpensive and abundance [4]. In 2020, the world corn pro-
duction was 885.3 million tons and China holds the second position with 260.7 million
tons [5]. That means about 41.5–46.1 million tons of corncob was generated in China from
corn processing industry. However, due to lack of policy support and poor management, a
large amount of corncob was burned or discarded, resulting in serious environmental pol-
lution and waste of resources. Therefore, it is urgent to develop an efficient approach for
the efficient utilization of this renewable feedstock. The mainly components of corncob are
cellulose (39–45%), hemicellulose (25–35%), and lignin (17–21%), and its ash and extrac-
tives content are very low [6, 7]. The efficient utilization and conversion of polysaccharide
components from cellulose and hemicellulose plays a crucial role to develop an economi-
cally feasible biorefinery process of lignocellulosic biomass.
Cellulose can be transformed into glucose by pretreatment and enzymatic hydrolysis,
and then glucose can be further converted to various fuels and organic acids via fermenta-
tion [8–10]. Unlike cellulose, hemicellulose is heteropolymer, including xylan, xyloglucan,
arabinoxylan, glucomannan, and glucuronoxylan. The hemicellulose of corncob is mainly
composed of xylan that can be transformed to xylose, furfural, furfuralcohol, xylitol, and
xylooligosaccharides (XOS) [11–13]. Among these products, XOS are acting as emerg-
ing functional oligosaccharides, which show favorable effects on human intestinal flora
by selectively promoting the growth of probiotic bacteria [14, 15]. The worldwide market
size for XOS is increasing yearly, and it is predicted to increase to $ 130 million by 2025,
which makes XOS become one of the most competitive products all over the world [16,
17]. Overall, the corncob biorefinery focused on XOS production can effectively boost the
agricultural waste processing industry economy [18].
The first and crucial step of lignocellulosic biorefinery is pretreatment, including enzy-
matic, alkaline, and acidic treatment methods [9, 19, 20]. Enzymatic pretreatment is not
associated with a pollution problem apart from its high cost, while alkaline is environmen-
tally problematic despite its low cost. Thus, the prospect of industrialization is still some
way off for both methods. In contrast, acid pretreatment with dual functions for producing
XOS and boosting enzymatic hydrolysis is preferable in adding values to lignocellulose
materials [20–22]. Acid pretreatment could be either mineral acid or organic acid, which
both of them have been reported to be capable of hydrolyzing xylan to produce XOS [23].
However, the use of strong mineral acids always leads to an excessive xylan degradation
to undesired by-products such as xylose and furfural, leading to a decrease in the yield of
XOS. Comparatively, organic acids tend to be more favorable for XOS generation because
of their considerable benefits, such as high yields of oligomers and lower amounts of deg-
radation by-products [24].
Regardless of the type of acids used, their separation and recovery are inevitable
steps to the production of XOS. However, using edible organic acids like acetic acid and
gluconic acid, which could be co-prepared with XOS as feed additives, could reduce the
production cost and water treatment cost [25, 26]. Although edible gluconic acid and
acetic acid have been reported to achieve high XOS yields of over 50%, the usage of
acid concentration over 10% resulted in a low XOS product purity when acid and XOS
were simultaneously co-prepared [27, 28]. Maleic acid (MA) is also a type of edible

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organic acid that has been mainly used in pharmaceutical, and the market price of food
food-grade MA with a purity of 95% is about $15/kg [29]. In addition, MA is a dicar-
boxylic and tiny molecule acid, which allow a low usage to achieve the same effect
compared with mono-carboxylic acids, such as acetic acid and gluconic acid. Therefore,
MA was used as an acid catalyst for the corncob pretreatment and XOS preparation in
this study. To get the highest yield of XOS, the optimum values of the reaction tem-
perature, MA concentration, and hydrolysis time were evaluated using response surface
methodology (RSM) experimental design [30]. The interactive effects of the variables
were also studied. Subsequently, the enzymatic hydrolysis of MA pretreated corncob
solids was evaluated. We have designed a new and cascade biorefinery process for the
co-production of XOS and glucose using MA as an acid catalyst.

Materials and Methods

Chemicals and Materials

Corncob was collected from fully mature maize, which provided by the local farmers
in the city of Linyi, China. Harvested in October 2020, it was ground to 60–80 mesh
and naturally air-dried to a constant moisture content of less than 10%. The air-dried
corncob powder was used as feedstock to conduct the subsequent experiments. The
chemical composition of corncob was determined by the National Renewable Energy
Laboratory’s standard method, and it mainly contained 33.1% glucan, 31.8% xylan,
19.0% lignin, and 4.2% ash [31]. MA, cellulase (310U/g, Cellic CTec2, Novozymes),
and the standards (glucose, xylose, and furfural) were purchased from Sigma-Aldrich
(Shanghai, China). The standards of xylobiose (X2), xylotriose (X3), xylotetraose (X4),
xylopentaose (X5), and xylohexaose (X6) were provided by Tokyo Chemical Industry
(Japan) which was supplied by Novozymes A/S (Bagsvaerd, Denmark).

Maleic Acid Pretreatment

The reaction temperature (x1), hydrolysis time (x2), and MA concentration (x3), as the
key factors for corncob hydrolysis, were investigated and optimized by the response sur-
face method (RSM). The software Design-Expert (Version 11.0) was used for the exper-
imental design and analysis. As shown in Table 1, a total of 13 experimental runs were
performed at the reaction temperature ranging from 130 to 170 °C with 0.25 to 0.75%
(w/v) MA concentration and hydrolysis time of 15 to 45 min.
The acidic hydrolysis of corncob was conducted in a 50-mL screw-top pressure-
resistant steel reactor. Three grams of corncob powder and 30 mL of MA solution
were mixed and stirred uniformly, and then, the reactor tube was sealed with caps and
immersed in the oil bath while it reached the preset temperatures, and held varying
durations accordingly. Once the reaction was finished, the reactor tube was immedi-
ately taken out and immersed into the cold water bath. The solution was centrifuged,
the supernatant was collected for XOS determination, and the solid residues were used
for the main components of glucan, xylan, and lignin analysis and enzymatic hydrolysis
process.

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Table 1  The experimental design and response value

Run Factor Furfural (%) Xylose (%) Response

x1 x2 x3 Y
Reaction tem- Hydrolysis MA concen- XOS yield (%)
perature (°C) time (min) tration (%)

1 130 15 0.5 0 0.75 1.52

2 130 30 0.25 0 0.44 0.83
3 130 30 0.75 0.2 4.5 18.67
4 130 45 0.5 0.1 3.34 14.12
5 150 15 0.25 0.3 7.41 6.11
6 150 15 0.75 0.88 16.73 36.24
7 150 30 0.5 1.2 24.3 52.39
8 150 45 0.25 0.42 11.33 18.14
9 150 45 0.75 4.75 42.93 12.61
10 170 15 0.5 2.44 28.5 42.52
11 170 30 0.25 2.6 30.27 28.05
12 170 30 0.75 9.79 57.93 11.58
13 170 45 0.5 12.06 62.69 8.71

Enzymatic Hydrolysis

The corncob residue pretreated with MA was first washed to neutrality by deionized water
and then air-dried to a constant weight. The enzymatic hydrolysis assay was performed using
a screw-capped 150-mL flask shaken at 50 °C and 150 rpm. The solids loading was 10% and
cellulase loading was 20 FPIU/g glucan. Sodium citrate buffer was used for maintaining the
pH at 4.8 (0.1 mol/L). After 72 h of the enzymatic hydrolysis process, the slurry was then cen-
trifuged at 6,000×g for 5 min, and the supernatant was collected.

Response Surface Method Analysis

The yield of XOS was used as the evaluation index of the response surface method (RSM). A
quadratic polynomial stepwise regression fitting was performed on the response values of the
indexes through a quadratic polynomial model to obtain the functional relationship between
the respective variables and the response values of XOS yield.
∑ ∑ ∑
Y = 𝛽0 + 𝛽 i xi + 𝛽ii xi 2 + 𝛽ij xi xj

In the above model, 𝛽0 was a constant term, while 𝛽i, 𝛽ii, and 𝛽ij were the coefficients of the
first and quadratic terms, respectively. Y represented the response value of xylooligosaccha-
rides yield. Analysis of variance was employed to test the significance of the RSM experiment.

Analytical Methods

Carbohydrates (xylose, arabinose, glucose, and cellobiose), MA, and furfural were deter-
mined with high performance liquid chromatograph (HPLC, Agilent 1260, USA) that

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was equipped with an Aminex Bio-Rad HPX-87 H column (Bio-Rad Laboratories, USA).
Xylobiose (X2), xylotriose (X3), xylotetraose (X4), xylopentaose (X5), and xylohexaose
(X6) were simultaneously detected with the high performance anion exchange chromato-
graph (HPAEC, Dionex ICS-5000, USA) coupled with a CarboPac™ PA200 column [32].
The yields of furfural, xylose, XOS, and enzymatic hydrolysis were calculated using the
following equations:
Furfural content in hydrolyates (g)
Furfural yield(%) = Initial furfural content in corncob (g)
× 100%

Xylose content in hydrolyates (g)

Xylose yield(%) = Initial xylan content in corncob (g)
× 100%

XOS content in hydrolyates (g)

XOS (X2-X6) yield(%) = Initial xylan content in corncob (g)
× 100%

Glucose content in enzymatic hydrolysate (g)

Enzymatic hydrolysis yield(%) = Glucan in raw material (g)
× 100%

Results and Discussion

Hydrolysis of Corncob by Maleic Acid

During the acidic hydrolysis process, hydronium ions (H+) can be released from MA
and help to break the glycosidic linkages in the interiors and/or exteriors of xylan, which
result in the generation of XOS. A higher temperature and acid concentration can effec-
tively improve the activity of molecules and collisions, increasing the reaction rate [30].
In addition, the reaction time should be controlled for obtaining desired products. There-
fore, reaction temperature, acid concentration, and reaction time were investigated in this
study, and the effects of these three factors on the degradation of corncob to produce XOS
were designed by RSM, using the minimum set of runs. The MA concentrations of 0.25
to 0.75% (w/v), hydrolysis time of 15 to 45 min, and reaction temperatures of 130 to 170
°C were selected for evaluating hydrolysis processes of xylan and XOS generation. The
experimental designs with 13 runs and the XOS yield are presented in Table 1.
Figure 1 shows the yields of xylose, X2, X3, X4, X5, X6, and furfural from the RSM
designed conditions. As depicted in Fig. 1a, when the reaction was conducted at 130 °C,
the XOS yield (the sum of the yields of X2, X3, X4, X5, and X6) increased from 0.8%
(0.25% MA, 30 min) to 18.7% (0.75% MA, 30 min) and 1.5% (0.5% MA, 15 min) to
14.1% (0.5% MA, 45 min). Although increased MA concentration and hydrolysis time
could slightly increase the reaction rates at the low reaction temperature, the yields of
xylose and XOS are still very low. Apparently, increase in the reaction temperature could
significantly boost the reaction rates, a XOS yield of 52.4% could be achieved at a tem-
perature of 150 °C with 0.5% MA and 30 min duration, which is shown in Fig. 2b. How-
ever, in the case of high reaction temperature, the XOS yield would drop sharply with the
increasing MA concentration and hydrolysis time. As shown in Fig. 1c, the XOS yield
decreased from 28.1% (0.25% MA, 30 min) to 11.6% (0.75% MA, 30 min) and 42.5%
(0.5% MA, 15 min) to 8.7% (0.5% MA, 45 min), while the furfural and xylose yields
were drastically increased. On the other hand, lower amounts of X5 and X6 but relatively
higher amounts of X2 and X3 were obtained.

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Fig. 1  Yields of furfural, xylose,

X2, X3, X4, X5, and X6 in
hydrolysate produced from corn-
cob with different MA concentra-
tions and times at (a) 130 °C, (b)
150 °C, and (c) 170 °C

The results indicated that reaction temperature, hydrolysis time, and MA concen-
tration significantly influenced the XOS yields. For the key goal of higher XOS, reac-
tions at low temperatures require prolonged hydrolysis time and more acid dosage,
which is economically unfavorable, but the excessive temperatures would result in XOS

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Fig. 2  Response surface plots showing interaction effects of reaction temperature and hydrolysis time (a);
reaction temperature and MA concentration (b); hydrolysis time and MA concentration (c) on XOS produc-
tion

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degradation and a large amount of xylose accumulation. Taken above, it suggests that
the higher levels of reaction temperature with short reaction duration is favored in the
formation of XOS and lower by-roducts.

Fitting Models

Design Expert software was employed to fit all polynomial models based on the experi-
mental results, which were summarized in Table 1. The data obtained were fitted to a
second order polynomial equation. The response values (yields of XOS) were calculated
according to the following equation:
Y = 17.04x1 + 11.01x2 + 630.38x3 − 0.0387x1 x2 − 1.716x1 x3
− 2.386x2 x3 − 0.0489x12 − 0.0715x22 − 288.44x32 − 1573.46

The coefficient of determination (­ R2 = 0.9644) and adjusted coefficient of determination

(Adj. ­R2 = 0.8574) indicated the feasibility of the fitted model for experimental results and
predicted values. Values of Adj. ­R2 and Adj. ­R2 greater than 0.80 show the goodness of fit
of the regression equation [33]. In addition, the Adeq Precision value of 10.634 (> 4) also
suggested that the obtained model by RSM analysis was reasonable. Overall, all data indi-
cated that the model had a good correlation.
The results of the analysis of variance (ANOVA) of the model were given in Table 2.
The F-value of 9.02 and the P-value of 0.0484 (< 0.05) suggested that the model was sig-
nificant. And it could be seen that the P-values of x1, x1 × 2, x12, x22, and x32 were all less
than 0.05, indicating all significantly affected the XOS yield. Smaller P-values represent
higher significance; therefore, the order of significance of each factor on XOS yields was
MA concentration, hydrolysis time, reaction temperature.
The 3D response surface and contour plots, graphical representations of a regression
equation, can reveal the interactive effects of two factors on XOS yields. Figure 2 represents
the interaction effect between two independent variables. The results indicated that slight
changes in the reaction temperature, hydrolysis time, and MA concentration significantly

Table 2  Analysis of variance in RSM model

Source Sum of squares DF Mean square F-value P-value

Model 2966.21 9 329.58 9.02 0.0484 Significant

x1-Temperature 387.95 1 387.95 10.61 0.0472
x2-Time 133.74 1 133.74 3.66 0.1517
x3-Concentration 84.89 1 84.89 2.32 0.2249
x1 x2 538.70 1 538.70 14.74 0.0312
x1 x3 294.29 1 294.29 8.05 0.0658
x2 x3 320.23 1 320.23 8.76 0.0595
x1 2 874.50 1 874.50 23.93 0.0163
x2 2 592.11 1 592.11 16.20 0.0276
x3 2 742.84 1 742.84 20.32 0.0204
Residual 109.65 3 36.55
Cor Total 3075.86 12
R2 0.9644

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affected the XOS yield. Furthermore, a higher amount of each independent variable led to
accelerated degradation of the corncob. As depicted in Fig. 2a, a maximal contour (XOS
yield 50%) could be determined under certain conditions (reaction temperature range from
150 to approximately 160 °C and hydrolysis time range from 21 to approximately 33 min),
but further increase in the reaction temperature or hydrolysis time would not improve the
XOS yield. Additionally, similar phenomena were observed in Fig. 2b and c, indicating the
interactive effects of reaction temperature vs. MA concentration and hydrolysis time vs.
MA concentration on XOS yield, respectively.
In the case of lower temperature, higher MA concentration or hydrolysis time was
required to improve the XOS yield; however, a consistent increase in the MA concentra-
tion or hydrolysis time did not continuously improve the XOS yield. On the other hand,
excessive temperature and hydrolysis time led to XOS degradation and increased xylose
yield. These results indicated that these parameters should be controlled to achieve the
expected XOS yield. Overall, the values of x1, x2, and x3 were in the ranges of 150~160
°C, 21~33 min, and 0.45~0.55%, respectively, where the yields of XOS were achieved
at approximately 50%.
The 3D response surface plots with convex shapes can suggest the optimum condition
for the highest response. In the fitted model, the optimal condition for obtaining the high-
est XOS yield was 155 °C reaction temperature, 26 min hydrolysis time, and 0.5% MA
concentration. The experiment was conducted in triplicate based on the predicted optimal
condition. The mean value of the highest XOS yield was 52.9%, with a total amount of
16.8 g/L, which was in agreement with the predicted value (53.8%). Additionally, the X2,
X3, X4, X5, and X6 contents in hydrolysate from xylan hydrolysis at optimized conditions
were 5.34, 3.69, 3.26, 2.48, and 2.01 g/L, respectively. The experimental result of XOS
yield was consistent with the predicted result from the fitted model, suggesting the accu-
racy of the established regression equation.

Evaluation of Enzymatic Hydrolysis Efficiency for Pretreated Corncob

According to previous reports, acid pretreatment can effectively improve the efficiency of
the enzymatic hydrolysis by increasing cellulose accessibility to cellulases [9, 34]. In the
case of the optimum condition (0.5% MA at 155 °C for 26 min) that yielded the maxi-
mum XOS, the pretreated residue of corncob was found to contain 56.1% glucan, 13.7%
xylan, and 24.8% lignin. MA pre-hydrolysis process for XOS production also simultane-
ously changed the composition of the corncob that featured an ample quantity of etched
and rougher surface. Most of the cellulose and lignin were preserved in the solid residues
after MA pretreatment. Generally, solids loading dosage is a crucial factor for enzymatic
hydrolysis, and an increase in solids loading can decrease water/energy consumption and
the cost of downstream processing [35]. Thus, to study the influence of solids loading on
enzymatic hydrolysis, 5, 10, and 15% (w/v) of solids loadings were subjected to enzymatic
hydrolysis process.
The results of enzymatic hydrolysis with different solids loading indicated that solids
loading significantly influenced the efficiency of enzymatic hydrolysis (Fig. 3). Although
the final glucose content increased with increasing solids loading, a final content of
73.1 g/L glucose could only be achieved with 15% solids loading and the yield was only
79.1%. Relatively higher enzymatic hydrolysis yields of 87.5% and 85.4% were obtained
from that of 5% and 10% solids loadings, respectively. The decrease in enzymatic hydroly-
sis yield may be caused by the lack of free water in the high solids loading enzymatic

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Fig. 3  Performance of enzymatic

hydrolysis of solid residue from
MA-pretreated corncob using 5,
10, and 15% solids loadings

system, which also resulted in difficulties in mass transfer [36]. In summary, 10% solids
loading is suitable for enzymatic hydrolysis of MA pretreated corncob solids to obtain glu-
cose with a high yield. In addition, it was noted that a small quantity of xylose would be
simultaneously released into hydrolysate during the process of enzymatic hydrolysis, and
the content ratio of glucose and xylose was 4:1. Thus, as a result starting from 1 kg corn-
cob, approximately 160 g of XOS (mainly X2, X3, and X4) was obtained in pre-hydro-
lysate by MA pretreatment; and 63 g xylose and 275 g glucose were simultaneously har-
vested by subsequently enzymatic hydrolysis with 10% solids loading. These results clearly
indicated that pretreatment of corncob with MA for co-production of glucose and XOS was
a profitable option, which could maximize the economic value of corncob.

Conclusions

A response surface methodology of pretreating corncob using edible MA to co-produce

XOS and glucose as high value products was successfully implemented to determine opti-
mal values of MA concentration, temperature, and time. The maximum yield of XOS
(52.9%) was achieved with 0.5% MA at 155 °C for 26 min; meanwhile, the enzymatic
hydrolysis yield of the retained solids residue was 87.5%. MA pretreatment provides an
economical and environmentally friendly method for processing the available lignocellu-
losic biomass.

Acknowledgements The authors acknowledge the support of the Advanced Analysis and Testing Center of
Nanjing Forestry University.

Author Contribution Zhina Lian performed the experiments, analyzed the data. Qibo Zhang prepared the
draft manuscript. Kankan Jiang and Xin Zhou conceived, designed the study and modified the manuscript.
Yong Xu reviewed and edited the manuscript.

Funding The research was supported by the National Natural Science Foundation of China (32171730).

Data Availability Not applicable.

Code Availability Not applicable.

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Declarations
Ethics Approval Not applicable.

Consent to Participate The authors declare that they consent to participate.

Consent for Publication The authors declare that they consent for publication.

Conflict of Interest The authors declare no competing interests.

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