Next Article in Journal
Optimization on Linkage System for Vehicle Wipers by the Method of Differential Evolution
Next Article in Special Issue
Advances in Pulp and Paper Technologies
Previous Article in Journal
Parametric Study on Analyzing the Effect of Soil–Cement Strength on the Uplifting Behavior of HSCM Piles Installed in Marine Soft Clay
Previous Article in Special Issue
Properties of Green Tea Waste as Cosmetics Ingredients and Rheology Enhancers
 
 
Search for Articles:
Title / Keyword
Author / Affiliation / Email
Journal
Article Type
 
 
Advanced Search
 
Section
Special Issue
Volume
Issue
Number
Page
 
Journals
Applied Sciences
Volume 13
Issue 1
10.3390/app13010334
applsci-logo
Submit to this Journal Review for this Journal Propose a Special Issue
► Article Menu

Article Menu

share Share announcement Help format_quote Cite question_answer Discuss in SciProfiles thumb_up
...
Endorse textsms
...
Comment
first_page
settings
Order Article Reprints
Font Type:
Arial Georgia Verdana
Font Size:
Aa Aa Aa
Line Spacing:
Column Width:
Background:
Article

High Cellulose Purity by Acid Hydrolysis Pretreatment on Kenaf Outer Bast

by
Virginia Ghita Firsty
1,
Ji Yeon Jeong
1,2,
Yang Mo Gu
2,3,
Jin Hyung Lee
2,* and
Soo-Jeong Shin
1,*
1
Department of Wood & Paper Science, Chungbuk National University, Cheongju 28644, Republic of Korea
2
Korea Institute of Ceramic Engineering and Technology, Cheongju 28160, Republic of Korea
3
Division of Chemical Engineering & Bio Engineering, Hanyang University, Seoul 06763, Republic of Korea
*
Authors to whom correspondence should be addressed.
Appl. Sci. 2023, 13(1), 334; https://doi.org/10.3390/app13010334
Submission received: 1 November 2022 / Revised: 2 December 2022 / Accepted: 23 December 2022 / Published: 27 December 2022
(This article belongs to the Special Issue Advances in Pulp and Paper Technologies)
Browse Figures
Review Reports Versions Notes

Abstract

:
Acid hydrolysis treatment of kenaf outer bast fiber can produce pure cellulose content and hydrolyzed hemicellulose to monosaccharides. The effects of various reaction temperatures (110–130 °C), acid concentrations of sulfuric acid (0.25–1.00 N), and reaction times (60–120 min) were investigated as the optimum condition to gain pure cellulose content. A 1H NMR spectroscopy was used to analyze the carbohydrate content in the reaction of acid hydrolysis treatment. The results showed that optimum conditions for acid hydrolysis refer to two treatment prospects. First, a higher reaction temperature of 130 °C was necessary to increase the reaction for the hydrolyzes of hemicellulose—the high yield content produced by 0.25 N sulfuric acid with a short reaction time of 60 min. to improve the purity of cellulose, provided by the high sulfuric acid solution of 1.00 N for 120 min. Hemicellulose was hydrolyzed at almost 100% based on the two optimal conditions. The analysis revealed that a high temperature of acid hydrolysis was the primary treatment to hydrolyze hemicellulose to increase high pure cellulose from the kenaf outer bast fiber.

1. Introduction

Kenaf is an annual herbaceous plant from the family Malvaceae, widely cultivated worldwide [1] because of its excellent biomass production among herbaceous plants [2]. The advantages of kenaf are its fast growth rate, expansive growth, robust reconciliation to the environment, and less cost of cultivation [3]. Kenaf stems are divided into outer, inner, and core layers [3]. Bast outer fibers have long fibers and impart excellent strength properties to paper or composites [4,5]. It is attracting attention as a raw material candidate for sustainable production in the future biorefinery industry due to its high biomass production [1,2,3,4,5].
The biorefinery industry uses cellulose, hemicellulose, and lignin components and extracts components for each purpose [6,7,8]. For this, a stable supply of raw materials is essential [6,7,8]. In the chemical composition of kenaf bast fiber were cellulose, hemicellulose, lignin, extractive, and ash content of 55.0%, 31.8%, 14.7%, 5.5%, and 5.4% [4], respectively. The holocellulose sourced from kenaf fiber approached 86.8% [4]. The long fiber of outer bast fibers is in high demand for practical implementation and good commercialization of the higher cellulose content [4,5].
Cellulose is the most abundant natural macromolecular resource on Earth [9]. The substitution reaction of cellulose requires high-purity cellulose as a raw material for methyl cellulose, ethyl cellulose, carboxy methyl cellulose, hydroxypropyl cellulose, and hydroxy ethyl cellulose [10,11]. Cellulose can be partially acid, hydrolyzed to produce microcrystalline cellulose and is widely used as an excipient in the pharmaceutical industry due to its excellent bonding strength and formulation ability [12]. High-purity cellulose suitable for this application is required, and cotton cellulose is used [12]. Purified cellulose can be the raw material for cellulose nanocrystals or cellulose nanofiber for cellulose nanomaterial production [13,14,15,16]. Cellulose nanocrystals could be applied in food processing, bioplastics, ceramics, pharmaceutical, and cosmetic sectors as value-added products and reinforcing fillers in bio-composite production fields [13,14]. In addition, cellulose nanofiber can be a good candidate for replacement for petrochemical-based materials and can surpass fossil-based materials such as electronics, biomedical applications, etc. [15,16].
In order to produce high-purity cellulose, lignin and hemicellulose must be effectively removed [17,18]. Chemical pulping and bleaching are required to remove lignin and hemicellulose [3]. The hemicellulose removal process is primarily [19] divided into essential treatments in which hemicellulose is dissolved using an appropriate base concentration and acid treatment [19,20]. Hemicellulose is hydrolyzed faster than cellulose in acidic conditions [20]. Dissolving pulp-grade cellulose used as a raw material for fine chemicals requires a purity of 90.0% or higher [6].
The process of selectively removing hemicellulose using sulfuric acid or other acids has been studied for producing pulp for dissolution. Hydrolyzed hemicellulose is a pretreatment process prior to enzymatic saccharification [21,22,23]. Xylan has the fastest decomposition rate in acid hydrolysis [24]. Glucomannan decomposes faster than cellulose [25]. Due to the difference in decomposition rate, it is possible to retain hemicellulose while leaving most cellulose. Therefore, this study explored the possibility of the selective removal of hemicellulose in dilute acid hydrolysis conditions to produce high-purity cellulose, a raw material for fine chemicals from kenaf cobs, from which lignin was removed.

2. Materials and Methods

2.1. Materials

2.1.1. Raw Material

Kenaf outer bast fiber is provided by Jeollabuk-do Agricultural Research and Extension Services, the Republic of Korea. The biomass was ground in a mill machine Hankook Co., Seoul, Korea, and passed through a 20-mesh screen with a particle size of 338 ± 20 μm using a particle size analyzer (LA-960; Horiba, Kyoto, Japan).

2.1.2. Chemical

Sulfuric acid (H2SO4) (95.0%) and acetone (C3H6O) (99.7%) were purchased from Samchun Pure Chemical Co., Ltd., Korea. Sodium hypochlorite (NaClO) was purchased from Sungju Industrial, Korea. Distilled water was prepared with Water Purification System from Human Science Korea. Deuterium oxide (D2O) from Sigma-Aldrich, U.S., and α-L(+)-rhamnose monohydrate from Wako Pure Chemical Industries, Ltd. Japan, was used for NMR analysis.

2.2. Experimental Methods

2.2.1. Delignification

Before acid hydrolysis, kenaf outer bast fiber was treated by bleaching for delignification. Bleaching was conducted two times by soaking with NaClO solution (4%), ratio solid/liquid 1:1 (w/w), for 18 h. After bleaching, the samples were washed and dried in the oven at 50 °C.

2.2.2. Acid Hydrolysis

Sulfuric acid concentrations to remove hemicellulose of 0.25, 0.50, and 1.00 N and reaction times of 60, 90, and 120 min. The condition was conducted at temperatures 110, 120, or 130 °C using an Autoclave from SH Scientific Co., Ltd., Korea. Kenaf outer bast samples (2.0 g) were mixed with sulfuric acid solution (20 mL) in tube bottle. After treatment, the samples were filtered using a glass filter (P4 type) to separate the solid and liquid fractions. The solid fraction was washed several times with distilled water to remove the acid for detoxification and dried in the oven at 80 °C for 24 h. Figure 1 shows the step of acid hydrolysis treatment.

2.3. Analysis of Chemical Constituents

2.3.1. Determination of acetone and water extractives

Unbleached kenaf outer bast fiber extractives were carried out using acetone followed by hot water extraction. First extraction, about 2 g of each sample was macerated with 20 mL acetone and left at room temperature for 8 h. Then, the sample was filtered using filter paper to separate filtrate and residue. The filtrate was dried to evaporate acetone, and the extractive was weighed. The residue was also dried at room temperature for further hot water extraction. Second extraction, about 1 g sample was soaked in distilled water and placed in an autoclave at 100 °C for 1 h. Then, the sample was filtered using filter paper and dried. Acetone and water extractives were calculated by following formula:
E x t r a c t i v e s   % = a × b a × 100
a : dry weight of the sample before extraction (g);
b : dry weight of the sample after extraction (g).

2.3.2. Determination of Polysaccharide Composition

Polysaccharide composition was determined using a Bruker AVANCE NMR Spectrometer (400 MHz) with various acid hydrolysis pretreatment conditions. First, the neutralized samples of kenaf outer bast fiber (0.004 g) were diluted with 72% sulfuric acid and reacted at 30 °C for 1 h in an incubator machine. Then, 3 mL of D2O was added to the reaction and heated in an oven at 100 °C for 1 h. The solution was filtered using filter paper size 110 Ømm and put into an NMR tube for NMR analysis. α-L(+)-rhamnose monohydrate was used to determine the sugar peak. After integrating each sugar peak, the glucose, xylose, and other sugar content were calculated according to calibration.

2.3.3. Determination of Lignin Content

The first hydrolysis of 0.275 g kenaf outer bast fiber was digested with 4.5 mL of 72% sulfuric acid in an incubator at 30 °C for 1 h. Then, for the second hydrolysis, diluted sulfuric acid into 3% and placed in the autoclave for 1 h at a temperature of 120 °C. The sample was filtered using a P4 glass filter and washed several times with hot water. Finally, it was dried at 80 °C for 24 h and weighed. Lignin content was calculated by using the following formula:
L i g n i n   c o n t e n t   % = a × b a × 100
a : dry weight of the sample before hydrolysis (g);
b : dry weight of the sample after hydrolysis (g).

3. Result and Discussion

3.1. Chemical Composition of Raw Kenaf Outer Bast Fiber

The chemical compositions of the kenaf outer bast fiber are shown in Table 1. As a minor component, hydrophilic by hot water extraction was a relatively higher percentage than hydrophobic extractive treatment. A similar trend was reported: goat willow has a higher content of hydrophilic extraction, 11.4%, than hydrophobic extraction, 0.8% [25]. The hydrophobic extraction contained fatty acids and alcohols, resin acids, other diterpenoids, and sterols, where the resin acids are the most abundant group of hydrophobic analytes [26]. Compared to the hydrophobic, hydrophilic by ethanol extraction was less complex in terms of the number of different chemical classes detected [26]. Both species were primarily dominated by lignans, flavonoids, and phenolics [26]. Therefore, kenaf fiber interfacial compatibility of hydrophilic kenaf fiber with the hydrophobic resin is poor [27].
Extractive-free kenaf fiber indicated lower lignin content than core fibers with higher cellulose and similar hemicelluloses [28]. As shown in Table 1, this fact was supported by kenaf bast fiber from Malaysia which reported 9.87% of lignin content [29]. On other hand, kenaf core fiber from Korea contains 18.5% of lignin [30]. The kenaf outer bast had been chosen over the core for its advantages with high cellulose content than other parts [31]. Meanwhile, other biomasses had different lignin with kenaf outer bast fiber such as other annual plants (12–15.1%) [32], hardwood (17.9%) [33], and softwood (32.9%) [34]. Hence, according to the previous work and our preliminary experiment of the low lignin content of kenaf outer bast fiber, bleaching was a great pretreatment as delignification prior to acid hydrolysis as the main treatment.
Furthermore, in carbohydrate composition, kenaf outer bast fiber contained 20.1% of hemicellulose and 57.2% of cellulose from 77.3% of holocellulose. In contrast, kenaf core fiber’s cellulose and hemicellulose content was 46.1% and 25.4%, respectively [30]. Meanwhile, the chemical composition of kenaf bast fiber from Malaysia containing 55.0%, 31.8%, 19.2%, and 10.9% was cellulose, hemicellulose, lignin, and others, respectively [35]. Therefore, kenaf’s outer bast makes its crops considered promising biorefinery materials to produce high-purity cellulose. Structural features and their chemical composition of it are primarily dependent on the morphological region, such as soil types, climate, and nutrition, and on the maturity stage (outer bast, inner bast until core), including age [28,35].
NMR spectroscopy was applied to report the carbohydrate content of the kenaf outer bast. The anomeric hydrogen peak integration method calculated the carbohydrate composition in 1H-NMR spectra [25]. The monosaccharide composition of polysaccharides was measured based on each monosaccharide having a different anomeric chemical shift using D2O solvent. Figure 2 shows the monosaccharides peak of glucose, xylose, and other sugar from raw kenaf outer bast. Besides high cellulose content, kenaf, an herbaceous plant, has a xylan as the dominant hemicellulose component, such as in hardwoods [36]. Furthermore, glucuronoxylans are the principal hemicellulose of hardwoods, with monosaccharide components are xylose, glucuronic acid, and some acetyl group [37]. This study used 1H-NMR spectra to measure polysaccharides to monosaccharides with various parameters.

3.2. Effects of Temperatures

As one of the essential variables in acid hydrolysis reaction, temperature is a significant factor during acid hydrolysis treatment [38]. Therefore, the alteration content of the kenaf outer bast composition was analyzed under different temperatures of acid hydrolysis treatment. The temperatures used were 110, 120, and 130 °C. Focus was on the effect of the temperatures; the other reaction conditions are 0.25 N acid concentration and 60 min reaction time. Indeed, the chemical composition effect of kenaf outer bast under different treatment temperatures is shown in Table 2. The yield of hemicellulose from 13.2% at 110 °C rapidly decreased to 2.5% with increasing the reaction temperature to 130 °C. This is related to the low power penetration of organic acids at lower processing temperatures and in reverse [39]. Inevitably, through an increase in temperature, cellulose was slightly decreased from 55.0% to 51.4% between 110 to 130 °C. Furthermore, the effective hydrolysis treatment used sulfuric acid into kenaf outer bast fiber was raised to high temperatures. Hence, the cleaved glycosidic bonds in the hemicellulose were facilitated by vital acid catalysis and hydrolyzing hemicellulose [40]. On the other hand, oil palm from Thailand decreased hemicellulose content from 13.1 to 0.8%, and cellulose slightly decreased during increased temperatures from 110, 120, and 130 °C on 1, 2, and 3% of sulfuric acid on 60 min [41]. Escalating 10 °C of the reaction temperature increased the hydrolyze rate [42].

3.3. Effects of Acid Concentration

Sulfuric acid as a catalyst cleaved the glycosidic linkages in polymeric carbohydrates from polysaccharides into monosaccharides [24]. Meanwhile, the acid concentration is one of the profound influences on exhibitor reaction. From the acid hydrolysis reaction, xylan hydrolysis was faster than cellulose hydrolysis. Furthermore, the acid concentration had been one of the variables in this experiment as an important parameter affecting the hydrolysis treatment to obtain a high yield of cellulose and selective removal of xylan [43]. Figure 3 shows the effect of different sulfuric acid concentrations in the NMR spectrum. The xylose peak decreased with increasing acid concentration. As shown in Table 3, the range of sulfuric acid concentration from 0.25 to 1.00 N remains from 2.2% to 0.8% of hemicellulose. Throughout that reaction, the yield of cellulose decreased from 50.2% to 47.9% at similar conditions. As supposed, increasing acid concentration tends to produce decreased hemicellulose content in the hydrolyzed solid residue. Xylan from hemicellulose decreased from 9.2 to 4.2%, and cellulose content decreased from 65.2 to 61.4%, as sulfuric acid concentration increased from 0.25, 0.5 to 1.00 N at 100 °C on 60 min with jute bast fiber [6]. The hydrolysis was optimized to dissolved xylan to xylose with assistance from acid concentration as the first step order reaction [44]. Meanwhile, the rate of glucose released slightly increased with the acid concentration. This can be associated with the high catalytic effect at high acid concentrations and the increased acid concentration [38]. Therefore, hemicellulose is more readily hydrolyzed and favorable to increasing the purity of cellulose on mass balance value and producing high cellulose content [43].

3.4. Effects of Times

Another variable considered in this hydrolysis treatment of kenaf outer bast fiber was the reaction time at the reaction temperature and acid concentration. All experiments were carried out with a hydrolysis rate that varied slightly with intervals of 30 min. The effect of reaction time was studied using sulfuric acid and temperature covering a wide range of reaction times, as shown in Figure 4. The total yield of hemicellulose decreased from 10.2 to 7.9% by increasing the reaction time from 60 min to 120 min. Hemicellulose yields showed that a reaction time could be expected in specific xylan and was hydrolyzed to xylose as monosaccharides. It also reported that 1% sulfuric acid at 140 °C could remove hemicellulose from 5.23% in 30 min, 4.50% in 60 min to 1.47% in 120 min [45]. The short times and higher temperatures were beneficial for decreasing hemicellulose, especially the increased purity of cellulose [46]. Furthermore, the reaction time dominates the degradation of soluble monosaccharides at reaction times over 100 min [47]. The reaction time does not appear to increase the hydrolysis efficiency significantly; its main effect was to estimate monosaccharides produced in hydrolyzing [47].

3.5. Optimum Conditions of Kenaf Outer Bast

The focus was on raising the high purity of cellulose content. Table 4 shows the optimum condition in this experiment. Regarding the high content of cellulose, the optimum condition has been divided into two potentials. A concentration of 0.25 N has a high yield of solid content, and a low concentration weakly removes hemicellulose content compared with high concentrations [48,49]. Meanwhile, a 1.00 N concentration of sulfuric acid powerfully removes hemicellulose. Unfortunately, the cellulose was followed by a hydrolyze with high acid concentration [6,24,25]. Hence, this suggests the lower acid concentration obtained a high yield of biomass, and hydrolyzed hemicellulose with high acid concentration improved the purity cellulose of kenaf outer bast content. The synergistic effect of the acid concentration of sulfuric acid as catalysis with a temperature on acid hydrolysis reaction to hydrolyze hemicellulose was significant [42,44]. Obtaining pure cellulose in this study requires 130 °C as the high temperature for each acid concentration. Furthermore, the effect of high temperature was a loss of yield content [41]. Otherwise, the low temperature obtained a small amount of hemicellulose with high yield content. The ideal reaction time for hydrolysis should completely hydrolyze hemicellulose into monosaccharides without high degradation of the cellulose. An increased reaction time of acid hydrolysis led to more degradation of produced glucose [24]. Therefore, the most appropriate way to remove hemicellulose and obtain high purity of cellulose is a high-temperature reaction with higher acid concentration and short reaction time.
This project aims to contribute to the scientific and industrial communities to produce biorefinery high-purity cellulose by selectively removing hemicellulose. From a biomass source, treatment, and chiefly the optimum treatment condition, is investigated to obtain high purity of cellulose. Several studies have analyzed the effectivity of acid hydrolysis hydrolyzed carbohydrates with different aims. On the other hand, 4% of sulfuric acid hydrolyzed kenaf bast fiber in 60 min at 140 °C contained 56.8% of cellulose [50]. In equibalance with that result, this study on 1.00 N of sulfuric acid at 130 °C 60 min collected 90.1% of cellulose.
Furthermore, considering a high yield content of the optimum condition acid hydrolysis kenaf outer bast, we found 96.6% purity of cellulose from the total yield. Meanwhile, cellulose purification from other kenaf fibers using the alkaline treatment and bleaching only contains 89.5% purity of cellulose [51]. This research identified acid hydrolysis, up to now, as worthy of a biorefinery step production purity of cellulose. Significantly, parameters to obtain optimum conditions of acid hydrolysis with high yield and high purity of cellulose could substantially contribute to scientific progress and industrial products to consider the biomass source and treatment conditions.
Nowadays, kenaf fiber is valued for biorefinery. Thus, treatment optimization studies are still needed to improve quality, low cost, and high effectiveness [7,51]. Furthermore, growing awareness of the eco-environmental risk of kenaf outer bast fiber as a raw material with a higher cellulose content than other compositions has become promising for biomass. Thus, the work was alleviated for spending energy during acid hydrolysis treatment. Especially, sulfuric acid is one of the inexpensive chemical solutions and, in cost analysis, can be minimized.

4. Conclusions

Kenaf outer bast fiber could improve the purity of cellulose content from acid hydrolysis treatment. The synergistic temperature and acid concentration of sulfuric acid have shown to be the most influential in investigating the total pure cellulose yield. Acid hydrolysis was adequate to hydrolyze almost the entire hemicellulose content. Sulfuric acid as a catalyst in hydrolysis treatment caused the strenuous hydrolyzing of hemicellulose at 0.25–1.00 N of sulfuric acid. Hence, based on the optimum conditions, acid hydrolysis treatment significantly obtained the purity cellulose content of kenaf outer bast with high yield. For maximum hydrolyzing of hemicellulose, the reaction temperature of hydrolysis treatment ought to rise at a high temperature of 130 °C and be assisted by the reaction time to prevent cellulose from degrading into glucose.

Author Contributions

Data curation, Y.M.G.; investigation, J.Y.J.; writing—original draft, V.G.F.; writing—review and editing, J.H.L. and S.-J.S. All authors have read and agreed to the published version of the manuscript.

Funding

This work was supported by the Jeonbuk Institute for Food-Bioindustry funded by the Regionally Balanced New Deal Project of the Ministry of the Interior and Safety and Jeollabuk-do. J.H.L. was supported by the National Research Foundation of Korea under the General Research Project (Grant No. 2020R1F1A1069515).

Acknowledgments

We acknowledge and appreciate the kenaf sample provided by Chan Ho Kang at Jeonbuk Agricultural Research & Extension Services.

Conflicts of Interest

The authors declare no conflict of interest.

References

  1. Alexopoulou, E.; Papatheohari, Y.; Christou, M.; Monti, A. Origin, description, importance, and cultivation area of kenaf. In Kenaf: A Multi-Purpose Crop for Several Industrial Applications; Springer: London, UK, 2013; pp. 1–15. [Google Scholar]
  2. Sh, L.; Lee, B.-H.; Lee, Y.-J.; Jeon, C.-H. Comparing the Physicochemical Properties of Upgraded Biomass Fuel by Torrefaction and the Ashless Technique. Appl. Sci. 2019, 9, 5519. [Google Scholar] [CrossRef] [Green Version]
  3. Tye, Y.Y.; Lee, K.T.; Abdullah, W.N.W.; Leh, C.P. Optimization of various pretreatments condition of kenaf core (Hibiscus cannabinus) fibre for sugar production: Effect of chemical compositions of pretreated fibre on enzymatic hydrolysability. Renew. Energy 2016, 99, 205–215. [Google Scholar] [CrossRef]
  4. Sreenivas, H.T.; Krishnamurthy, N.; Arpitha, G.R. A comprehensive review on light weight kenaf fiber for automobiles. Int. J. Lightweight Mater. Manuf. 2020, 3, 328–337. [Google Scholar] [CrossRef]
  5. Saba, N.; Paridah, M.T.; Jawaid, M. Mechanical properties of kenaf fibre reinforced polymer composite: A review. Constr. Build. Mater. 2015, 76, 87–89. [Google Scholar] [CrossRef]
  6. Rahmini, R.; Zahra, A.; Lim, D.Y.; Shin, S.J. Dilute Acid Hydrolysis of Jute Bast Fiber for Selected Xylan Removal. J. Korea TAPPI 2021, 53, 65–73. [Google Scholar] [CrossRef]
  7. Szulczyk, K.R.; Badeeb, R.A. Nontraditional sources for biodiesel production in Malaysia: The economic evaluation of hemp, jatropha, and kenaf biodiesel. Renew. Energy 2022, 192, 759–768. [Google Scholar] [CrossRef]
  8. Li, T.; Chen, C.; Brozena, A.H.; Zhu, J.Y.; Xu, L.; Driemeier, C.; Dai, J.; Rojas, O.J.; Isogai, A.; Wågberg, L.; et al. Developing fibrillated cellulose as a sustainable technological material. Nature 2021, 590, 47–56. [Google Scholar] [CrossRef]
  9. Nasrollahzadeh, M.; Sajjadi, M.; Iravani, S.; Varma, R.S. Starch, cellulose, pectin, gum, alginate, chitin and chitosan derived (nano) materials for sustainable water treatment: A review. Carbohydr. Polym. 2021, 251, 116986. [Google Scholar] [CrossRef]
  10. Nasatto, P.L.; Pignon, F.; Silveira, J.L.; Duarte, M.E.R.; Noseda, M.D.; Rinaudo, M. Methylcellulose, a cellulose derivative with original physical properties and extended applications. Polymers 2015, 7, 777–803. [Google Scholar] [CrossRef] [Green Version]
  11. Ohkawa, K.; Hayashi, S.; Nishida, A.; Yamamoto, H.; Ducreux, J. Preparation of pure cellulose nanofiber via electrospinning. Text. Res. J. 2009, 79, 1396–1401. [Google Scholar] [CrossRef]
  12. Hindi, S.S.Z. Microcrystalline cellulose: The inexhaustible treasure for pharmaceutical industry. Nanosci. Nanotechnol. Res. 2017, 4, 17–24. [Google Scholar]
  13. Fitriani, F.; Aprilia, S.; Arahman, N.; Bilad, M.R.; Amin, A.; Huda, N.; Roslan, J. Isolation and Characterization of Nanocrystalline Cellulose Isolated from Pineapple Crown Leaf Fiber Agricultural Wastes Using Acid Hydrolysis. Polymers 2021, 13, 4188. [Google Scholar] [CrossRef]
  14. Gallardo-Sánchez, M.A.; Diaz-Vidal, T.; Navarro-Hermosillo, A.B.; Figueroa-Ochoa, E.B.; Ramirez Casillas, R.; Anzaldo Hernández, J.; Rosales-Rivera, L.C.; Soltero Martínez, J.F.A.; García Enríquez, S.; Macías-Balleza, E.R. Optimization of the Obtaining of Cellulose Nanocrystals from Agave tequilana Weber Var. Azul Bagasse by Acid Hydrolysis. Nanomaterials 2021, 11, 520. [Google Scholar] [CrossRef]
  15. Oyekanmi, A.; Saharudin, N.; Hazwan, C.; HPS, A.K.; Olaiya, N.; Abdullah, C.; Alfatah, T.; Gopakumar, D.; Pasquini, D. Improved Hydrophobicity of Macroalgae Biopolymer Film Incorporated with Kenaf Derived CNF Using Silane Coupling Agent. Molecules 2021, 26, 2254. [Google Scholar] [CrossRef]
  16. Wang, J.; Wang, Q.; Wu, Y.; Bai, F.; Wang, H.; Si, S.; Lu, Y.; Li, X.; Wang, S. Preparation of Cellulose Nanofibers from Bagasse by Phosphoric Acid and Hydrogen Peroxide Enables Fibrillation via a Swelling, Hydrolysis, and Oxidation Cooperative Mechanism. Nanomaterials 2020, 10, 2227. [Google Scholar] [CrossRef]
  17. Siqueira, G.; Várnai, A.; Ferraz, A.; Milagres, A.M. Enhancement of cellulose hydrolysis in sugarcane bagasse by the selective removal of lignin with sodium chlorite. Appl. Energy 2013, 102, 399–402. [Google Scholar] [CrossRef]
  18. An, S.; Li, W.; Xue, F.; Li, X.; Xia, Y.; Liu, Q.; Chen, L.; Jameel, H.; Chang, H.M. Effect of removing hemicellulose and lignin synchronously under mild conditions on enzymatic hydrolysis of corn stover. Fuel Process. Technol. 2020, 204, 106407. [Google Scholar] [CrossRef]
  19. Norrrahim, M.N.F.; Ariffin, H.; Yasim-Anuar, T.A.T.; Hassan, M.A.; Ibrahim, N.A.; Yunus, W.M.Z.W.; Nishida, H. Performance Evaluation of Cellulose Nanofiber with Residual Hemicellulose as a Nanofiller in Polypropylene-Based Nanocomposite. Polymers 2021, 13, 1064. [Google Scholar] [CrossRef]
  20. Chandel, A.K.; Antunes, F.A.; Arruda, P.V.D.; Milessi, T.S.; Silva, S.S.D.; Almeida Felipe, M.D.G.D. Dilute acid hydrolysis of agro-residues for the depolymerization of hemicellulose: State-of-the-art. In d-xylitol; Springer: Berlin/Heidelberg, Germany, 2012; pp. 39–61. [Google Scholar]
  21. Tyufekchiev, M.; Finzel, J.; Zhang, Z.; Yao, W.; Sontgerath, S.; Skangos, C.; Duan, P.; Schmidt-Rohr, K.; Timko, M.T. A New Method for Solid Acid Catalyst Evaluation for Cellulose Hydrolysis. Sustain. Chem. 2021, 2, 645–669. [Google Scholar] [CrossRef]
  22. Kildegaard, G.; Balbi, M.D.P.; Salierno, G.; Cassanello, M.; De Blasio, C.; Galvagno, M. A Cleaner Delignification of Urban Leaf Waste Biomass for Bioethanol Production, Optimised by Experimental Design. Processes 2022, 10, 943. [Google Scholar] [CrossRef]
  23. Luo, X.; Gong, Z.; Shi, J.; Chen, L.; Zhu, W.; Zhou, Y.; Huang, L.; Liu, J. Integrating Benzenesulfonic Acid Pretreatment and Bio-Based Lignin-Shielding Agent for Robust Enzymatic Conversion of Cellulose in Bamboo. Polymers 2020, 12, 191. [Google Scholar] [CrossRef] [PubMed]
  24. Hernández, I.P.; Pérez-Pimienta, J.A.; Messina, S.; Saldaña Durán, C.E. Dilute sulfuric acid hydrolysis of tropical region biomass. J. Renew. Sustain. Energy 2012, 4, 021201. [Google Scholar] [CrossRef]
  25. Yoon, S.Y.; Han, S.H.; Shin, S.J. The effect of hemicelluloses and lignin on acid hydrolysis of cellulose. Energy 2014, 77, 19–24. [Google Scholar] [CrossRef]
  26. Füchtner, S.; Brock-Nannestad, T.; Smeds, A.; Fredriksson, M.; Pilgård, A.; Thygesen, L.G. Hydrophobic and hydrophilic extractives in Norway spruce and Kurile larch and their role in brown-rot degradation. Front. Plant Sci. 2020, 11, 855. [Google Scholar] [CrossRef] [PubMed]
  27. Ren, Z.; Wang, C.; Zuo, Q.I.; Yousfani, S.H.S.; Anuar, N.I.S.; Zakaria, S.; Liu, X. Effect of alkali treatment on interfacial and mechanical properties of kenaf fibre reinforced epoxy unidirectional composites. Sains Malays. 2019, 48, 173–181. [Google Scholar] [CrossRef]
  28. Silvy, N.; Reza, S.; Uddin, N.; Akther, M. Comparison between different components of some available hardwood and softwood in Bangladesh. IOSR J. Biotechnol. Biochem. 2018, 4, 1–5. [Google Scholar]
  29. Amel, B.A.; Paridah, M.T.; Sudin, R.; Anwar, U.M.K.; Hussein, A.S. Effect of fiber extraction methods on some properties of kenaf bast fiber. Ind. Crop. Prod. 2013, 46, 117–123. [Google Scholar] [CrossRef]
  30. Jeun, J.P.; Lee, B.M.; Lee, J.Y.; Kang, P.H.; Park, J.K. An irradiation-alkaline pretreatment of kenaf core for improving the sugar yield. Renew. Energy 2015, 79, 51–55. [Google Scholar] [CrossRef]
  31. Marzuki, N.H.; Wahit, M.U.; Arsad, A.; Othman, N.; Yusoff, N.I.S.M. The effect of kenaf loading on the mechanical properties of kenaf-reinforced recycled poly (ethylene terephthalate)/recycled poly (propylene)(rPET/rPP) composite. Mater. Today Proc. 2021, 39, 959–964. [Google Scholar] [CrossRef]
  32. Bledzki, A.K.; Franciszczak, P.; Osman, Z.; Elbadawi, M. Polypropylene biocomposites reinforced with softwood, abaca, jute, and kenaf fibers. Ind. Crop. Prod. 2015, 70, 91–99. [Google Scholar] [CrossRef]
  33. Gellerstedt, G.; Tomani, P.; Axegård, P.; Backlund, B. Lignin recovery and lignin-based products. In Integrated Forest Biorefineries—Challenges and Opportunities; Royal Society of Chemistry: London, UK, 2013; pp. 180–210. [Google Scholar]
  34. Edmunds, C.W.; Peralta, P.; Kelley, S.S.; Chiang, V.L.; Sharma-Shivappa, R.R.; Davis, M.F.; Harman-Ware, A.E.; Sykes, R.W.; Gjersing, E.; Cunningham, M.W.; et al. Characterization and enzymatic hydrolysis of wood from transgenic Pinus taeda engineered with syringyl lignin or reduced lignin content. Cellulose 2017, 24, 1901–1914. [Google Scholar] [CrossRef]
  35. Saba, N.; Jawaid, M.; Hakeem, K.R.; Paridah, M.T.; Khalina, A.; Alothman, O.Y. Potential of bioenergy production from industrial kenaf (Hibiscus cannabinus L.) based on Malaysian perspective. Renew. Sustain. Energy Rev. 2015, 42, 446–459. [Google Scholar] [CrossRef]
  36. Gao, X.; Kumar, R.; Wyman, C.E. Fast hemicellulose quantification via a simple one-step acid hydrolysis. Biotechnol. Bioeng. 2014, 111, 1088–1096. [Google Scholar] [CrossRef]
  37. Vuong, T.V.; Master, E.R. Enzymatic production of 4-O-methyl d-glucaric acid from hardwood xylan. Biotechnol. Biofuels 2020, 13, 1–10. [Google Scholar] [CrossRef] [Green Version]
  38. Guerra-Rodríguez, E.; Portilla-Rivera, O.M.; Jarquín-Enríquez, L.; Ramírez, J.A.; Vázquez, M. Acid hydrolysis of wheat straw: A kinetic study. Biomass Bioenergy 2012, 36, 346–355. [Google Scholar] [CrossRef]
  39. Franco, A.P.; Yamamoto, L.Y.; Tadini, C.C.; Gut, J.A. Dielectric properties of green coconut water relevant to microwave processing: Effect of temperature and field frequency. J. Food Eng. 2015, 155, 69–78. [Google Scholar] [CrossRef]
  40. Peng, M.; Zhu, J.; Luo, Y.; Li, T.; Xia, X.; Qin, C.; Liang, C.; Bian, H.; Yao, S. Enhancement of separation selectivity of hemicellulose from bamboo using freeze–thaw-assisted p-toluenesulfonic acid treatment at low acid concentration and high temperature. Bioresour. Technol. 2022, 363, 127879. [Google Scholar] [CrossRef]
  41. Noparat, P.; Prasertsan, P.; Sompong, O.; Pan, X. Dilute acid pretreatment of oil palm trunk biomass at high temperature for enzymatic hydrolysis. Energy Procedia 2015, 79, 924–929. [Google Scholar] [CrossRef] [Green Version]
  42. Rafiqul, I.S.M.; Sakinah, A.M. Kinetic studies on acid hydrolysis of Meranti wood sawdust for xylose production. Chem. Eng. Sci. 2012, 71, 431–437. [Google Scholar] [CrossRef]
  43. Kumar, S.; Dheeran, P.; Singh, S.P.; Mishra, I.M.; Adhikari, D.K. Kinetic studies of two-stage sulphuric acid hydrolysis of sugarcane bagasse. Renew. Energy 2015, 83, 850–858. [Google Scholar] [CrossRef]
  44. Wang, W.; Yuan, T.; Cui, B.; Dai, Y. Investigating lignin and hemicellulose in white rot fungus-pretreated wood that affect enzymatic hydrolysis. Bioresour. Technol. 2013, 134, 381–385. [Google Scholar] [CrossRef] [PubMed]
  45. Wolf, M.; Berger, F.; Hanstein, S.; Weidenkaff, A.; Endreß, H.U.; Oestreich, A.M.; Ebrahimi, M.; Czermak, P. Hot-Water Hemicellulose Extraction from Fruit Processing Residues. ACS Omega 2022, 7, 13436–13447. [Google Scholar] [CrossRef]
  46. Amicucci, M.J.; Galermo, A.G.; Nandita, E.; Vo, T.-T.T.; Liu, Y.; Lee, M.; Xu, G.; Lebrilla, C.B. A rapid-throughput adaptable method for determining the monosaccharide composition of polysaccharides. Int. J. Mass Spectrom. 2019, 438, 22–28. [Google Scholar] [CrossRef]
  47. Kapu, N.S.; Yuan, Z.; Chang, X.F.; Beatson, R.; Martinez, D.M.; Trajano, H.L. Insight into the evolution of the proton concentration during autohydrolysis and dilute-acid hydrolysis of hemicellulose. Biotechnol. Biofuels 2016, 9, 224. [Google Scholar] [CrossRef] [PubMed] [Green Version]
  48. Al-Rudainy, B.; Galbe, M.; Wallberg, O. Hemicellulose recovery from spent-sulfite-liquor: Lignin removal by adsorption to resins for improvement of the ultrafiltration process. Molecules 2020, 25, 3435. [Google Scholar] [CrossRef]
  49. Guo, A.; Sun, Z.; Satyavolu, J. Impact of chemical treatment on the physiochemical and mechanical properties of kenaf fibers. Ind. Crops Prod. 2019, 141, 111726. [Google Scholar] [CrossRef]
  50. Tuerxun, D.; Pulingam, T.; Nordin, N.I.; Chen, Y.W.; Kamaldin, J.B.; Julkapli, N.B.; Lee, H.V.; Leo, B.F.; Johan, M.R. Synthesis, characterization and cytotoxicity studies of nanocrystalline cellulose from the production waste of rubber-wood and kenaf-bast fibers. Eur. Polym. J. 2019, 116, 352–360. [Google Scholar] [CrossRef]
  51. Jalali Torshizi, H.; Dahmardeh Ghalehno, M.; Khalili Gasht Roudkhani, A.; Esmaeili, M.H. Dissolving pulp production from auto-hydrolyzed Kenaf stalk fibers by Soda-AQ process in biorefinery approach. For. Wood Prod. 2019, 71, 357–366. [Google Scholar]
Applsci 13 00334 g001 550
Figure 1. Illustration of acid hydrolysis treatment process.
Figure 1. Illustration of acid hydrolysis treatment process.
Applsci 13 00334 g001
Applsci 13 00334 g002 550
Figure 2. Anomeric hydrogens in the NMR spectrum of monosaccharides in kenaf outer bast.
Figure 2. Anomeric hydrogens in the NMR spectrum of monosaccharides in kenaf outer bast.
Applsci 13 00334 g002
Applsci 13 00334 g003 550
Figure 3. Different acid concentrations of sulfuric acid hydrolyze different xylan in the hemicellulose of kenaf outer bast by NMR spectrum.
Figure 3. Different acid concentrations of sulfuric acid hydrolyze different xylan in the hemicellulose of kenaf outer bast by NMR spectrum.
Applsci 13 00334 g003
Applsci 13 00334 g004 550
Figure 4. Chemical composition of kenaf outer bast with different reaction times of acid hydrolysis with 0.5 N sulfuric acid at 110 °C.
Figure 4. Chemical composition of kenaf outer bast with different reaction times of acid hydrolysis with 0.5 N sulfuric acid at 110 °C.
Applsci 13 00334 g004
Table
Table 1. Materials’ balance of raw kenaf outer bast.
Table 1. Materials’ balance of raw kenaf outer bast.
Chemical CompositionsRaw Samples (%)
Carbohydrates
 Cellulose57.2
 Hemicellulose20.1
     Xylan14.4
     Others Sugar5.7
Lignin7.7
Extractives
  Hydrophilic a13.7
  Hydrophobic b0.5
a by hot water extraction; b by acetone extraction.
Table
Table 2. Chemical composition of kenaf outer bast with different reaction temperatures of acid hydrolysis.
Table 2. Chemical composition of kenaf outer bast with different reaction temperatures of acid hydrolysis.
Temp a (°C)Acid Con b
(N)		Time
(min)		Yield (%)Chemical Composition
Cellulose (%)Hemicellulose (%)Lignin (%)
1100.256068.8 ± 0.455.0 ± 0.113.2 ± 0.20.6 ± 0.2
1200.256063.3 ± 0.152.6 ± 0.210.1 ± 0.20.6 ± 0.1
1300.256054.4 ± 0.151.4 ± 0.12.5 ± 0.10.6 ± 0.5
a Temperature; b Acid concentration.
Table
Table 3. Chemical composition of kenaf outer bast with a different acid concentration of acid hydrolysis.
Table 3. Chemical composition of kenaf outer bast with a different acid concentration of acid hydrolysis.
Acid Con b
(N)		Temp a (°C)Time
(min)		Yield (%)Chemical Composition
Cellulose (%)Hemicellulose (%)Lignin (%)
0.2513012052.9 ± 0.250.2 ± 0.12.2 ± 0.10.5 ± 0.4
0.5013012050.7 ± 0.448.5 ± 0.21.6 ± 0.10.5 ± 0.2
1.013012049.6 ± 0.147.9 ± 0.10.8 ± 0.20.8 ± 0.1
a Acid concentration; b Temperature.
Table
Table 4. The optimal condition of dilute acid hydrolysis on kenaf outer bast.
Table 4. The optimal condition of dilute acid hydrolysis on kenaf outer bast.
Optimal forAcid Con a (N)Temp b (°C)Time
(min)		Yield (%)Chemical Composition
Cellulose (%)Hemicellulose (%)Lignin (%)
Higher yield0.251306054.4 ± 0.151.4 ± 0.12.5 ± 0.10.6 ± 0.1
Purer cellulose1.0013012049.6 ± 0.147.9 ± 0.10.8 ± 0.20.8 ± 0.1
a Acid concentration; b Temperature.
Disclaimer/Publisher’s Note: The statements, opinions and data contained in all publications are solely those of the individual author(s) and contributor(s) and not of MDPI and/or the editor(s). MDPI and/or the editor(s) disclaim responsibility for any injury to people or property resulting from any ideas, methods, instructions or products referred to in the content.

Share and Cite

MDPI and ACS Style

Firsty, V.G.; Jeong, J.Y.; Gu, Y.M.; Lee, J.H.; Shin, S.-J. High Cellulose Purity by Acid Hydrolysis Pretreatment on Kenaf Outer Bast. Appl. Sci. 2023, 13, 334. https://doi.org/10.3390/app13010334

AMA Style

Firsty VG, Jeong JY, Gu YM, Lee JH, Shin S-J. High Cellulose Purity by Acid Hydrolysis Pretreatment on Kenaf Outer Bast. Applied Sciences. 2023; 13(1):334. https://doi.org/10.3390/app13010334

Chicago/Turabian Style

Firsty, Virginia Ghita, Ji Yeon Jeong, Yang Mo Gu, Jin Hyung Lee, and Soo-Jeong Shin. 2023. "High Cellulose Purity by Acid Hydrolysis Pretreatment on Kenaf Outer Bast" Applied Sciences 13, no. 1: 334. https://doi.org/10.3390/app13010334

Note that from the first issue of 2016, this journal uses article numbers instead of page numbers. See further details here.

Article Metrics

Back to TopTop