CHEM. RES.

CHINESE UNIVERSITIES 2010, 26(4), 667671

Isolation of Hemicellulose from Wood Chips via Extraction with Kraft Green Liquor
SUN Hui1*, XU Ying-kai2 and XU Guo-zhi1
1. Department of Material Science and Engineering, China National Center for Quality Supervison & Test of Plastic Products, Beijing Technology and Business University, Beijing 100048, P. R. China; 2. Department of Surgery, University of Pittsburg, 3459 Fifth Avenue, Pittsburgh PA, USA Abstract The present paper covers the extraction of hemicelluloses from woods, i.e., Eucalyptus Globulus, white fir and Douglas fir via green liquor pretreatment and alkali post-treatment with sodium hydroxide. The effects of such extraction conditions as extraction time, temperature on the yields of hemicellulose and the degree of deliginification were investigated. Sugar analyses using Dionex indicate that xylose, glucose and mannose are the main sugar types present in the hemicellulose from Eucalyptus. Other sugar components such as arabinose and galactose were also found in Dogulas fir hemicellulose. The highest yield of hemicellulose was 8.4% for Eucalyptus extracted with green liquor at 130 C for 3.5 h. Further sodium hydroxide extraction for 5 h gave a hemicellulose yield of about 20%. The use of green liquor for the extraction of wood hemicellulose is believed to be the first attempt. Keywords Hemicellulose; Lignin; Wood; Green liquor; Alkali extraction Article ID 1005-9040(2010)-04-667-05

Introduction

Globally increasing environmental awareness and the possibility of increasing price and dwindling supply of petroleum-based products have led to increasing research attention on materials from renewable resources[13]. Cellulose, hemicellulose and lignin as the three main components of wood, straw, corn stalk and other biomasses have been extensively investigated[46]. Cellulose being one of the most abundant natural occurring polymers has a number of applications such as paper, packaging, lacquer technologies, pharmaceutical coatings and so on. In addition, cellulose and its derivatives have also found biomedical applications as hemodialysis membranes, biosensors, coating materials for drugs, wound dressing and so on[7]. Hemicelluloses are a group of polysaccharides with a lower degree of polymerization compared to cellulose. The main sugar components of hemicelluloses are D-xylose, D-mannose, D-glucose, D-galactoses, L-arabionose, D-glucuronic acid, 4-Omethyl-D-glucuronic acid and D-galacturonic acid, while the minor sugar components present are L-fucose, L-rhamnose, and O-methylated sugars[5].

Hemicelluloses are commonly used as adhesives, stabilizers, thickeners, and emulsifiers and so on. During the past two decades, the isolation of wood hemicelluloses by steam explosion[3], microwave-assisted extraction[8], hot water and alkali extractions[9,10] has been reported with the aim of preparing hemicellulose-based hydrogels for biomedical applications. Magnus Palm and Guido Zacchi[8] have reported the extraction of hemicellulosic oligosaccharides from spruce via microwave assistance or steam treatment. Their results show that the maximum of hemicelluloses extracted was 12.5 g/100 g dry wood by means of microwave treatment at 200 C for 5 min. Heat treatment at a higher temperature for longer time produces more monomer sugars which are undesirable in terms of the synthesis of hydrogels. However significant decreasing temperature and time result in lower amounts of oligosaccharides extracted. These data would be useful for the optimization of experimental conditions. By comparing the two methods, i. e., microwave and steam treatments, the authors suggest the use of the later method at 200 C for 2 min since the hemicellulosic oligosaccharides extracted have a

*Corresponding author. E-mail: sunhui@btbu.edu.cn Received October 21, 2009; accepted February 27, 2010. Supported by Scientific and Technological Development Programs of Beijing Municipal Education Commission, China (No.KM201010011004) and the Scientific Research Foundation for the Returned Overseas Chinese Scholars, Ministry of Education, China.

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higher mean molecular weight and are thus more suitable for the synthesis of hydrogels. Lindblad et al.[11] also reported the preparation of hydrogels based on hemicellulose which was isolated from spruce through a procedure in which wood chips(Picea abies ) were treated with saturated steam at 190200 C for 25 min. Lawther et al.[12] have reported the various procedures for extracting hemicellulose and cellulose from wheat straw holocellulose via aqueous solutions of potassium, sodium or lithium hydroxide. The maximum yield of hemicellulose extracted was found to be 34.93%[12]. Gabrielii et al.[13] reported the preparation of hemicellulose-based hydrogels and their physical aspects like the stimuli-responsive properties, the mechanism of hydrogel formation and the formation of microporous structures. The later(microporous structures) may be an important aspect for considering this type of hydrogel in medical application, such as scaffolds. Kraft green liquor has been used in the pretreatment of softwood chips[14,15]. It was found that green liquor pretreatment contributes to the delignification. We have applied green liquor pretreatment in wood hemicellulose isolation. Here in this paper, we report the hemicelluloses isolated from Eucalyptus Globulus and Douglus fir chips via this route. The yield of hemicellulose isolated was found to be up to 8% of dry wood. Extended post-extraction of wood chips with alkali gives a maximum hemicellulose yield of around 20%. To our knowledge, this is the first time that green liquor has been used in the extraction of hemicellulose from wood.

wood powder of an appropriate amount and green liquor in a mass ratio of 4:1 or 10:1 of green liquor to wood. The reactor was placed in an oil bath and allowed to be extracted for a certain period of time (1, 2, 3 and 3.5 h) at 60 or 130 C. After the extraction, the mixture of wood and green liquor was filtered and the wood residue was washed with water. The filtrate was acidified with hydrochloric acid to pH=2.3 and the portion of lignin was recovered. After filtration the filtrate was neutralized and hemicellulose was recovered by coagulation in methanol. 2.3 Lignin Content Determination

The lignin content of wood fibres was determined via the TAPPI method[16]. Briefly ca. 100 mg of wood fiber was reacted with 1.5 mL of 72% sulfuric acid at room temperature for 2 h under stirring. Then the solution was diluted with water to 3% sulfuric acid and refluxed for another 4 h. The suspension was filtered, and the acid-insoluble lignin was determined gravimetrically. The filtrate was diluted to 100 mL with deioned water, and the acid-soluble lignin was determined spectrophotometrically at 205 nm with an extinction coefficient of 110 au Lg1cm1[16]. The lignin content was reported as the total sum of both acid-insoluble and acid-soluble lignins. 2.4 Sugar Analysis with Dionex

2
2.1

Experimental
Materials

Wood chips of Eucalyptus Globulus, white fir and Douglas fir were ground with a Wiley mill(Arthur H. Thomas Co., Philadelphia, USA) to pass a 40-mesh size screen. The ground wood powder was then dried in a vacuum oven at 40 oC for 24 h. The oven dried wood samples were Soxhlet extracted with acetone for 48 h and then kept in a vacuum oven at 40 oC for 24 h prior to use. Green liquor composed of sodium hydroxide and sodium sulfide with pH=13 was used in this study. 2.2 Green Liquor Pretreatment To a stainless steel parr reactor were charged

Analysis of sugar contents was performed on a Dionex DX-3000HPLC using a Dionex PA1 column, which was equipped with a pulsed amperometric detector and a Dionex autosampler. The column was equilibrated with 0.2 mmol/L NaOH. Pure water was used as eluent at a flow rate of 0.8 mL/min. Sugars used as calibration standards were arabinose, glucose, galactose, mannose, xylose and 5-hydroxymethylfurfural. Fucose was used as internal standard. Three sets of sugar standard solutions were prepared to cover the sugar concentration ranges of the samples to be determined.

3
3.1

Results and Discussion

Extraction with Green Liquor

Green liquor was used in the isolation of hemicelluloses from several wood chips such as white fir, Eucalyptus and Douglas fir. Different reaction conditions, i.e., varying extraction temperatures(130 C,

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60 C and room temperature), extraction time(1, 2, 3 and 3.5 h) and green liquor/wood ratios, G/W(mass ratio 4:1 and 10:1) were examined in an attempt to optimize the experimental conditions to give the highest yield of sugars(hemicelluloses) isolated. Steps involved in the isolation of hemicelluloses included acidification, neutralization, centrifugation and coagulation. During the process, additional salts, either sodium chloride or sodium sulfate depending on the acid used in acidification, were introduced. In view of this, recovered hemicellulose had to be purified. The hemicellulose in the supernatant after centrifugation was coagulated in ethanol/methanol. Owing to the slight solubility of sodium hydroxide in alcohol, a portion of the salts could be removed. 3.2 Effects of Treatment Time and Temperature on Total Wood Mass Loss It was experimentally found that the wood percentage mass loss increased with increasing the green liquor treatment time. During the initial treatment period up to about 2 h, the mass loss increased remarkably with green liquor treatment time. Thereafter, the increase in wood mass loss became relatively slowly and leveled off after treatment for about 3 h. This indicates that an optimized treatment time could be 3 h. The highest mass loss was found to be 32% which was observed for white fir at 130 C within a treatment time of 3.5 h and 28.6% for Eucalyptus under similar treatment conditions. As expected, green liquor treatment at a lower temperature, e. g. 60 C gave a lower percentage mass loss up to 20% for white fir and 19% for Eucalyptus. 3.3 Effects of Treatment Time and Temperature on Yield of Lignin The amount of lignin extracted was always increased with increasing green liquor treatment time as shown in Fig.1. Similarly, the increase during the first 2 h is faster than that after 2 h. Up to 10.3% and 10.1% of lignin could be recovered for white fir after 3.5 h green liquor treatment at 130 and 60 C, respectively. In contrast to white fir, the percentages of the lignin isolated from Eucalyptus were relatively lower: 9.6% at 130 C and 7.9% at 60 C, indicating that the soft wood has more lignin than the hard wood investigated here.

Fig.1

Plots of lignin extracted as a function of green liquor treatment time or temperature

a. White fir, 130 C; b. white fir, 60 C; c. Eucalyptus, 130 C; d. Eucalyptus, 60 C.

As expected, lignin analyses of the wood chips after green liquor treatment show that the lignin content decreased with increasing both treatment temperature and/or time. As is evident from Fig.2, the lignin content of Eucalyptus decreased to 16.9% and 18.8% after treatment for 3 h at 130 and 60 C, respectively.

Fig.2

Plots of percentages of lignin remaining in wood as a function of green liquor treatment time and temperature
a. Eucalyptus, 60 C; b. Eucalyptus, 130 C; c. white fir, 60 C; d. white fir, 130 C.

The decrease was not so significant for the 20.1% lignin content in the untreated wood fiber. In contrast to this, the deligninfication of white fir chips is more effective. The lignin content significantly decreased to 15.9% and 13.44% after treatment for 3 h at 60 and 130 C respectively from 28.2% for untreated white fir. 3.4 Effects of Treatment Time and Temperature on the Yield of Hemicellulose Isolated The yields of hemicelluloses isolated via green liquor route increased with increasing green liquor treatment time. The highest yield of 8.1% was observed at 130 C after 3.5 h extraction of Eucalyptus as shown in Fig.3. Post extraction with sodium hydroxide after the green liquor treatment gave much

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higher yields of hemicellulos up to 19.8% after 3.5 h extraction with soudium hydroxide.

Fig.3

Effects of green liquor treatment time and post alkali extraction on the yield of isolated hemicellulose from Eucalyptus Globulus
a. Green liquor; b. GL+NaOH(extended NaOH extraction of 5 h).

3.5

Hemicellulose Sugar Analysis

Hydrolyses of hemicelluloses in 3%(mass fraction) sulfuric acid within a hydrolysis time of up to 7 h were performed(Fig.4). It was found that with increasing hydrolysis time, the concentrations of three sugars, i.e., xylose, glucose and mannose, were increased. The increases were rapid during the first 3 h, after which the concentrations essentially remained constant: 10.5, 3.6 and 0.4 mg/L for xylose, glucose and mannose, respectively.

hydrolysates of thus isolated hemicellulose shows that besides the three sugars found in the hemicellulose isolated from Eucalyptus, i.e., mannose, glucose and xylose, galactose and arabinose were also found, though in relatively smaller amounts. These sugar contents are slightly lower than those reported in literature[17], where hemicellulose-derived sugars were isolated from steam-exploded softwood. Displayed in Fig.5 is the comparison of the compositions of various monosugar types with green liquor extractions at both 130 and 100 C for 3.5 h. As seen from Fig.5, in most cases, monosugar compositions at an extraction temperature of 130 C are obviously lower than those at an extraction temperature of 60 C. In addition to these sugar types, smaller amounts of other components, furfural and hydroxymethylfurfural(HMF) were also found, suggesting the occurrence of the degradation of mono sugars by dehydration and condensation reactions which might take place when the extraction temperature was high with longer extraction hours. An explanation for this could be that the pentoses were transformed into furfural and hexoses into hydroxymethylfurfural. In fact this phenomenon was reported previously in a literature[18] where the effect of increasing severity of steam explosion on the yield of hemicelluose and its derived sugar contents were investigated.

Fig.4 Effects of acid hydrolysis time of hemicellulose isolated from Eucalyptus Globulus on the contents of xylose(a), glucose(b) and mannose(c)

Fig.5

The dependence of xylose yield on sulfuric acid concentration showed that, within each hydrolysis time, the yield of xylose always increased with sulfuric acid concentration increase(1%, 2% and 3%, not shown in Figure). As mentioned above, the highest yield obtained with 3%(mass fraction) sulfuric acid was 10.5 mg/mL, which is much higher than those obtained with 2% and 1% sulfuric acid which are 8.8 and 5.8 mg/mL, respectively. Douglas fir was also extracted with green liquor for hemicellulose isolation. Sugar analysis of the

Sugar compositions of hemicelluloses isolated from Douglas fir

a. Mannose; b. galactose; c. xylose; d. arabinose; e. glucose; f. furfural; g. HMF.

Conclusions

For the first time, kraft green liquor was used in the extraction of hemicellulose from wood chips. It was found that up to 8% hemicellulose was isolated from Eucalyptus Globulus with green liquor extraction. When this combined with post alkali extraction, the yield of hemicellulose extracted was as high as ca. 19.8%. Xylose, glucose and mannose were found

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[6] [7] 1998, 69(8), 1661

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Gabrielii I., Gatenholm P., Journal of Applied Polymer Science, Argyropoulos D. S., Ed., Materials, Chemicals and Energy from Forest Biomass, American Chemical Society, Washington D. C., 2007, 25

to be the main sugars present in Eucalyptus hemicellulose. Other sugar components such as arabinose and galactose were also found in Dogulas fir hemicellulose. Green liquor treatment can lead to the delignification of wood to some extent. This was essentially completed after 3 h treatment. A higher temperature favors delignification. Lignin extracted amounted to up to 10.3%(mass fraction) of dry wood for softwood and 9.4% for hardwood. However, considerable amounts of lignin remained in the fibre, namely, 13% for white fir and 16.8% for Eucalpytus. References
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