The effect of methylbenzene/ethanol ratios on chemical composition of extractives from Eucalyptus gr

For. Stud. China,2012,14(3):235-239DOI10.1007/11632012-0311-2RESEARCH ARTICLIThe effect of methylbenzene/ethanol ratios on chemical compositionof extractives from eucalyptus grandisZHANG Bin, WU Shu-bin, GUO Da-liangState Key Laboratory of Pulp and Paper Engineering, South China University of Technology, Guangzhou 510640,P. R. ChinaC Beijing Forestry University and Springer-Verlag Berlin Heidelberg 2012Abstract Chemical components of methylbenzene/ethanol extractives of Eucalyptus grandis were identified by GC/MS and differentmethylbenzene/ethanol solutions (9/1, 4/1, 2/1, 1/1, 1/2)were used to describe their distinctions. The distributions of micro particlesin each extractive were studied simultaneously. The results show that there were significant differences between the various extractives, although the extractives were essentially the same, i. e, alcohols, alkanes, esters and acids. With the increase of ethanol compo-ion in the solutions, the total amount of extractives increased; in solvent with higher amounts of ethanol, some acidic structures ords, such as glutaric acid, could be seen. An investigation of micro particles indicated that the distribution of particle size of eachimple did not change greatly between the solutions. a slight decrease in size was seen with the reduction in the amount of methyl-benzeneKey words extractives, Eucalyptus grandis, micro particles1 Introductionto be a high value-added process. Eucalypt speciesowe their popularity as pulp wood due to their fastIn biorefineries considerable attention is paid to the so- growth rates in high yield plantations with excellentcalled three main components of woody biomass, i. e, pulp grades and unique combinations of physical arcellulose, hemicellulose and lignin(Agarwal, 2007; optical properties(Khristova et al., 2006). EucalyptaHuang et al., 2008). But wood is composed not only grandis has been widely planted in the south of China,of these three main components but also of organic where it is largely used as wood stock in the papercomponents, such as phenolic compounds. Many of making industry. Hence, to make clear the composithese extractives can be removed by solvent extraction tion of the extractives is of great importancewith water and/or various organic solvents. In tradiIn this study, the traditional benzene/ethanol extrac-tional light industries, these organic components, i. e, tion method was improved and various methy lbenpharmaceuticals, fine chemicals and spices, play sig- zene/ethanol solutions were adopted to describe thenificant roles. But in paper making processes, the pres- distinctive characteristics of E. grandis extractiveence of wood extractives results in large amounts of with the purpose of describing the rules of extractiveadditional- chemicals, i.e., bleaching agents and adhe- bleaching. GC/Ms(gas chromatography-mass spec-sives which have great effect on paper quality, causing trometry) analyses were carried out to identify themore difficulties in the treatment of both waste water types of extractives. We investigated the size distribu-and black-liquid (Ishida et al, 2007 ). Many attempts tion of the examined material by micro particle sizehave been made in pretreatment of wood chips before detectionstarting the paper milling process. Although the effectof pretreatments on paper increased its quality(Sun etal, 2003; Brito et al., 2008; Qin et al, 2009; Martin- 2 Materials and methodsSampedro et aL, 2011; Romani et al., 2011), the treatment of waste water from the pretreatment of wood 2.1 Materia中国煤化工chips became an additional and urgent issue(Penget al, 2007). Recycling of waste water did not seemCNMHGEucalyptus g….nically crushedAuthor fcespondence.E-mail:shubinwu(@scut.edu.cn236Forestry Studies in China, VoL 14, No 3, 2012into chips of 10 mm x 30 mm at the Yueyang Paper Table 1 Total amount of different extractivesMill, Hunan Province. The chips were washed with SamplAmount (%)deionized water to remove float ash. methylbenzene I35and ethanol were of chromatography grade and ex- 22.47actly combined in ratios of 9/1, 4/1, 2/1, 1/1 and 1/2.3453.353.42.2 Methylbenzene/ethanol extractionThe crushed chips were dried by a vacuum condenser,accurately weighted and divided into five groups, ofwas a clear increase between Nos. 2 and 3, with slightincreases both between Nos. 1 and 2 as well as be-10 g each on a dry weight basis. Each sample was ex- tween Nos. 4 and 5. Wood extractives are thoughttracted with its corresponding solution by the Soxhletextraction method at 95 C for 4h. After extractionto be related to the method of extraction such as thechoice of the solution and extraction time the polar-the liquids extracted were filtered for GC/MS analysisand micro particle size detectionity of solutions also has a great effect on wood extrac-tives. Under normal conditions, high polarity leads toa high amount of extractives. Hence, we consideredthat the polarity change was slight between Nos. I and2.3 GC/MS analysis2. The same conclusion was reached for the changeGC/MS analysis was carried out on a Finnigan Tracebetween Nos 4 and 5GC-MS(Thermo Finnigan Company, USA). The GCcolumn temperature was programmed as follows: from3.2 Identification of extractivesroom temperature to 40C at intervals of 5oC min,holding for 2 min; from 40C to 70C again at intervals of 5C min", holding for 10 min and from 700Identification of extractives was carried out by GC/MSto 250C at intervals of 5%C min -. The mass to chargeanalyses. Figure I represents the total ion chromatoratio(m/z) ranged from 35 to 335grams of the extractives of five E. grandis samplesThe components given by the ms data are provided inTable 2From the analytical results of Fig. I and Table 2, the2. 4 Micro particle size detectiomain common extractives of the five samples appearedto be Dl-leucine, benzeneacetaldehyde, butyronitrile,The filtered extracted liquids were diluted 200 times 2-phenyl-ethylbenzene, o-dimethylbenzene and m-xy-(Peng and Wu, 2008)with deionized water and pre- lene Alkanes and cyclanes were found in each sampletreated ultrasonically in order to activate the solutionalthough their total amounts did not change much. InMicro particle size detection was carried out with a solvents with higher ethanol contents, some acidiczetasizer Nano-ZS(Malvern Instruments, England)structures or acids, such as glutaric acid were foundEach time, 2 mL of a diluted extracted liquid was addThe last of the recognized substances were benzenesed to the sample pool. Particle sizes were calculatedfor which their relative amounts did not change much,directly via a connected computerexcept in sample No. 1. Actually, from our calculatedresults we concluded that the amount of ethanol in thesolvent had an effect on the dissolution of higher po-3 Results and discussionlarity substances, while in the lower polarity substances or non- polar ones the effect was limited. Similar3.1 Total amount of extractivesresults about plant extractives and the relationship between solution polarity and extractive kinds were alsoThe total amount of the five extractives (Nos. 1-5), reported by Yao et al.(2000), Liu et al.(2010)andrepresenting five different ratios of methylbenzene/ Peng et al.(2010). Peng et al.(2010)studied the exethanol, i.e., 9/1, 4/1, 2/1, 1/1, 1/2, was calculated by tractive from Cornus wilsoniana seeds in five differ-the difference in mass after extraction. Table 1 lists the ent organic solvents and concluded that the total massresultsof five extracAs can be seen from Table 1 the total amount of the ied. yao et afive extractives changed from 2.35%-3.44%, which extractivesH中国煤化工 ompounds var-es of five birchCNMHnts. Liu et alagrees with a number of previous studies( Cheng, (2010)studied poplar extractives from water, benzene/1995; Ou and li, 1996). It also can be seen that there alcohol and methy benzene extractions and found thatZHANG Bin et al. The effect of methylbenzene/ethanol ratios on chemical composition30A308162400000016Time(min)Fig. 1 Total ion chromatogram of E. grandis extractives as a function of different solutionsthe main compounds of water extraction were ketones, Table 2 Analytical results of chemical components of Econsisted of furans, alcohols, aldehydes, ketones and in ratios of 9/1(A), 4/1( B), 2/1( C), I/1(D)and In(E)onsphenols and esters, extractives from benzene/alcohol grandis extractives with five methylbenzene/ethanol solutionsphenols, while methylbenzene extractives were mainlyalkanes, alkenes and alcoholsNo. R1Relativearea(%)3.3 Micro particle size distribution2.50063.53EthylcyclopentaneTable 3 presents the micro particle size distribution of 36.892-Phenyl-butyronitrile50.19E. grandis extractives as a function of different solu7.53DL-Leucine23.22tions(Nos. 1-5)8.64 1, 2, 3-Propanetriol, I-acetateThis table shows the division of seven zones of par9.23 cis-1, 3-Dimethylcyclohexaneticle size distribution. It is clear that the main v zones9.85 1-Methyl-3-ethylcyclopentane 0.59(volume fraction)were 55.4-100.6 nm, 106.0-156.610.98Octanenm,164.0-255.0nm,287.3-3934 nm and455.31123.3 nm These five zones accounted for nearly 95%11.65 cis-1, 4-Dimethylcyclohexane0.27of the V distribution. Accordingly, the main N zones1015.30Ethy hexanol0.81(numerical fraction)were 55.4-100.6 nm, 106.0-156.6 11 21.470.83nm and 1 64.0-255.0 nm which accounted for nearl23.72O-Dimethylbenzene0.5890% of the n distribution. From the size calculation(To be continuedwe concluded that one half of the molecules were ofsize 55.4-100. 6 nm. Rowell (1984)suggested that theapertures of E. grandis on cell walls were less than function o中国煤化工 of ethanol froml0 nm while molecules larger than 400 nm wouldNos. 1 to 5. wbe impediments in leaching of extractives(Zharin the solverCNMH Gount of ethanoluavs of the smalleraL., 2007). Another obvious rule, demonstrated from molecules, i.e. of sizes 21.0-51.2 nm 55.4-100.6 nmthe listed data, was a change in the distribution as a and 106.0-156.6 nm, increased, while these two num238Forestry Studies in China, VoL 14, No3, 2012Table 2(continued)DRelativComponentRelativeminarea(%)(min")area(%)2.50BenzeneBe3.78Heptane295Heptane0.373.370.753.372.403.53Ethylcyclopentane0.523.53Ethylcyclopentane2-Phenyl-butyronitrile6.37Benzeneacetaldehyde7.53DL-Norleucin2-Phenyl-butyronitrile156167899.43 cis-1, 3-Dimethylcyclohexane 1.03DL-Norleucine24.069.85 1-Methyl-3-ethylcyclopentane 0.648.64 1, 2-Ethanediol monoacetate78910.96Octane9.25 cis-1, 3-Dimethylcyclohexane0.6210 11.56 cis-1, 4-Dimethylcyclohexane10 9.85 1-Methyl-3-ethylcyclopentane 0.7012.27Ethylcyclopentane1110.752, 4-Dimethylhe1215.30Ethylcyclohexane12 11.65 cis-1, 4-Dimethylcyclohexane 0. 2213 15.96 1, 3, 5-TrimethylcyclohexaneEthylcyclopentane1421.39Ethylbenzene5.4214 14.53 n-Propylcyclopentane152281o-Dimethylbenzene10.51Ethylcyclohexane1623.69m-Xylene1.61621.47amylbenzene9.02E22.42Benzeneacetaldehyde16.0RTponent1823.72o-Dimethylbenzenearea(%)BenzeneRTComponentRelativeHeptane(min")area(%)234Cyclohexylmethane149Ethylcyclopentane2950.01682-Phenyl-butyronitrile3.422-Methoxyfuran0.197.49DL-Norleucine3.53Ethylcyclopentane0.178.88Glutaric acid6.37Benzeneacetaldehyde6781, 3-Dimethylcyclohexane0.882-Phenyl-butyronitrile15619.88 1-Methyl-3-ethylcyclopentan 0.621010.550.638.23Methyl 3-0-acetyl-23.03exane0230.058.86sovaleric acid20.361315.29Ethylcyclohexane0.7210 9.42 cis-1, 3-Dimethylcyclohexane0.961421.37Ethylbenzene11 10.02 1-Methyl-3-ethylcyclopentane 0.43O-Dimethy benzene1210.95Octane1623.56m-Xylene11.63 cis-1, 4-Dimethylcyclohexane0.19Isoxazole00214.335-Methyl-2-hexanol0.02bers for the larger molecules decreased1615.01Neohexane0.03171566Ethylhexanol18 15.91 1, 3, 5-Trimethylcyclohexane 0.164 Conclusions19 16.88 3-Ethyl-2-methylhexane2018.883-Methyl-l-hexanol0.03The main conts af methylbenzene/ethanol ex-212145ethylen3.63tractive of中国煤化工anes, esters and2223.72acids. TheC MH Actives changedp-Xylene0.75from 2.35%-3.44% along with an increase in theamount of ethanol in the tested solutions. In solventsZHANG Bin et al. The effect of methylbenzene/ethanol ratios on chemical compositionTable 3 Size distribution of the leached particle in five different solutionsarticle size(nm21.0-51.255.4-100.649410.251.253.614.514.9541060-156617.528.318.228.721.928.622.79.2164.0-255016.314.223.522.0287.3-393.422921,518.3455.3-1123.324.521.70.318.90.20.2128806440.01.21.00.70.7Note: V represents volume fraction and N represents numerical fractionwith higher amounts of ethanol, some acidic structuresand chemical properties of extractives from polar. Paper Scior acids, such as glutaric acid, developed. As well,Technol, 29(6): 120-126( in Chinese with English abstract)with an increase in the amount of ethanol in the sol-Martin-Sampedro R, Eugenio M E, Villar J C. 2011. Biobleachvent. the v and n number of smaller molecules of sizeing of Eucalyptus globulus kraft pulps: Comparison between21.0-51.2nm,55.4-100.6 nm and106.0-1566nmpulps obtained from exploded and non-exploded chips. Bio-resour Technol, 102(6): 4530-4535increased while these two numbers in larger moleculesOu Y F, Li Z Z. 1996. A preliminary study on chemical com-ponent and structural type of extractives in Eucalypt woodJ Nanjing Forest Univ, 20(3): 1-5(in Chinese with EnglishAcknowledgementsPeng H, Han D P, Liu Y H, Zhang J S, Ruan R S. 2010. GCMS analysis of fatty acid composition of different organicsolvent extracts from Cornus wilsoniana seeds. Food SciThis work was financially supported by the China31(12): 197-199(in Chinese with English abstract)Postdoctoral Science Foundation(No 20100480754) Peng WX, Li K F, Wu Y Q, Zhang D Q, Ma Q Z. 2007.Deter-and National Natural Science Foundation of chinamination of chemical components of benzene/ethanol extracNo.21176095)tives of Eucalyptus urograndis wood by GC/MS. Acta SciNat Univ Sunyatseni, 46(suppl ) 316-317Peng Wx, Wu S B. 2008. Leaching laws of micro/nano par-ticles from Eucalyptus camaldulensis wood. J South ChinaReferencesUniv Technol (Nat Sci Edn), 36(7): 11-15 (in Chinese withAgarwal A K. 2007. Biofuels(alcohols and biodiesel) applica- Qin MH, XuQ H, Shao Y, Gao Y, Fu Y J, Lu xM, Gao P J,tions as fuels for internal combustion engines. Prog EnergyCombust Sci, 33: 233-271and hydrophilic extractives of wheat straw. Bioresour TechBrito JO. Silva F G. Leao mm. Almeida G. 2008. 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