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Bioresource Technology 98 (2007) 1951–1957 Autohydrolysis of agric ultural residues: Study of reaction byproducts Gil Garrotejcparajo@uvigo.es (J.C. Parajó). 0960-8524/$ - see front matter © 2006 Published by Elsevier Ltd. doi:10.1016/j.biortech.2006.07.049 complex phenolic compounds as dimmers or trimmers ( Bunzel et al., 2005 ) can be present in this type of materials, binding lignin with polysaccharides ( Pan et al., 2002 ). When autohydrolysis of a xylan-containing LCM is car- ried out under suitable operational conditions, the major reaction products are substituted xylooligomers (SXO), which have food and pharmaceutical applications ( Váz- quez et al., 2001 ). Considered as food additives, SXO have prebiotic properties ( Fooks and Gibson, 2002; Rycroft et al., 2001 ), derived from their preferential utilization by Bi W dobacteria ( Izumi and Kojo, 2003 ) and ability for inhib- iting the growth of Clostridium ( Izumi and Azumi, 2001 ). In the autohydrolysis media, SXO can be hydrolyzed to sugars, which can be decomposed ( Garrote et al., 2004a ). On the other hand, acetyl groups are partially saponi W ed, extractives are removed from the solid phase, a part of ashes are dissolved, compounds belonging to the acid-solu- ble lignin fraction are extracted and proteins may react with sugars to give Maillard Reaction Products. Because of these side e V ects, the compositions of autohydrolysis media are complex and SXO must be re W ned before application. Re W ning of liquors has been carried out by solvent extrac- tion and other separation operations ( Vázquez et al., 2001 ). The interest in performing a solvent extraction stage of SXO-containing autohydrolysis liquors lies in the following " id="pdf-obj-0-2" src="pdf-obj-0-2.jpg">
Bioresource Technology 98 (2007) 1951–1957 Autohydrolysis of agric ultural residues: Study of reaction byproducts Gil Garrotejcparajo@uvigo.es (J.C. Parajó). 0960-8524/$ - see front matter © 2006 Published by Elsevier Ltd. doi:10.1016/j.biortech.2006.07.049 complex phenolic compounds as dimmers or trimmers ( Bunzel et al., 2005 ) can be present in this type of materials, binding lignin with polysaccharides ( Pan et al., 2002 ). When autohydrolysis of a xylan-containing LCM is car- ried out under suitable operational conditions, the major reaction products are substituted xylooligomers (SXO), which have food and pharmaceutical applications ( Váz- quez et al., 2001 ). Considered as food additives, SXO have prebiotic properties ( Fooks and Gibson, 2002; Rycroft et al., 2001 ), derived from their preferential utilization by Bi W dobacteria ( Izumi and Kojo, 2003 ) and ability for inhib- iting the growth of Clostridium ( Izumi and Azumi, 2001 ). In the autohydrolysis media, SXO can be hydrolyzed to sugars, which can be decomposed ( Garrote et al., 2004a ). On the other hand, acetyl groups are partially saponi W ed, extractives are removed from the solid phase, a part of ashes are dissolved, compounds belonging to the acid-solu- ble lignin fraction are extracted and proteins may react with sugars to give Maillard Reaction Products. Because of these side e V ects, the compositions of autohydrolysis media are complex and SXO must be re W ned before application. Re W ning of liquors has been carried out by solvent extrac- tion and other separation operations ( Vázquez et al., 2001 ). The interest in performing a solvent extraction stage of SXO-containing autohydrolysis liquors lies in the following " id="pdf-obj-0-4" src="pdf-obj-0-4.jpg">

Bioresource Technology 98 (2007) 1951–1957

Bioresource Technology 98 (2007) 1951–1957 Autohydrolysis of agric ultural residues: Study of reaction byproducts Gil Garrotejcparajo@uvigo.es (J.C. Parajó). 0960-8524/$ - see front matter © 2006 Published by Elsevier Ltd. doi:10.1016/j.biortech.2006.07.049 complex phenolic compounds as dimmers or trimmers ( Bunzel et al., 2005 ) can be present in this type of materials, binding lignin with polysaccharides ( Pan et al., 2002 ). When autohydrolysis of a xylan-containing LCM is car- ried out under suitable operational conditions, the major reaction products are substituted xylooligomers (SXO), which have food and pharmaceutical applications ( Váz- quez et al., 2001 ). Considered as food additives, SXO have prebiotic properties ( Fooks and Gibson, 2002; Rycroft et al., 2001 ), derived from their preferential utilization by Bi W dobacteria ( Izumi and Kojo, 2003 ) and ability for inhib- iting the growth of Clostridium ( Izumi and Azumi, 2001 ). In the autohydrolysis media, SXO can be hydrolyzed to sugars, which can be decomposed ( Garrote et al., 2004a ). On the other hand, acetyl groups are partially saponi W ed, extractives are removed from the solid phase, a part of ashes are dissolved, compounds belonging to the acid-solu- ble lignin fraction are extracted and proteins may react with sugars to give Maillard Reaction Products. Because of these side e V ects, the compositions of autohydrolysis media are complex and SXO must be re W ned before application. Re W ning of liquors has been carried out by solvent extrac- tion and other separation operations ( Vázquez et al., 2001 ). The interest in performing a solvent extraction stage of SXO-containing autohydrolysis liquors lies in the following " id="pdf-obj-0-8" src="pdf-obj-0-8.jpg">

Autohydrolysis of agricultural residues: Study of reaction byproducts

Gil Garrote a , Elena Falqué b , Herminia Domínguez a , Juan Carlos Parajó a,¤

a Department of Chemical Engineering, Faculty of Science, University of Vigo (Campus Ourense), As Lagoas, s/n. 32004 Ourense, Spain b Department of Analytical Chemistry and Food Science, Faculty of Science, University of Vigo (Campus Ourense), As Lagoas, s/n. 32004 Ourense, Spain

Received 19 June 2006; received in revised form 20 July 2006; accepted 22 July 2006 Available online 6 October 2006

Abstract

Samples of rice husks and corn cobs were subjected to hydrothermal treatments in aqueous media under conditions leading to maxi- mal xylooligomer concentration, and the reaction liquors were extracted with dichloromethane (DCM) to assess the type and amount of reaction byproducts with potential application as food ingredients and cosmetics. The identiWed DCM-soluble compounds were classiWed in four categories (sugar-derived compounds, lignin-derived compounds, nitrogen-containing compounds and fatty acids). The experi- mental results were compared with literature data. © 2006 Published by Elsevier Ltd.

Keywords: Autohydrolysis; Byproducts; Corn cobs; Hydrothermal treatments; Rice husks

1. Introduction

Treatments of lignocellulosic materials (LCM) in aque- ous media (autohydrolysis or hydrothermal treatments) under optimized conditions lead to the solubilisation of hemicelluloses, leaving a solid phase enriched in both cellu- lose and lignin (Garrote et al., 1999). This solid phase can be subjected to further processing for obtaining a variety of commercial products, for example enzymatic hydrolysis and further fermentation of hydrolyzates, (Lasser et al., 2001; Rivas et al., 2004), allowing an integrated beneWt of the raw material. The hemicellulosic fraction of LCM accounts usually for 14–50% of the raw material dry weight, and is made up of amorphous heteropolysaccharides containing diVerent structural units (including xylose, arabinose, mannose, galactose or rhamnose), which can be substituted with phe- nolic, uronic or acetyl groups. Xylan (made up of a main backbone of xylose units) is the main hemicellulose compo- nent in hardwoods and many agricultural products (includ- ing corncobs and rice husks). Arabinose substituents and esteriWed ferulic acid (Parker et al., 2000, 2005) or more

* Corresponding author. E-mail address: jcparajo@uvigo.es (J.C. Parajó).

0960-8524/$ - see front matter © 2006 Published by Elsevier Ltd.

doi:10.1016/j.biortech.2006.07.049

complex phenolic compounds as dimmers or trimmers (Bunzel et al., 2005) can be present in this type of materials, binding lignin with polysaccharides (Pan et al., 2002). When autohydrolysis of a xylan-containing LCM is car- ried out under suitable operational conditions, the major reaction products are substituted xylooligomers (SXO), which have food and pharmaceutical applications (Váz- quez et al., 2001). Considered as food additives, SXO have prebiotic properties (Fooks and Gibson, 2002; Rycroft et al., 2001), derived from their preferential utilization by BiWdobacteria (Izumi and Kojo, 2003) and ability for inhib- iting the growth of Clostridium (Izumi and Azumi, 2001). In the autohydrolysis media, SXO can be hydrolyzed to sugars, which can be decomposed (Garrote et al., 2004a). On the other hand, acetyl groups are partially saponiWed, extractives are removed from the solid phase, a part of ashes are dissolved, compounds belonging to the acid-solu- ble lignin fraction are extracted and proteins may react with sugars to give Maillard Reaction Products. Because of these side eVects, the compositions of autohydrolysis media are complex and SXO must be reWned before application. ReWning of liquors has been carried out by solvent extrac- tion and other separation operations (Vázquez et al., 2001). The interest in performing a solvent extraction stage of SXO-containing autohydrolysis liquors lies in the following

  • 1952 G. Garrote et al. / Bioresource Technology 98 (2007) 1951–1957

points: (i) compounds derived from extractives and acid- soluble lignin can be removed from the media; (ii) the sepa- ration can be carried out without signiWcant losses of SXO; (iii) the solvent-soluble fractions have antioxidant and anti- microbial activities, which make them potentially suitable for food or cosmetic application (Garrote et al., 2004b, Moure et al., 2001). This work deals with the identiWcation and quantiWca- tion of reaction products from hydrothermal processing of corn cobs and rice husks, a basic information for assessing further puriWcation processes and developing possible applications of the extracted fractions.

2. Methods

  • 2.1. Materials

Rice husks (supplied by “Procesadora Gallega de Ali- mentos”, Lalín, Pontevedra, Spain) and locally collected corncobs were air-dried. Corncobs were milled to pass a 1 mm screen. Homogenised lots of milled corncobs and rice husks were prepared to avoid diVerences in composition among aliquots, and stored. Aliquots from the above homogenised lots were subjected to moisture determination (TAPPI standard T-264-om-88) and to conventional quan- titative acid hydrolysis with 72% H 2 SO 4 . The solid residue after hydrolysis was considered as Klason lignin after correction for ashes. Hydrolysates were analyzed for mono- saccharides (glucose coming from cellulose; xylose and arabinose coming from hemicelluloses) and acetic acid (coming from acetyl groups) by HPLC as reported else- where (Garrote et al., 1999). Uronic acids were determined spectrophotometrically (Blumenkrantz and Asboe-Hansen, 1973) using galacturonic acid as a standard for quantiWca- tion. Proteins were determined from the nitrogen content of samples, which was measured by elemental analysis (Flash

  • 1112 Series, Termo Finningan). Ashes were determined by

calcination (TAPPI standard T-244-om-93).

  • 2.2. Autohydrolysis

Lignocellulosic materials were contacted with water in a batch stainless steel reactor of 3.75 L (Parr Instruments Company, Moline, Illinois) with temperature control using a liquid/solid ratio of 8:1 kg/kg and heated to the desired temperature following the standard temperature proWle of the reactor. The Wnal temperatures leading to optimal SXO concentrations were 205 °C for rice husks (Vila et al., 2002) and 202 °C for corncobs (Garrote et al., 2002). Solid and liquid phases were separated by Wltration. The solid residue was washed, dried and used to measure the solid yield. Aliquots of the liquid phase were oven-dried at 105 °C to constant weight to measure the content of non-volatile components (NVC). Samples of liquors from hydrothermal treatments were Wltered through 0.45 m membranes and used for direct HPLC determination of glucose, xylose, arabinose, 5-hydroxy-2-methylfurfural (HMF), furfural,

and acetic acid, using IR detection for determination of glucose, xylose, arabinose and acetic acid, and DAD detec- tion for determination of furfural and HMF. Analysis were performed with a Biorad Aminex HPX-87H column eluted with 0.003 M H 2 SO 4 . A second sample of liquors was sub- jected to quantitative posthydrolysis (with 4% H 2 SO 4 at 121 °C for 40 min) before HPLC analysis and uronic acid determination. The increase in the concentrations of mono- saccharides and acetic acid caused by posthydrolysis pro- vided a measure of the oligomer concentration.

  • 2.3. Extraction

Liquors (150 mL) were treated with dichloromethane (DCM) in three-stage, crossXow extraction (employing 15, 7.5 and 7.5 mL in the respective stages), with 5 min of con- tact time and magnetic stirring at 600 rpm, and intermediate periods of 5 min for phase separation. The organic phases were mixed and concentrated under N 2 prior analysis.

  • 2.4. Gas chromatography–mass spectrometic analysis

GC–MS was performed using a Hewlett-Packard 5890- II gas chromatograph coupled to a mass spectrometer HP- 5970 using He as carrier gas (125,000 Pa). Analyses were carried out in splitless mode. Separation was performed using a 60 m £ 0.25 mm £ 0.25 m Wlm thickness HP-Inno- wax capillary column. Temperature was kept at 45 °C for 1 min, programmed to 230 °C at 3 °C/min, and then held for 30 min. Mass spectrometer was in EI mode (electron energy 70 eV; source temperature 250 °C), and data acquisition was made in scanning mode from 30 to 300 amu/s and 1.9 spectra/s. Compounds were identiWed by comparison of the retention time and mass spectra with library data of mass spectra and authentic compounds. Quantitation was performed by the internal standard method (using 3-octa- nol and 3,4-dimethylphenol as standards) using model compounds for calibration.

3. Results and discussion

  • 3.1. Composition of raw materials and liquors

Tables 1 and 2 show the composition of raw materials and liquors, as well as the standard deviation of data (based on six replicate determinations). The raw materials are deWned by their contents of glucan (corresponding to cellulose), xylan (measured as xylose equivalent, which form the main polymer backbone), xylan substituents (arabinose units, reported as arabinan expressed in sugar equivalent, and acetyl groups), lignin, ash, protein and other components. Xylan and xylan substituents accounted jointly for 20.0 and 40.6 wt% of rice husks and corncobs (in oven-dry basis). Autohydrolysis caused a substantial solubilisation of the feedstocks (21.0 and 36.2 o.d. wt% of rice husks and corn- cobs, respectively), yielding volatile components (mainly ace-

G. Garrote et al. / Bioresource Technology 98 (2007) 1951–1957

1953

Table 1 Compositional data of raw materials (wt%, oven-dry basis)

Fraction

Rice husks (% o.d. weight)

SD a

Corn cobs (% o.d. weight)

SD a

Glucan (cellulose)

36.7

0.74

34.3

0.53

Xylan

15.6

0.12

31.1

0.45

Arabinan

1.68

0.01

3.01

0.40

Acetyl groups

1.62

0.14

3.07

0.01

Uronic acids

1.14

0.17

3.45

0.31

Lignin

21.3

0.08

18.8

0.21

Ash

14.3

0.09

1.30

0.05

Protein

2.50

0.09

3.25

0.12

Others (by diVerence)

5.16

1.72

Results have been calculated from six replicate determinations. a SD D standard deviation.

Table 2 Compositional data of raw liquors (expressed weight percent of untreated, oven-dry raw material)

 

Rice husks (% o.d. weight)

Corn cobs (% o.d. weight)

Average

SD a

Average

SD a

Dissolved solid b

21.03

0.071

36.19

0.085

Non-volatile compounds

19.63

0.043

34.59

0.099

(NVC) Volatile compounds (VC, by diVerence) Volatile compounds identi Wed

1.40

1.60

Acetic acid

0.64

0.011

0.48

0.008

HMF

0.03

0.001

0.10

0.002

Furfural

0.26

0.011

0.47

0.011

Non-volatile compounds identiWed Arabinose

0.61

0.024

1.14

0.024

Glucose

0.79

0.034

0.47

0.005

Xylose

0.98

0.044

2.17

0.044

Gluco-oligosaccharides (GO)

2.23

0.054

0.49

0.005

Xylo-oligosaccharides (XO)

9.16

0.121

18.29

0.211

Arabino-oligosaccharides

0.36

0.007

1.01

0.019

(ArO) Acetyl groups-

0.38

0.008

1.51

0.021

oligosaccharides (AcO) Uronic acids

0.81

0.041

2.13

0.106

Others (by diVerence)

3.38

6.33

Results have been calculated from six replicate determinations. a SD D standard deviation. b Dissolved solid calculated as 100 – solid yield.

tic acid, furfural and HMF, but also volatile extractives not identiWed) and non-volatile components (NVC). NVC are made up of monosaccharides (glucose, xylose and arabi- nose), oligosaccharides (glucooligosaccharides GO, xylooli- gosaccharides XO and arabinooligosaccharides ArO, used to quantify the arabinose units linked to oligosaccharides), acetyl groups linked to oligosaccharides (AcO) and a frac- tion denoted “others”, calculated by diVerence respect to the total NVC content, which included uronic substituents of oligosaccharides and non-saccharide components, includ- ing proteins and protein-reaction products, phenolic com- pounds derived from the acid-soluble lignin fraction, dis- solved in-organic components and extractive-derived

compounds. As expected, SXO (calculated as the sum of XO and XO substituents) were the main reaction products, accounting for 65.9% and 67.7% of NVC for rice husks and corn cobs.

3.2. Analysis of DCM-soluble compounds

Solvent extraction has been frequently used to fraction- ate reaction liquors. Karagöz et al. (2004, 2006) extracted acidiWed autohydrolysis liquors from pine sawdust (treat- ment conditions, 180 °C and 280 °C) with diethyl ether, obtaining yields of 0.8% and 1.3% g soluble material/100 g o.d. sawdust, whereas Sun et al. (2003) achieved 0.56 g material soluble in DCM/100 g o.d. substrate in the liquid phase from water treatments of wheat straw (performed at 95 °C). In this work, the yields of DCM-soluble material were 0.322 and 0.514 g/100 g o.d. feedstock for rice husks and corncobs, respectively. In related studies, the direct extraction of lignocellulosic raw materials with DCM has been considered. Yields of 0.26, 0.44, 0.45 and 1.17 g/100 g o.d. raw material have been reported for Eucalyptus wood (Gutiérrez et al., 1999; Freire et al., 2002a), Eucalyptus bark

(Freire et al., 2002b), rice straw (Xiao et al., 2001) and

wheat straw (Sun et al., 2003). To our knowledge, no detailed studies have been reported on the quantiWcation of autohydrolysis reaction byproducts. IdentiWcation of compounds from this type of media has been reported for treatments of pine sawdust, hinoki bark, cellulose and wheat straw (Ehara and Saka, 2005; Karagöz et al., 2004; Quitain et al., 2003; Sun et al., 2003). Related studies have been published for aqueous treatments in catalyzed media, usually at temperatures in the range 280–400 °C. This information refers to media cat- alyzed with RbOH and CsOH (Karagöz et al., 2005), K 2 O 3

(Karagöz et al., 2006), Na 2 CO 3 (Klinke et al., 2002), NaOH (Taner et al., 2004), acetic acid (Taner et al., 2004) and

HNO 3 (Luo et al., 2002), but the distribution of products was strongly modiWed by the presence of catalysts. Fig. 1a and b shows the results obtained in the GC–MS analysis of the DCM-soluble fraction of liquors from hydrothermal treatments of corn cobs and rice husks, and Table 3 lists data concerning the respective compositional analysis. In order to allow an easier discussion of results, the compounds in Table 3 have been classiWed in to four groups: sugar-derived compounds (SDC), lignin-derived compounds (LDC), nitrogen-containing compounds (NCC) and fatty acids (FA). SDC accounted for 35.0 and 32.3 wt% of total mass identiWed in samples from corn cobs and rice husks, respec- tively. Furfural was the main compound belonging to this group, in amounts of 887.1 and 456.3 mg/kg for corncobs and rice husks; which corresponded to 83.3 and 76.7 wt% of the respective SDC fractions. Furfural (mainly from pentose dehydration in acidic media) has been found in related studies (Ciccioli et al., 2001; Guillén and Manzanos, 1999, 2002; Karagöz et al., 2004, 2005, 2006; Klinke et al., 2002; Quitain et al., 2003) and in studies with pure sugars

  • 1954 G. Garrote et al. / Bioresource Technology 98 (2007) 1951–1957

1954 G. Garrote et al. / Bioresource Technology 98 (2007) 1951–1957 Fig. 1. GC–MS chromatograms of

Fig. 1. GC–MS chromatograms of the dichloromethane soluble of hydro- thermal liquors from (a) corncobs, (b) rice husks. Numbers of peaks corre- spond to the compounds listed in Table 3.

(Srokol et al., 2004). In our work, 5-hydroxy-2-methylfur- fural was determined in liquors (see Table 2), but it was not detected in DCM-soluble fractions. Other reported sugar- degradation products obtained under harsh conditions (including pyruvaldehyde, levoglucosan or erythrose), whose occurrence has been reported (Sasaki et al., 1998; Ehara and Saka, 2005), did not appear in the analyzed fractions, probably owing to the comparative low severity of hydro- thermal treatments carried out in this work. Additional compounds of this group, including 2,5-hexane-dione, 5- methylfurfural, or cyclotene, already identiWed by Karagöz et al. (2004, 2005, 2006) in autohydrolysis media, were found and quantiWed in this work (see Table 3). Other major com- pounds found in the analysed fractions were 5-methylfurf- ural (in amounts corresponding to 10.4% and 16.2% of SDC for corn cobs rice husks, respectively), 4,5-dimethyl- furfural (in amounts corresponding to 1.9% and 2.0% of SDC for the same samples) and 2-acetylfuran (accounting for 1.2 and 1.8 of SDC for the respective samples). Com- pounds such as 2-acetylfuran, 2,5-hexanedione, 5-methyl- furfural, -butyrolactone, furfuryl alcohol, -valerolactone, dihydropyran or cyclotene, whose presence in LCM com- bustion smokes has been reported in literature (Ciccioli et al., 2001; Fine et al., 2004; Guillén et al., 1999, 2002) have been found in the DCM soluble fraction of autohydrolysis liquors from corn cobs and rice husks (see Table 3). 2-Acet- ylfuran, 2,5-hexanedione, 5-methylfurfural or furfuryl

alcohol have been reported to be also generated from mela- noidin decomposition (Adams et al., 2003, 2005), whereas autohydrolysis of glucose-glycine mixtures leads to the for- mation of cyclotene and lactones (Inoue et al., 2004). LDC fractions were obtained at yields of 1799.9 mg/kg from corn cobs and 1111.0 mg/kg from rice husks, corre- sponding to 59.2 and 60.4 wt% of the total mass identiWed for the respective substrates. Thirty aromatic compounds have been identiWed in the LDC fraction, the major ones being vanillin (accounting for 36.3 and 19.5 wt% of the LDC fractions obtained from corn cobs and rice husks, respectively), 4-vinylphenol (accounting for 13.8 wt% of LDC for both raw materials), 4-vinylguaiacol (16.1 and 8.1 wt% of LDC from corn cobs and rice husks, respec- tively), syringaldehyde (accounting for 8.0 and 8.7 wt% of LDC from the respective feedstocks) and 4-hydroxy-2- methoxycinnamaldehyde (accounting for 4.4 and 12.2 wt% of LDC from the respective feedstocks). 3-methylphenol was the major LDC component in pine sawdust autohydro- lysis media, followed by guaiacol, homovanillic alcohol, 4- ethylguaiacol, catechol, 4-methylguaiacol and phenol (Karagöz et al., 2006). Klinke et al. (2002) found a wide variety of phenolic compounds in the alkaline wet oxida- tion of wheat straw, being vanillic acid and vanillin the major components, followed by 4-hydroxybenzaldehyde, syringaldehyde, syringic acid, coumaric acid and guaiacol. Autohydrolysis treatments of wheat straw carried under mild conditions (Sun et al., 2003) led to a related distribu- tion of phenolic compounds, the most important being syringaldehyde, cinnamic acid, vanillic acid and vanillin, but at a much lower yield. Other compounds quantiWed in this work (including guaiacol, 4-ethylguaiacol, eugenol, 4-vinylguaiacol, syringol, isoeugenol, vanillin, acetovanil- lone, guaiacylacetone, methoxyeugenol, syringaldehyde, homovanillic acid and acetosyringone) were identiWed in liquors from wood treatments with supercritical water at 380 °C for 8 s (Ehara et al., 2005; Takada et al., 2004); whereas guaiacol, 2,4-ditertbutylphenol and 1,3-ditertbutyl- benzene have been found in autohydrolysis liquors from hinoki bark (Quitain et al., 2003). A variety of phenolic compounds have been identiWed in samples from rice and corn, some of them also found in this work: for example, Jezussek et al. (2002) found vanillin, guaiacol, 4-vinyl-guaiacol and 4-vinyl-phenol in simples of brown rice, whereas Fontaine et al. (2003) identiWed vanillin, 4-ethylphenol, 4-methylguaiacol, 4-vinylguaiacol, 4-vinylphenol, syringol, eugenol, guaiacylacetone, meth- oxyeugenol, syringaldehyde, coniferyl alcohol and acetosy- ringone in neutral detergent Wbre from corn. NCC were found in limited amounts (1.1% and 1.3% of total DCM soluble fraction from corncobs and rice husks, respectively). The major NCC were 1-pyrrol-2-carboxalde- hyde and methylpyrrolecarboxaldehyde. Related structures have been reported to be present in aqueous media contain- ing melanoidins from reactions of glucose and glycine (Inoue et al., 2004; Adams et al., 2003, 2005), as well as in roasted earth almond (Cantalejo, 1997).

G. Garrote et al. / Bioresource Technology 98 (2007) 1951–1957

1955

Table 3 Composition of the DCM-soluble fractions from corn cobs and rice husks (expressed as mg/kg of oven-dry raw material)

No.

t (min)

Name

Corn cobs

Rice husks

 

Average

SD a

Average

SD a

Sugar derived compounds

1065.1

595.2

  • 1 22,72

Furfural

887.1

13.7

456.3

1.6

  • 2 23,80

2-Acetylfuran

12.8

0.7

10.8

1.7

  • 3 23,93

2,5-Hexanedione

5.0

<0.05

2.9

0.5

  • 5 26,51

5-Methylfurfural

111.1

1.9

96.3

1.4

  • 7 27,96

4,5-Dimethylfurfural

20.6

0.5

12.0

0.4

  • 8 28,46

-Butyrolactone

3.6

<0.05

  • 10 29,43

Furfuryl alcohol

6.3

1.0

4.1

0.3

  • 11 30,52

-Valerolactone

5.2

0.3

3.0

0.1

  • 12 32,62

Dihydropyran

5.2

<0.05

3.9

0.5

  • 16 35,68

Cyclotene

4.4

0.1

5.9

0.2

  • 20 38,39

Furfural acetone

3.8

<0.05

Lignin derived compounds

1799.9

1111.0

  • 4 24,50

Benzaldehyde

7.0

0.7

3.8

0.8

  • 9 29,20

Benzeneacetaldehyde

9.3

0.3

3.6

0.2

  • 14 33,90

Acetophenone

10.8

0.1

1.4

0.4

  • 15 3,5-Dimethylbenzaldehyde

35,43

10.4

0.6

4.7

<0.05

  • 18 36,59

Guaiacol

48.2

0.3

44.0

2.4

  • 19 37,15

Benzyl alcohol

7.7

0.1

  • 23 41,46

Phenol

19.9

0.3

13.0

1.2

  • 25 42,30

4-Ethylguaiacol

6.4

0.1

  • 27 46,52

4-Eugenol

5.6

0.4

  • 28 46,75

4-Ethylphenol

3.3

0.5

2.5

0.1

  • 30 2,3-Dihydroxybenzaldehyde

47,12

9.5

0.7

3.4

<0.05

  • 31 47,56

4-Vinylguaiacol

289.8

7.2

89.6

4.3

  • 32 2,5-Dihydroxyacetophenone

48,25

9.6

0.5

  • 34 49,50

Syringol

32.5

2.5

30.7

2.4

  • 35 51,09

2,4-Ditertbutylphenol

22.5

1.5

16.6

1.0

  • 36 51,90

Isoeugenol

15.8

1.2

18.8

0.5

  • 37 52,94

4-Vinylphenol

248.0

5.3

153.4

19.3

  • 39 58,16

Vanillin

653.2

40.8

216.7

11.4

  • 40 58,70

Homovanillyl alcohol

13.7

1.1

7.6

0.5

  • 41 59,73

Acetovanillone

80.8

3.1

73.6

1.2

  • 42 60,18

Guaiacylacetone

12.1

1.1

62.0

4.2

  • 43 61,55

Methoxyeugenol

7.4

0.2

  • 44 61,98

Coniferyl alcohol

6.6

<0.05

20.5

0.3

  • 47 68,17

Syringaldehyde

144.7

7.7

96.9

5.1

  • 48 68,23

4-Hydroxybenzaldehyde

12.9

<0.05

  • 49 69,16

Homovanillic acid

41.2

0.9

  • 50 69,90

Acetosyringone

25.1

0.9

45.6

5.1

  • 51 70,39

Acetylphenol

8.2

0.3

6.9

0.1

  • 52 1-(2,6-Dihydroxy-4-methoxyphenyl)-ethanone

70,74

18.1

1.8

  • 53 4-Hydroxy-2-methoxycinnamaldehyde

76,78

79.2

1.6

136.1

8.6

Nitrogen-containing compounds

34.3

23.1

6

27,49

2-Acetylpyridine

4.7

0.6

2.5

0.1

  • 22 40,29

2-Acetylpyrrol

3.9

0.1

  • 24 1-Pyrrol-2-carboxaldehyde

41,90

17.4

2.1

7.1

0.6

  • 33 Methylpyrrolecarboxaldehyde

48,39

12.2

0.1

9.7

0.3

Fatty acids

142.9

111.1

  • 13 Pentanoic acid (valeric acid)

32,70

4.0

<0.05

  • 17 Hexanoic acid (caproic acid)

36,35

9.0

0.7

17.7

0.9

  • 21 Heptanoic acid (enanthic acid)

39,98

5.1

0.6

2.9

0.2

  • 26 Octanoic acid (caprylic acid)

43,48

2.7

<0.05

5.4

0.4

  • 29 Nonanoic acid (pelargonic acid, 9:0)

46,89

2.5

<0.05

3.9

0.2

  • 45 Tetradecanoic acid (myristic acid, 14:0)

62,09

28.4

2.3

6.8

0.3

  • 46 Hexadecanoic acid (palmitic acid, 16:0)

67,60

40.3

0.8

27.9

2.3

  • 54 Octadecanoic acid (stearic acid, 18:0)

77,23

30.0

1.7

23.8

<0.05

  • 55 9-Octadecenoic acid (oleic acid, 18:1)

78,52

13.0

0.6

13.5

1.0

  • 56 9,12-Octadecanedioic acid (linoleic acid, 18:2)

81,47

11.7

<0.05

5.2

0.5

Results have been calculated from three replicate determinations. a SD D standard deviation.

  • 1956 G. Garrote et al. / Bioresource Technology 98 (2007) 1951–1957

The contents of FA in samples from corn cobs and rice husks accounted for 142.9 mg/kg and 111.1 mg/kg, respec- tively, corresponding to 4.7 and 6.0 wt% of the DCM-solu- ble material. FA make part of LCM, and their content has been recently studied for a variety of feedstocks, including Eucalyptus wood (Gutiérrez et al., 1999; Freire et al., 2002a), yellow birch (Lavoie and Stevanovic, 2005), Xax (Gutiérrez and del Río, 2003; Morrison and Akin, 2001) or barks (Fre- ire et al., 2002b, HaWzoflu et al., 2002). Even though the total amount of FA and the relative proportions of individ- ual compounds vary in a wide range with the source studied, the most abundant FA have chains with more than 14 carbon atoms, and particularly chains of 18 carbon atoms (for example, octadecanoic, 9-octadecenoic and 9,12-octa- decanedioic acids). Tetradecanoic, 9-octadecenoic and 9,12- octadecanedioic acids also appear in important proportions. In related studies with other LCM, the predominant FA have been reported to be octadecanoic and hexadecanoic acids (Quitain et al., 2003) and heneicosanoic and hexadeca- noic acids (Sun et al., 2003). Saturated fatty acids with chains of 5, 6, 7, 8 and 9 carbon atoms have been found in this work, accounting for 13.6% and 30.5% of total FA in corncobs and rice husks. As these compounds do not appear in the DCM extractives of the untreated LCM, they must have been generated by hydrolytic reactions during the hydrothermal processing. This same compounds have been detected in smokes from Pinus pinea and wheat straw (Cic- cioli et al., 2001), sage and oak (Guillén et al., 1999, 2002) and woods (including white oak, red maple, sugar maple, douglas Wr and loblolly pine) (Fine et al., 2004).

4. Conclusions

Autohydrolysis liquors from rice husk and corn cob pro- cessing were extracted with dichloromethane (DCM). The yields in soluble material were 0.322 and 0.514 g/100 g oven dry feedstock for rice husks and corncobs, respectively. The identiWed compounds were classiWed in four groups: sugar- derived compounds (SDC), lignin-derived compounds (LDC), nitrogen-containing compounds (NCC) and fatty acids (FA). SDC accounted for 35.0 and 32.3 wt% of total mass identiWed in samples from corn cobs and rice husks, respectively. LDC corresponding to 59.2 and 60.4 wt% of the total mass were identiWed in samples from corn cobs and rice husks, respectively. NCC were found in limited amounts (1.1% and 1.3% of total DCM soluble fraction from corncobs and rice husks, respectively). The contents of FA in samples from corn cobs and rice husks accounted for 4.7 and 6.0 wt% of the DCM-soluble material from corn- cobs and rice husks, respectively. Furfural was the most abundant compound, followed by vanillin, 4-methylphenol and 4-vinylguaiacol.

Acknowledgements

Authors are grateful to the Spanish Ministry of Science of Technology for the Wnancial support of this work (in the

framework of the Research Project “Development of tech- nologies for the integral bene Wt of industrial byproducts”, Ref. CTQ2005-00745), which had partial Wnancial support from the FEDER funds of the European Union. Dr. Gil Garrote is a researched hired by the “Ramón y Cajal” Pro- gram of the Spanish Ministry of Education and Science.

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