chemical engineering research and design 8 8 ( 2 0 1 0 ) 633640

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Chemical Engineering Research and Design

journal homepage: www.elsevier.com/locate/cherd

Acid hydrolysis of olive tree biomass

I. Romero, E. Ruiz, E. Castro, M. Moya
Department of Chemical, Environmental and Materials Engineering, Campus Las Lagunillas, University of Jan, 23071 Jan, Spain

a b s t r a c t
Olive tree cultivation generates a great amount of biomass residues which have no industrial application. Pruning residues are usually grindered or burnt on elds, causing economical costs and environmental concerns. An alternative issue for these renewable sugar-containing feedstocks may be the conversion into fuel ethanol by hydrolysis and fermentation. As a rst step in the bioconversion process, the acid hydrolysis of olive tree pruning is studied and a mathematical model predicting both ber content and sugar release as a function of operation variables is proposed. Sulphuric acid concentration in the range 032% (w/w), process temperature between 60 and 90 C and hydrolysis time from 0 to 240 min were used as hydrolysis conditions. The process was modelled by rst-order reaction kinetics. The apparent kinetic constant relating acid concentration to ber hydrolysis and sugar release shows a potential dependence; on the other hand, an Arrhenius-type equation has enabled the evaluation of activation energy values of 26.4 and 25.9 kJ/mol for ber hydrolysis and sugar generation, respectively. 2009 The Institution of Chemical Engineers. Published by Elsevier B.V. All rights reserved. Keywords: Olive tree pruning; Hemicellulose; Cellulose; Acid hydrolysis; Kinetic modelling; Reducing sugars

1.

Introduction

The production of energy from renewable resources has deserved a great deal of interest in the last two decades. Face to fossil fuels, bioethanol represents an attractive option. Nevertheless, bioethanol production costs are still relatively high. The use of lignocellulose materials like agricultural residues may contribute to the economy of the global conversion process (Sun and Cheng, 2002) due to their large availability, low cost, need of disposal and the lack of economic applications. Other advantages of using bioethanol as a fuel include a net reduction of CO2 emissions and a decrease in fuel imports dependence. Olive tree cultivation is spread throughout Mediterranean countries where it represents one of the main agricultural land uses. Due to olive oil health benets olive tree cultivation is getting more and more widespread. Olive tree pruning is a periodical culture operation by means of which less productive branches are cut off and trees are rejuvenated. This action generates an annual volume of lignocellulosic residues estimated at 3000 kg/ha (Snchez et al., 2002), thus constituting a widely available, renewable, cheap sugar resource. Just in Spain, the main olive oil producer in the world, some 7 106 t/year of

olive tree pruning biomass are available. A typical pruning lot includes leaves, thin branches and wood. To prevent propagation of vegetal diseases, these residues are commonly grinded and abandoned in the elds or burnt with associated costs, environmental concerns and, till date, no economical alternatives. Olive tree wood has a limited application as domestic rewood; the possibility of being used as a raw material for bioethanol production has been reported (Cara et al., 2006; Romero et al., 2007a). Like any other lignocellulosic residue, olive tree pruning primarily comprises three major fractions cellulose, hemicellulose and lignin plus lesser amounts of minerals (ash) and other compounds often termed extractives. The conversion process of lignocellulosic residues into ethanol implies basically two operations, hydrolysis of cellulose and hemicellulose bers for yielding monomers (sugars) and fermentation by microorganisms. The hydrolysis step may be carried out either enzymatically or by acid treatment. Enzymic hydrolysis is conducted at mild conditions but requires a pre-treatment of the raw material to improve the enzymatic digestibility (Sun and Cheng, 2005) and longer retention times (Ingram et al., 1999). Moreover, the production and recovery of enzymes may affect this option from

Corresponding author. Tel.: +34 953212195. E-mail address: mmoya@ujaen.es (M. Moya). Received 12 February 2009; Received in revised form 4 September 2009; Accepted 20 October 2009 0263-8762/$ see front matter 2009 The Institution of Chemical Engineers. Published by Elsevier B.V. All rights reserved. doi:10.1016/j.cherd.2009.10.007

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an economic point of view (Iranmahboob et al., 2002). Acid hydrolysis may be carried out either at dilute or concentrate acid conditions. Dilute acid hydrolysis attacks polysaccharides, especially those from the hemicellulose fraction which is easier to hydrolyse than cellulose. In addition, no acid recovery steps are required and acid losses are not important. On the negative side, the yield on glucose from cellulose is low. Concentrated acid hydrolysis enables high ethanol yield because of almost quantitative conversion of cellulose into glucose, although acid recovery is required as well as more resistant reactors. Comparing with dilute acid hydrolysis, lower temperatures and pressures are needed with shorter retention time, yielding higher ethanol yields (Iranmahboob et al., 2002). Sulphuric acid is the most commonly used in lignocellulosic residues hydrolysis (Baudel et al., 2005; Larsson et al., 1999) although other mineral acids like hydrochloric acid (Lavarack et al., 2002), nitric acid (Rodrguez-Chong et al., 2004) or phosphoric acid (Romero et al., 2007b) have also been assayed. In this work olive tree pruning residues have been submitted to sulphuric acid hydrolysis, under atmospheric pressure, at different conditions of acid concentration and temperature. The objective of this work was to propose a mathematical model so that the evolution of both ber hydrolysis and sugar generation can be predicted as a function of operational variables. Such information will be very useful for next research works in the study of an integrated biomass-to-ethanol process.

liquid fraction was analyzed for d-glucose and reducing sugars concentrations. To validate results predicted from sugar and ber kinetic models, a number of independent experiments, at different acid concentrations and temperatures, were also performed.

2.3.

Analytical methods

The raw material and the solid residues resulting at the end of each hydrolysis were characterized by determining moisture (TAPPI method T257), lignin (TAPPI method T222 os-74), neutral detergent ber (NDF), acid detergent ber (ADF) (Van Soest and Wine, 1967) and ash (TAPPI method T211). According to these methods, hemicellulose and cellulose contents are expressed as g/100 g of dry raw material: Hemicellulose = NDFADF Cellulose = ADFlignin The sum of hemicellulose and cellulose contents are referred as ber (Fiber = NDFlignin). The samples taken during hydrolysis were analyzed for the concentration of reducing sugars, using dinitrosalicylic acid (DNS) method (Miller, 1959) with xylose as a standard, and d-glucose by enzymatic methods (Boehringer Mannheim kit reference number 716 251).

2.4.

Fitting of data and modelling

2.
2.1.

Materials and methods

Raw material

Olive tree pruning residues were locally collected, air-dried at room temperature to equilibrium moisture content of about 9%, milled using a laboratory hammer mill (Retsch) and the resulting ground residue (particle size below 40 ASTM mesh) was then homogenized in a single lot and stored until used. The global composition of olive tree pruning (referred to dry matter) is (% w/w): hemicellulose (23.2 0.8), cellulose (30.6 0.8), lignin (20.9 0.5) and ash (3.5 0.2) (Romero et al., 2007a).

The experimental data were tted to the proposed models using commercial software (SigmaPlot v.11, Systat Sotware Inc., San Jose, CA, USA). The curve tter uses the MarquardtLevenberg algorithm to nd the coefcients (parameters) of the independent variable(s) that give the best t between the equation and the data based on the minimization of the sum of the squared differences between the observed and predicted values of the dependent variable.

3.
3.1.

Results and discussion

Fiber composition

2.2.

Sulphuric acid hydrolysis

The residue was hydrolysed at atmospheric pressure with sulphuric acid in a 1-l glass batch reactor provided with agitation and temperature control. The operation conditions were as follow: sulphuric acid concentration (C) was modied between 0 and 32% (w/w); the hydrolysis temperature (T) ranged between 60 and 90 C and the process time (t) from 0 to 240 min. The mechanical stirring was 150 rpm and the solid to liquid ratio was set to 1:10 (w/v) in all cases. Each batch charge consisted in 100 g of raw material and 1 l preheated acid solution. The evolution of the hydrolysis was surveyed by sampling (5 mL), at xed intervals. Sample volumes were taken into account for calculation. Triplicate experiments were performed and mean results are shown. The samples were centrifuged and reducing sugars and dglucose content of supernatants were measured. At the end of hydrolysis, two fractions were separated by ltration: a solid residue and a sugar solution. The former was waterwashed until neutral pH, air-dried and characterized. The

To study the inuence of hydrolysis conditions (acid concentration and temperature) the composition of the hydrolysed solids was referred to original raw material by introducing the unsolubilised fraction, FU (g/100 g raw material). This variable showed a linear dependence on temperature and a potential dependence on acid concentration: FU = (102.1 0.35 T) C0.11 (adjusted R2 = 0.994) (1)

This equation enables a line to be drawn in Fig. 1(a), similarly to that from Eq. (2) (see below). Fig. 1(a) and (b) shows remaining ber contents after 240 min acid hydrolysis as a function of acid concentration and temperature, respectively. As can be observed, increasing the treatment severity results in higher ber solubilisation, reaching total hemicellulose hydrolysis at 4.5% acid concentration, 90 C and 240 min. For comparison purposes, the composition of raw material is also included (discontinuous lines in Fig. 1). As expected, ber contents in the insoluble fraction resulting from hydrolysis decreased as long as acid concentration or temperature was increased. The average cellulose content determined at the end of hydrolysis remained constant (at the same value of the raw material) for all hydrolysis tem-

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Fig. 1 Fiber composition, referred to raw material, for dried solids after hydrolysis at different (a) sulphuric acid concentrations and (b) hydrolysis temperatures.

Fig. 2 Time evolution of reducing sugar yields at different (a) sulphuric acid concentrations and (b) hydrolysis temperatures. Experimental results (symbols) and model prediction (lines). On the other hand, lignin content determinations performed on hydrolysed solids were almost constant and similar to that of original raw material, no matter what the experimental hydrolysis conditions were. This indicates that there is virtually no lignin degradation caused by temperature or acid concentration at the assayed operational conditions and that modications on detergent bers contents are attributable only to the hydrolysis of hemicellulose and cellulose.

peratures and when low acid concentrations were used. Only when the hemicellulose fraction was solubilised (e.g. C = 4.5% at 90 C), the nal cellulose content decreased as long as acid concentration was increased, showing a sequential hydrolysis of bers, beginning with that of hemicellulose. This is in agreement with other authors results who report that it is not possible to reach total and simultaneous conversion of cellulose and hemicellulose from sugar cane bagasse by acid hydrolysis (Gmez et al., 2006). Following the tendency observed in Fig. 1, experimental ber-remaining (FR ) data have been adjusted to: FR = (90.05 0.556 T) C0.18 (adjusted R2 = 0.997) (2)

3.2.

Sugar yields

Eq. (2) allows the ber content to be predicted at different conditions for temperature and acid concentration. Continuous lines in Fig. 1 have been drawn using Eq. (2); as can be seen, agreement between experimental (symbols) and calculated values is found. Eq. (2) shows that hydrolysis temperature exerts, under these conditions, a constant solubilisation effect on olive tree pruning ber. Regarding sulphuric acid concentration, the derivative of Eq. (2) with respect to this variable shows a sharp hydrolysing effect at little concentrations, vanishing as acid concentration is raised. It seems that, based just on the hydrolysis yield, acid concentrations of approximately 5% might be enough.

From concentrations of reducing sugar and d-glucose determined in the hydrolysis samples, and taking into account the variations in the reactor volume, the yields in reducing sugars and d-glucose, Y (g/100 g dried raw material) were calculated. Reducing sugar yields obtained at 90 C are shown for some of the experiments performed at varying acid concentrations in Fig. 2(a) and at different hydrolysis temperatures and 4.8% acid concentration in Fig. 2(b). Except for the hydrolysis without acid, an increase in the sugar yields (both reducing sugars and d-glucose) with time was detected in all cases. This increase was sharper at the beginning of the process and when higher acid concentrations and temperatures were used; however, as long as the hydrolysis proceeds, it seems that sugar generation rates slow down. As can be seen, maxima yields are different at each temperature and acid concentration condition. More-

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Table 1 Kinetic model parameters for reducing sugar and d-glucose yields. a
Reducing sugar d-Glucose 5.90 1.32

b
0.25 0.049

m
0.17 0.23

Y0 , g/100 g
2.7 0.52

k0 , min1
38.4 24.8

E, kJ mol1
25.9 24.8

n
0.79 0.68

Adjusted R2
0.977 0.973

over, once the maximum yield was attained, no time changes were detected. The sugar yield obtained in the hydrolysis performed just with distilled water (C = 0.0) remained constant from the beginning throughout the experiment; this behaviour may be attributable to the presence of a fraction of ber that was instantaneously hydrolysed.

3.3.

Kinetic model for sugar generation

Most of proposed kinetic models on ber hydrolysis and sugar generation assume that there are two types of bers, i.e. a fast-reacting fraction and a slow-reacting one and that the overall ber hydrolysis is the sum of two irreversible, simultaneous, rst-order reactions (Esteghlalian et al., 1997; Ynez et al., 2004). In this work, the model that best t experimental data was that proposed by Saeman (1945), initially derived for cellulose hydrolysis but also applied by other researchers to hemicellulose fraction from agricultural residues (Tllez-Luis et al., 2002). Saemans model considers a rst order, irreversible reaction. Taking into account that, at each acid concentration and temperature assayed, there is a minimum sugar concentration at the beginning of olive tree pruning residue hydrolysis and a maximum sugar concentration attainable at high process time, Ymax (see Fig. 2), the sugar generation may be expressed by: dY = k (Ymax Y) dt t=0 t= Y = Y0 Y = Ymax

Fig. 2, there is no sugar degradation at the experimental conditions. Furfural or other sugar degradation compounds were actually not measured because it was assumed that operational conditions, especially in that concerning pre-treatment temperature, were soft enough to ensure that sugar degradation could take place in only a very limited extension. Using olive tree pruning biomass, furfural concentrations below 3.3 g/100 g raw material were detected in the liquid fractions issued from steam explosion pre-treatment at steam temperatures as high as 200 C, when the biomass was previously impregnated with 1.4% sulphuric acid (Cara et al., 2007). By integration, it can be deduced: Y = Y0 exp[k t] + Ymax (1 exp[k t]) (4)

According to Fig. 2(a), the maximum sugar yield attainable in the hydrolysis process is dependent on the sulphuric acid concentration in each experiment, rather than on a unique value corresponding to total ber hydrolysis. From experimental results, a potential relationship may be established between sugar yields and sulphuric acid concentration, and a linear one between sugar yields and hydrolysis temperature, in a similar way to that previously obtained for ber analysis, Eq. (2). Assuming these dependences and considering that the initial sugar concentration is independent from both acid concentration and temperature, the maximum sugar yield may be stated as the following equation: Ymax = (a + b T) (C)
m

(3)

(5)

where k stands for the apparent kinetic constant (min1 ), assuming that sugar generation is produced in several consecutive steps starting with ber hydrolysis, and Y0 is the initial sugar concentration obtained following instantaneous hydrolysis of ber. It is assumed that, according to data in

where a, b, and m are adjust parameters. As far as the kinetic constant is concerned, most of proposed models accept a potential dependence on acid concentration and an Arrhenius-type dependence on temperature (Aguilar et al., 2002; Eken-Saracoglu et al., 1998; Herrera

Table 2 Maximum yield in reducing sugars (YRSmax ) and d-glucose (YGmax ), and hydrolysable bers (FHmax , FHNmax and FGmax , see text for details), g/100 g of dry raw material. C, %
T = 90 C 0.0 0.5 1.5 2.4 3.6 4.5 9.2 17.5 25.0 31.8

YRSmax
2.7 14.5 17.5 19.1 20.5 21.3 24.2 27.1 28.8 30.0

YGmax
0.52 2.6 3.4 3.8 4.2 4.4 5.3 6.1 6.6 7.0

FHmax
10.4 13.1 14.5 15.7 16.3 19.0 21.5 23.1 24.2

FHNmax
2.4 3.1 3.4 3.7 3.9 3.9 3.9 3.9 3.9

FGmax
1.9 2.6 3.0 3.3 3.5 4.3 5.0 5.5 5.8

T, C
C = 4.8% 60 70 80 90

YRSmax
10.1 15.0 18.3 21.6

YGmax
1.9 3.1 3.8 4.5

FHmax
8.0 10.9 13.8 16.7

FHNmax
1.9 2.6 3.2 3.9

FGmax
1.7 2.3 2.9 3.6

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Fig. 4 Time evolution of hydrolysable ber at varying acid concentrations and 90 C. (f = 132/150 for pentoses and f = 162/180 for hexoses). Assuming that ber solubilisation is the slowest process step, the ber hydrolysis rate should be equal to the sugar generation rate. So, considering rst-order kinetic reaction for ber hydrolysis, and Eq. (3), the following equation is derived: f dY dFH = f k (Ymax Y) = dt dt = kH FH t=0 t= Y = Y0 , Y = Ymax , FH = FHmax FH = 0 (7)

Fig. 3 Reducing sugar yields surface as a function of acid concentration and process time (hydrolysis temperature: 90 C). et al., 2003; Palmqvist and Hahn-Hgerdal, 2000): k = k0 exp E R TK (C)
n

(6)

where k0 is the pre-exponential parameter (min1 ), E is the activation energy for sugar generation (kJ/mol) according to the proposed model in Eq. (3), R = 8.3143 103 kJ/(mol K), TK is the temperature in K, and n is an adjust parameter. The parameters in Eqs. (4)(6) have been calculated by nonlinear adjusts from the results of reducing sugar and d-glucose yields obtained for all hydrolysis experiments. The parameter values, at a 95% condence level, are summarized in Table 1. The model predicted that initial reducing sugar yield and d-glucose yield were 2.7 g/100 g and 0.52 g/100 g, respectively, a close value to those obtained experimentally when only distilled water was used for hydrolysis (Fig. 2(a)). Once parameters in Eq. (4) have been determined, lines in Fig. 2 have been drawn, showing a good agreement between experimental results and model prediction. Table 2 summarizes maxima yields in reducing sugars (YRSmax ) and d-glucose (YGmax ), taking into account total sugars present in the solution, as a function of operation variables. An increase in maxima yields is detected as either hydrolysis temperature or acid concentration is increased. Fig. 3 shows the surface representation of Eq. (4) at 90 C hydrolysis temperature over the total range of acid concentration and process time. This kind of response surface provides useful information about operational conditions and results. For example, for obtaining the highest reducing sugar yield (2530 g/100 g), 15% acid concentration at least is required. In contrast, just a little lower sugar yield may be obtained in a wide range of acid concentration and time mild conditions (approximately from 4 to 8% and 120 to 40 min, respectively).

3.4.

Kinetic model for ber hydrolysis

The time evolution of ber at each temperature and acid concentration may be calculated from Eq. (4) and parameters in Table 1, taking into account ber/sugar conversion factor

where kH is the apparent kinetic constant for ber hydrolysis and FH is the amount of ber (g/100 g raw material) yielding sugars, others than those obtained from instantaneous solubilisation. Assuming the same value for both apparent kinetic constants in Eq. (7), k and kH , the time evolution of ber may be evaluated at any acid concentration and hydrolysis temperature, thus obtaining similar graphics to that depicted in Fig. 4. In the same way, d-glucose producing bers (FG ) may be determined by applying Eq. (7) to d-glucose results. By using Eq. (7) at the beginning of the experiment and the value for Ymax , the maximum amount of hydrolysed bers which generate sugars is determined at each trial (FHmax and FGmax ), Table 2. Considering that Eq. (7) cannot predict the amount of bers that are instantaneously hydrolysed, this is calculated from Y0 values for reducing sugars and d-glucose (Table 1) and the respective conversion factor (2.4 g/100 g and 0.47 g/100 g). By applying Eq. (7) to the acid concentration at which all hemicellulose is solubilised (C = 4.5%) and zero time, the maximum value of the hemicellulose that generates reducing sugars (FHmax = 16.3 g/100 g) is calculated, as well as the hemicellulose fraction that only produces d-glucose (FGmax = 3.5 g/100 g). As olive tree pruning contains 23.2 g hemicellulose/100 g de raw material, it can be concluded that only 80.6% of this fraction contributes to reducing sugar generation and 17.2% produces just d-glucose (taking into account also the fraction that is instantaneously hydrolysed at the beginning of the process). There is hence a fraction of hydrolysed ber (19.4% of the total hemicellulose) that yields no sugar (FHN ) and so the amount that is solubilised at the beginning can be estimated at 0.6 g/100 g. Globally, 3 g/100 g raw material are instantaneously hydrolysed, equivalent to 12.9% of the initial hemicellulose. As an example, Fig. 4 shows the time evolution of hydrolysable bers at 90 C and different acid concentration,

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Table 3 Kinetic model results for total hydrolysable bers. aH

Reducing sugar d-Glucose 8.20 1.39

bH
0.26 0.042

mH
0.20 0.26

kH0 , min1
44.3 25.6

EH , kJ mol1
26.4 24.8

nH
0.82 0.67

including the hemicellulose fraction that yields no sugars. As can be observed, the highest values are obtained at zero time, corresponding to the maximum value of hydrolysable bers at each acid concentration, which shows the signicant inuence that acid exerts on the hydrolysis process. A similar gure can be obtained when hydrolysis temperature is considered. By integrating Eq. (7): FH = FHmax exp[kH t] (8)

where FHmax stands for the maximum amount of hydrolysable bers at any particular operational conditions. Assuming that FHmax depends linearly on temperature and potentially on acid concentration (similarly to that observed with reducing sugars), an Arrhenius-type dependence on temperature of the apparent kinetic constant, kH , and potential dependence on acid concentration, both FHmax and kH can be evaluated as: FHmax = (aH + bH T) (C) kH = kH0 exp EH RTK
mH

(9) t (10)

determination method would only allow the monomers to be measured. According to Fig. 5(a), the initial hydrolysis rate increased with increasing sulphuric acid concentration. This allows different hydrolysis times to be used for different acid concentrations. For example, hydrolysis at 50 min time and 1.5% acid concentration yields a ber solubilisation of approximately 40% of maximum attainable at that acid concentration (which means 17% of total residue ber); if 9.2% acid concentration is used, up to 86% of maximum attainable are solubilised (equivalent to 46% of total residue ber). At 25% acid concentration, total ber solubilisation is reached in less than 50 min hydrolysis time, representing 58% of total residue bers. Water exerts no hydrolysing action on the residue, except for the amount initially hydrolysed that accounts for 5.3% of the total ber. Regarding temperature, Fig. 5(b) shows an increasing effect on hydrolysis as temperature increases. As far as hydrolysis time is concerned, an operation time beyond 100 min does not improve hydrolysis results in terms

(C)

nH

where aH , bH , mH and nH are adjust parameters, kH0 is the preexponential parameter (min1 ) and EH is the activation energy for ber hydrolysis (kJ/mol). The results of bers (those obtained by Eq. (8) plus the hemicellulose fraction that produces no sugars) have been adjusted by non-linear regression. The resulting parameter values are summarized in Table 3 and, as continuous lines, in Fig. 4. As can be observed, the model predicts an activation energy for ber hydrolysis of 26.4 kJ/mol. This value is lower than those reported for other lignocellulosic residues, in the range 53142 kJ/mol (Lavarack et al., 2002), which may indicate that, under the operational conditions assayed, the hemicellulosic fraction of olive tree pruning residue is easier to hydrolyse than that of other residues. By applying Eq. (8) to the hemicellulose content of the initial raw material (without considering the fraction instantaneously solubilised) and setting temperature to 90 C and time to 0 min, the acid concentration at which hemicellulose is completely solubilised may be evaluated. The value obtained was 4.7%, close to 4.5% determined experimentally (Fig. 1(a)). The evolution of hydrolysable bers as a function of temperature and acid concentration may be also predicted by Eq. (8). From this equation and adding the ber fraction that is instantaneously solubilised, the amount of bers remaining in the solid at any time is calculated (Fig. 5). As can be deduced from FHmax and FGmax -columns in Table 2, the kinetic model predicting d-glucose generation from bers is valid only at acid concentrations below 9%; beyond this point the model underestimates hydrolysis effect in comparison with experimental results. The reason may lie in the DNS sugar determination method (Miller, 1959), resulting in the fact that glucose as monomer is obtained up to 7 g/100 g while the remaining glucose stay in oligomeric form. As reported by Jeffries et al. (1998) the DNS reagent produces a partial hydrolysis of oligosaccharides while the enzymatic glucose

Fig. 5 Time evolution of remaining bers at (a) 90 C and different sulphuric acid concentrations and (b) varying hydrolysis temperatures and C = 4.8%.

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References
Aguilar, R., Ramrez, J.A., Garrote, G. and Vzquez, M., 2002, Kinetic study of the acid hydrolysis of sugar cane bagasse. J Food Eng, 55: 309318. Baudel, H.M., Zaror, C. and de Abreu, C.A.M., 2005, Improving the value of sugarcane bagasse wastes via integrated chemical production systems: an environmentally friendly approach. Ind Crops Prod, 21: 309315. Cara, C., Ruiz, E., Ballesteros, I., Negro, M.J. and Castro, E., 2006, Enhanced enzymatic hydrolysis of olive tree wood by steam explosion and alkaline-peroxide delignication. Process Biochem, 41: 423429. Cara, C., Ruiz, E., Oliva, J.M., Sez, F. and Castro, E., 2007, Conversion of olive tree biomass into fermentable sugars by dilute acid pre-treatment and enzymatic saccharication. Bioresour Technol, 99: 18691876. Eken-Saracoglu, N., Ferda Mutlu, S., Dilmac, G. and Cavusoglu, H., 1998, A comparative kinetic study of acidic hemicellulose hydrolysis in corn cob and sunower seed hull. Bioresour Technol, 65: 2933. Esteghlalian, A., Hashimoto, A.G., Fenske, J.J. and Penner, M.H., 1997, Modeling and optimization of the dilute-sulphuric-acid pretreatment of corn stover, poplar and switchgrass. Bioresour Technol, 59: 129136. Gmez, S., Gonzlez-Cabriales, J.J., Ramrez, J.A., Garrote, G. and Vzquez, M., 2006, Study of the hydrolysis of sugar cane bagasse using phosphoric acid. J Food Eng, 74: 7888. Herrera, A., Tllez-Luis, S.J., Ramrez, J.A. and Vzquez, M., 2003, Production of xylose from sorghum straw using hydrochloric acid. J Cereal Sci, 37: 267274. Ingram, L.O., Aldrich, H.C., Borges, C.C., Causey, T.B., Martnez, A. and Morales, F., 1999, Enteric bacterial catalysts for fuel ethanol production. Biotechnol Prog, 15(5): 855866. Iranmahboob, J., Nadim, F. and Monemi, S., 2002, Optimizing acid-hydrolysis: a critical step for production of ethanol from mixed wood chips. Biomass Bioenerg, 22: 401404. Jeffries, T.W., Yan, V.W. and Davis, M.W., 1998, Comparative study of xylanase kinetics using dinitrosalicylic, arsenomolybdate, and ion chromatographic assays. Appl Biochem Biotechnol, 7072: 257265. Larsson, S., Palmqvist, E., Hahn-Hgerdal, B., Tenborg, C., Stenberg, K., Zacchi, G. and Nilvebrant, N.O., 1999, The generation of fermentation inhibitors during dilute acid hydrolysis of softwood. Enzyme Microb Technol, 24: 151 159. Lavarack, B.P., Grifn, G.J. and Rodman, D., 2002, The acid hydrolysis of sugarcane bagasse hemicellulose to produce xylose, arabinose, glucose and other products. Biomass Bioenerg, 23: 367380. Miller, G.L., 1959, Use of dinitrosalicylic acid reagent for determination of reducing sugar. Anal Chem, 31: 426428. Palmqvist, E. and Hahn-Hgerdal, B., 2000, Fermentation of lignocellulosic hydrolysates. II. Inhibitors and mechanisms of inhibition. Bioresour Technol, 74(1): 2533. Rodrguez-Chong, A., Ramrez, J.A., Garrote, G. and Vzquez, M., 2004, Hydrolysis of sugar cane bagasse using nitric acid: a kinetic assessment. J Food Eng, 61: 143152. Romero, I., Snchez, S., Moya, M., Castro, E., Ruiz, E. and Bravo, V., 2007, Fermentation of olive tree pruning acid-hydrolysates by Pachysolen tannophilus. Biochem Eng J, 36: 108115. Romero, I., Moya, M., Snchez, S., Ruiz, E., Castro, E. and Bravo, V., 2007, Ethanolic fermentation of phosphoric acid hydrolysates from olive tree pruning. Ind Crops Prod, 25: 160168. Saeman, J.F., 1945, Hydrolysis of cellulose and decomposition of sugars in dilute acid at high temperature. Ind Eng Chem, 37: 4352. Snchez, S., Moya, A.J., Moya, M., Romero, I., Torrero, R., Bravo, V. and San Miguel, M.P., 2002, Aprovechamiento del residuo de poda del olivar. Ing Qum, 34: 194202. Sun, Y. and Cheng, J., 2002, Hydrolysis of lignocellulosic materials for ethanol production: a review. Bioresour Technol, 83: 1 11.

Fig. 6 Comparison between ber values of solid residues determined experimentally and according to the proposed model, at different sulphuric acid concentrations ( ) and hydrolysis temperatures ( ).

of ber solubilisation, except for the smallest acid concentrations. According to Fig. 5, the hydrolysis effect will be the best when using the temperature as high as possible, although the risk of getting sugar degradation will concomitantly increase as reported by others researchers (Herrera et al., 2003). Fig. 6 compares the content in remaining ber after 240 min hydrolysis time both experimentally determined (Fig. 1) and predicted by the model (also shown in Fig. 5). The good agreement observed indicates that no sugar degradation is produced under the operational conditions assayed and that the proposed kinetic model described adequately the hydrolysis process in the range of sulphuric acid concentrations, temperature and time used.

4.

Conclusions

The hydrolysis of bers from olive tree pruning residues is a sequential process starting with hemicellulose solubilisation followed by that of cellulose. A small fraction of hemicellulose is instantaneously hydrolysed regardless of the acid concentration used. Only 80.6% of the hemicellulose produces reducing sugars as a consequence of hydrolysis process and 17.2% yields glucose. The temperature and the acid concentration have an important inuence on the maximum amount of bers that can be hydrolysed in each experiment. Although this maximum value increases with increasing variables values, acid concentrations beyond 6% and hydrolysis times greater than 100 min are not useful in terms of process yield improvement. It is better to increase operation temperature. An activation energy value of 26.4 kJ/mol has been determined for olive tree pruning residues hydrolysis, representing approximately a quarter of that calculated for other lignocellulosic residues, showing a greater tendency for sugars to be liberated. In conclusion, this largely available, renewable agricultural residue is susceptible to be hydrolysed and then fermented to ethanol.

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