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Industrial Crops and Products 42 (2013) 421428

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Industrial Crops and Products


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Furfural from midribs of date-palm trees by sulfuric acid hydrolysis


Hisham S. Bamueh , Yahia A. Alhamed, Muhammad A. Daous
Department of Chemical & Materials Engineering, Faculty of Engineering, King Abdulaziz University, P.O. Box 80204, Jeddah 21589, Saudi Arabia

a r t i c l e

i n f o

a b s t r a c t
Samples of midribs of Sukkaria date-palm tree obtained from several farms in Saudi Arabia as a waste material were rst analyzed using different ASTM standard procedures. Such samples were then subjected to acid hydrolysis using H2 SO4 at different concentrations, temperatures and liquid to solid ratios (LSR) to produce furfural. Analysis of the samples using the standard test of the Association of Ofcial Analytical Chemists (36D-AOAC) revealed that the pentosan content in these midribs was 14.54 wt.%. A maximum furfural concentration of 1114 g/m3 , corresponding to 53% furfural yield was obtained using 15 wt.% H2 SO4 and 50 ml/g LSR at 140 C. A reaction scheme for pentosan hydrolysis to produce furfural was proposed and a kinetic model for furfural production was developed. Regression analysis of the proposed model was applied to the experimental data. The tting of the data yields excellent predictions with R2 (0.960.99). Modied Arrhenius correlations of the regressed kinetic parameters were developed with acceptable accuracy of R2 (0.860.99). 2012 Elsevier B.V. All rights reserved.

Article history: Received 3 April 2012 Received in revised form 24 May 2012 Accepted 2 June 2012 Keywords: Furfural Palm-tree Midribs Hydrolysis Sulfuric acid

1. Introduction Furfural and its derivatives are considered in many instances strategic chemicals based on their various applications and use (Mansilla et al., 1998). Hydrogenation of furfural yields furfuryl alcohol which is employed in the chemical industry as an additive or solvent in the production of resins of different characteristics (Merlo et al., 2009). Moreover, one of the common and important usages of furfural is as a selective solvent for separating saturated from unsaturated compounds in petroleum rening, gas oil and diesel fuel (Mansilla et al., 1998). Furfural is exclusively produced from lignocelluloses biomass by dehydrating pentose (mainly xylose) which is present in significant amounts in the hemicelluloses of some agriculture residues and hardwoods. Feed stocks for furfural production are those with high pentosan content. The preferred feedstock are agricultural residues because these are homogenous and regularly available in large amounts from food processing plants (Montane et al., 2002). Furfural is also used as a feedstock for furfuryl alcohol in the production of thermosetting furan resin and furan cement by reacting phenols with such furfural derivatives (Brydson, 1999; Ibeh, 1999). These resins have excellent chemical and heat transfer resistances and nd industrial applications as foundry resins, as chemically resistant cements and binders, and as laminates in chemical plants (Brydson, 1999). Furfural is also used as a fungicide, weed killer and for the production of tetrahydrofuran (THF) (Zeitsch, 2000a).

Corresponding author. Tel.: +966 26952000x68811; fax: +966 26952257. E-mail address: hbamueh@kau.edu.sa (H.S. Bamueh). 0926-6690/$ see front matter 2012 Elsevier B.V. All rights reserved. http://dx.doi.org/10.1016/j.indcrop.2012.06.008

Several researchers investigated the production of furfural by hydrolysis of lignocellulosic waste materials in the presence of mineral acid as catalyst, such as HCl (Herrera et al., 2004, 2003; Lavarack et al., 2002), HNO3 (Rodriguez-Chong et al., 2004), H2 SO4 (Yat et al., 2008; Rahman et al., 2006; Aguilar et al., 2002; Montane et al., 2002), and H3 PO4 (Lenihan et al., 2010; Vazquez et al., 2007; Gamez et al., 2006). Raw materials reported in the literature included sugar cane bagasse (Gamez et al., 2006; Rodriguez-Chong et al., 2004; Aguilar et al., 2002; Lavarack et al., 2002), timber (Yat et al., 2008), sorghum straw (Vazquez et al., 2007; Herrera et al., 2004, 2003; Tellez-Luiz et al., 2002), olive stones (Rodrguez et al., 2008; Montane et al., 2002), olive trees (Romero et al., 2010), corncobs (Garrote et al., 2001; Eken-Saracoglu et al., 1998) and rice hulls (Mansilla et al., 1998). Other studies investigated furfural production at higher pressures (1025 bar) and temperatures (220240 C) (Karimi et al., 2006), and employing short reaction times (Montane et al., 2002; Eken-Saracoglu et al., 1998). Furfural is usually produced in a series of different hydrolysis reaction steps followed by a dehydration step. These reactions are preferred to take place in an acidic medium where breaking up of the polymeric pentosan molecules can take place relatively fast in the hydrolysis step. Moreover, furfural yield as well as reaction rate increase with increasing H+ ion concentration at elevated temperatures. Furfural yield, however, decreases during the dehydration step, due to the formation of condensation products and residue formation. Thus, in order to obtain higher yields of furfural, it must be removed right after the hydrolysis step and before residue formation takes place (Zeitsch, 2000b). The maximum theoretical yield of furfural is reported at 72.7% (Zeitsch, 2000a), while, depending on reaction temperature and acid concentration,

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a maximum practical furfural yield of 5065% can be obtained (Montane et al., 2002). Hydrolysis reactions of lignocelluloses in an acidic medium are very complex, mainly because the substrate is in a solid phase while the catalyst is in a liquid phase (Herrera et al., 2003). Various suggested mechanisms for such hydrolysis reaction have been reported by different investigators. Due to the difculty in modeling these processes, however, simplied empirical models are commonly used to represent these reactions and to determine their kinetics (Aguilar et al., 2002). Acid hydrolysis may be carried out using either dilute or concentrated acids. Dilute acid hydrolysis attacks polysaccharides, especially those from hemicellulose fraction which is easier to hydrolyze than cellulose. Concentrated acid enables high conversion of cellulose thus high yield of furfural may be obtained (Romero et al., 2010). The use of lignocellulosic materials like agriculture residues can appreciably contribute to the global economy of alternative energy production due to their large availability, low cost, need for their proper disposal, and of course their suitability to yield value added products (Romero et al., 2010; Herrera et al., 2003). Date palm trees are an abundant natural resource in the Kingdom of Saudi Arabia. Current statistics show that there are more than 23 million palm trees in the Kingdom as reported by ministry of agriculture in Saudi Arabia (http://www.moa.gov.sa/les/stat24/5/12.htm). The yearly trimmed palm tree branches are about 250,000 t reported by Agricultural Development Fund in Saudi Arabia (http://www.adf.gov.sa/agricultural/NewsDisplay.aspx). Therefore, nding ways to economically exploit the abundant wastes of this natural resource to produce valuable product such as furfural is extremely appealing. Studies available on furfural production from dates palm tree wastes are scarce, relatively old and limited in scope (Daous and Yorulmaz, 1989; Bassat, 1975). The objective of this work is to investigate the production of furfural from midribs of date palmtrees using a sulfuric acid catalyzed hydrolysis process. The effect of various operating parameters such as reaction temperature, liquid to solid ratio, acid concentration and reaction time are investigated and their optimum conditions to maximize furfural yield is determined. A kinetic model of the hydrolysis reaction is also developed based on experimental data generated. 2. Experimental 2.1. Raw material preparation Samples of midribs of Sukkaria (a popular type of dates palm tree in Saudi Arabia) were obtained from a palm-tree farm in Saudi Arabia. Fresh midribs were thoroughly washed, cleaned and dried. Size reduction was initially carried out by manual chopping, followed by grinding using a disc mill. Samples were then sieved using mechanical shaking screens based on ISO test sieve series. Particle sizes in the range of 0.250.5 mm were utilized for this study. Representative samples of this waste raw material were then subjected to necessary analysis for their composition of pentosan, moisture, ash and acid insoluble lignin. 2.2. Raw material characterization Midribs samples were characterized using different ASTM procedures, such as (ASTM D-1106) for moisture content, (ASTM D-1102) for ash content, (ASTM D-1107) for ethanolbenzene solubility, (ASTM D-1107) for ethanoltoluene solubility, and (ASTM D-1106) for acid-insoluble lignin. On the other hand, pentosan content of these samples was determined according to AOAC Phloroglucinol Method, the Association of Ofcial

Analytical Chemists AOAC-36D, which is the ofcial method acknowledged by AOAC for the determination of pentosans. AOAC-36D standard test is based on 100% conversion of the pentosan to furfural and measuring the furfural thus obtained, which means that furfural losses by resinication (reaction of furfural with itself) and by condensation (reaction of furfural with intermediates of the pentose-to-furfural conversion) must be completely avoided (Zeitsch, 2000b). 2.3. Hydrolysis reaction Hydrolysis reaction was conducted in a Parr batch reactor, model number 5112. It is made of a 1500 ml stirred type glass jacketed reactor with a maximum pressure of 10 bars. The reactor head and internal ttings are of Hastelloy B2 while all externals are made of stainless steel. The reactor is equipped with a solid sample addition arrangement, and a sampling mechanism to withdraw small samples of liquids for analysis of reaction products. At the start of each experiment, the required volume of acid of a given concentration was placed in the reactor. The required amount of raw material was also placed in the sample holder tted in the inner part of the reactor head. Once the reactor was carefully sealed and the cover properly tightened, heating of the reactor was commenced by circulating hot silicone (polydimethyl siloxane) oil in the reactor jacket, while the mixer was operated at 300 rpm to continuously stir the acid. When the desired acid temperature was reached and maintained, the solid sample was then introduced into the reactor mixture by pressurizing the sample holder, thus releasing the Teon cap holding the sample inside the sample holder. This procedure insured that the solid sample was instantaneously released into the hot acid solution. Reaction time monitoring was started at this instance and liquid samples from the reaction mixture were collected at relatively short intervals of 510 min in the initial 60 min of the reaction and at 30 min intervals beyond that. To maintain a relatively constant volume reaction system throughout a given experiment, the total volume of samples withdrawn throughout the experiment was less than 10% of the initial volume of the liquid. Experimental runs were performed at three different acid concentrations of 5, 10, and 15 wt.%, three levels of liquid to solid weight ratios of 50, 70, and 100 ml/g, and three different temperatures of 100, 120, and 140 C. 2.4. Product analysis Small liquid samples from the hydrolysis reaction were periodically collected, ltered in a Whitman lter paper and diluted with distilled water (1:100, v/v). Exactly, 20 l of the diluted sample was injected into a Shimadzu HPLC unit using a liquid sampling valve. A 4.6 mm i.d. 50 mm Shim-Pack XR-ODS column was utilized to achieve the desired separation of targeted hydrolysis products. A mixture of 84% of 0.01 N H2 SO4 and 16% of acetonitrile was used as a carrier liquid. A 0.5 ml/min ow rate at 4.9 MPa was maintained throughout the analysis. A programmable UV detector set at 280 nm for most components and 215 nm for only a few was found to be the most optimum operating conditions for the HPLC analysis. Thus, the HPLC was programmed to switch on the required UV wavelengths at the retention times of the corresponding targeted components in each test. Peak areas for each component were recorded and utilized to quantify the components with the help of previously calibrated components response factors. Furfural yield was calculated by the following equation %Yield = Yact 100 Yth (1)

where Yact is the experimentally determined yield, and Yth is the maximum theoretical yield based on a 100% conversion of

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pentosan to furfural in grams, which are calculated by the following two equations respectively Yact = C V Yth = MwtF Mwtp %P 100 W (2) (3)

Table 1 Chemical analysis of midrib samples by different standard methods. Physical property Pontosan, % Moisture content, % Ash content, % Ethanolbenzene solubility, % Ethanoltoluene solubility, % Acid-insoluble lignin, % Method AOAC-36D ASTM D-1106 ASTM D-1102 ASTM D-1107 ASTM D-1107 ASTM D-1106 wt.% 14.52 5.16 3.52 10.83 6.04 13.72

where C is the furfural measured concentration in g/m3 , V is the mixture volume in m3 , W is the mass of midrib sample used in grams, %P is the pentosan wt.% in midrib, MwtF and Mwtp are the molecular weights of furfural and pentosan, respectively. 3. Kinetics model Developing actual detailed mechanisms for hydrolysis reactions of lignocellulosic materials is quite a difcult and a cumbersome task. It is, therefore, a common practice to use simplied models to determine the kinetics of such hydrolysis. Commonly proposed models in the literature use pseudo-homogenous irreversible rst order reactions to describe such kinetics (Romero et al., 2010; Herrera et al., 2004, 2003; Aguilar et al., 2002). A similar approach is employed here, which further assumes that pentosan existing in the raw material is composed of two fragments; a fragment readily susceptible to hydrolysis (a fast decomposing fraction) and another more resisting and hence more difcult to hydrolyze (a slow decomposing fraction). The parameter is used in the kinetic model to dene the mass ratio of the fast decomposing pentosan to total pentosan in the raw material (Aguilar et al., 2002; Rodrguez et al., 2008). The chemical reactions in series responsible for the formation of furfural are proposed as follows (Herrera et al., 2004; Aguilar et al., 2002).
k1 k2 k4

where Cp0 is the total pentosan available in the raw material, leads to the following solutions of the above differential equations for the pentosan, pentose, and furfural concentrations as a function of hydrolysis time. 4. Results and discussions 4.1. Characterization of Dates midribs Table 1 shows a chemical analysis and characterization of datepalm tree midribs pertinent to this study. The data show that the midribs pentosan-content is 14.52 wt.%, which constitute an adequate content comparable to that found in wheat hulls, cotton seeds, and nut shells commonly used for furfural production. Because of the current importance of lignin as a raw material for the production of bioproducts and biofuels (Buranov and Mazza, 2008), midribs samples were also analyzed for their acid insoluble lignin using (ASTM D-1106) standard test. Table 1 shows that acid insoluble lignin constitute 13.72% of tested date-palm tree midribs, while their moisture and ash contents are 5.16%, and 3.52%, respectively.

Pentosan (s)Pentose (aq)Furfural (aq)Decomposition products (aq)Decomposition products (aq) where k1 is the hydrolysis reaction rate constant of the of the fast decomposing pentosan fraction, k2 is the rate constant of the decomposition reaction of pentose to furfural. k3 and k4 are the rate constants of pentose and furfural loss reactions to decomposition products, respectively. All k values are in min1 . The differential equations describing the rates of these reactions can be written as follows dCp = k1 Cp dt dCS = k1 Cp k2 CS k3 CS dt (5) (6)

k3

(4)

Remaining matter of midribs untested for in this study is expected to be celluloses and hemicelluloses. Values of pentosan and acid insoluble lignin contents for midrib samples determined in this study are closely comparable to those reported by Bassat (1975) for similar midrib samples. 4.2. Furfural production As mentioned earlier, the hydrolysis reaction tests were carried out at various values of acid concentration, reaction temperature, and liquid to solid weight ratio to study the effect of these operating parameters on furfural production kinetics and yield. The outcomes of these tests are discussed hereafter. 4.2.1. Effect of acid concentration Fig. 1 shows a plot of furfural concentration versus time for the hydrolysis reactions, carried out at 120 C and a liquid solid ratio of 50, at three levels of acid concentrations of 5, 10, and 15 wt.%. The gure clearly reects the effect of acid concentration on both the hydrolysis reaction kinetics and the furfural yield. The data show that the hydrolysis reaction proceeds much slower at the lower acid concentrations of 5 and 10 wt.% than that observed at 15 wt.% acid concentration. Moreover, at 15 wt.% acid, a maximum furfural concentration of 710 g/m3 (34% furfural yield) is obtained at around 150 min. This is much higher than that achieved at the lower two acid concentrations within the experimental time frame used, or can be anticipated to be achieved by using these lower concentrations for any extent of reaction time. The gradual decrease in furfural concentration beyond the maximum value achieved indicates that beyond certain achieved furfural concentration the rate of furfural loss to decomposition products becomes higher than the rate of furfural production.

where Cp is the concentration of the readily hydrolysable pentosan fraction (mol/l) and CS is the concentration of pontose (mol/l). The reaction step representing furfural loss consists of both a resinication reaction resulting from furfural reaction with itself and condensation reactions resulting from furfural reactions with intermediate products. Thus, the furfural rate equation can be written as follows dCF = k2 CS k4 CF dt (7)

where CF is the concentration of furfural in (mol/l). Using the following initial conditions CP = Cp0 , and CS = CF = 0 at t = 0, Cp = Cp0 ek1 t CS = CF = k1 Cp0 (ek1 t e(k2 +k3 )t ) (k2 + k3 ) k1 k1 k2 Cp0 (k2 + k3 ) k1 ek1 t ek4 t e(k2 +k3 )t ek4 t k4 k1 k4 (k2 + k3 ) (8) (9)

(10)

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800

1200
LSR= 50

Furfural Concentration, gm/m 3

Furfural concentration, gm/m 3

700 600 500 400 300 200 100 0 0 50 100 150 200 250 300
5 wt.% acid conc. 10 wt.% acid conc. 15 wt.% acid conc. model

1000 800 600 400 200 0 0 50 100 150

LSR= 70 LSR= 100 model

200

250

Hydrolysis time, min


Fig. 1. Furfural concentration versus reaction time at different acid concentrations using 0.250.5 mm dates tree midribs, LSR = 50, reaction temperature = 120 C.

Hydrolysis time, min


Fig. 3. Furfural concentration versus hydrolysis time at different liquid to solid weight ratio, using 15 wt.% H2 SO4 concentration at 120 C.

4.2.2. Temperature effect Fig. 2 shows a plot of furfural concentration versus time at three different hydrolysis reaction temperatures of 100, 120 and 140 C, while using 15% acid concentration and 50 ml/g liquid to solid ratio. The data show that a much faster increase in furfural concentration with time is observed when hydrolyzing at 140 C, and a maximum furfural concentration of 1114 g/m3 (a maximum furfural yield of 53%) is achieved after only 30 min of hydrolysis. However, beyond this maximum value, furfural concentration starts to fall rapidly and reaches values lower than those observed at the lower reaction temperatures at similar reaction times. This indicates that higher hydrolysis temperature favors both a higher furfural yield and faster formation kinetics up to the maximum achieved concentration, beyond which the rate of furfural loss becomes much faster than its rate of formation. Lower furfural yield and formation kinetics is observed at 120 C. At this temperature, it takes 120 min to achieve the maximum furfural concentration of only 710 g/m3 (a maximum furfural yield of 34%). However, the net rate of furfural loss beyond this maximum is much slower than that observed beyond the maximum achieved at the higher temperature of 140 C. At the lower temperature of 100 C, the hydrolysis reaction rates further slows down and no maximum furfural concentration is observed within the experiment run time.

An increase in hydrolysis reaction temperature leads to a decrease in hydrogen ion concentration of sulfuric acid, which becomes completely dissociated at higher temperature due to the decrease in the dielectric constant of water at higher temperatures. Thus, it is expected that at higher hydrolysis temperatures, the effect of acid concentration on reaction rate and furfural yield diminishes while that resulting from the growing energy of the reacting molecules gains dominance. 4.2.3. LSR effect Fig. 3 depicts the effect of the liquid to solid weight ratio, LSR, on the observed furfural concentration in a hydrolysis reaction carried out at 120 C and 15 wt.% acid concentration. The data show that increasing LSR results in a decrease in the obtained furfural concentration with time as a consequence of starting with lower pentosan concentration, which acts as a limiting reactant in the LSR range used. Moreover, not only the maximum furfural concentration obtained decreases from 710 g/m3 at a LSR of 50 to only 340 g/m3 at a LSR of 100, but also the reaction time at which these maxima occurs decreases from 150 min at the lower LSR value to only 90 min at the higher value. This is due to the earlier onset of a faster rate of furfural decomposition than production taking place at the higher than the lower LSR values. It has to be noted here, however, that the observed characteristics of the effects of the liquid to solid weight ratio cited above is a result of having pentosan present in the solid waste material as the limiting component. If, on the other hand, the hydrolyzing acid was the limiting component, such as when using a sufciently diluted acid solution concentration, a reversed effect of the liquid to solid weight ratio on furfural yield would then be expected. 4.3. Furfural yield and formation of side products Among the important factors that inform and affect the economics of furfural production and its process design is the maximum achievable furfural yield as well as the formation of side products. The latter factor obviously also affects the cost of separation, purity and quality of the nal product. Table 2 provides a summary of the maximum achieved furfural concentration and yield at different experimental conditions, and the reaction time to reach these maximum values along with the corresponding concentration of some important and valuable side products such as furfuryl alcohol, 5 hydroxymethyl furfural (5HMF), 5 methyl furfural (5MF), and 2 acetyl furan. As shown in Table 2, the highest obtained furfural yield was 53% achieved in 30 min of hydrolysis

1400

Furfural concentration, gm/m 3

T= 100 C

1200 1000 800 600 400 200 0 0 30 60

T= 120 C T= 140 C model

90 120 150 180 210 240 270 300 330

Hydrolysis time, min


Fig. 2. Furfural concentration versus hydrolysis time at different reaction temperatures, 15 wt.% H2 SO4 concentration, and LSR = 50.

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Table 2 Summary of maximum achieved furfural concentration and yields at the various hydrolysis conditions tested along with the corresponding concentrations of valuable side products. Acid conc. (wt.%) LSR (ml/g) Temp ( C) Time (min) Max. furfural concentration (g/m3 ) Max. furfural yield% Concentration of side products corresponding to maximum furfural concentration (g/m3 ) 5HMF 5 10 10 10 15 15 15 15 15 50 50 50 50 50 50 50 70 100 120 120 140 120 100 120 140 120 120 240 210 150 180 240 150 30 120 90 564 566 235 366 306 710 1114 470 340 22 20 11 25 15 34 53 32 32 34 25 30 20 16 54 44 20 13 5MF 4 3 1 3 2 12 7 2 0 Furfural alcohol 15 12 8 7 8 29 12 8 5 2Acetyl furan 26 26 10 3 22 1 0 0 6

using 15 wt.% acid concentration at 140 C and a liquid to solid ratio of 50. The remarkable increase in furfural yield and the corresponding decrease in hydrolysis reaction time realized at the highest yield conditions compared to those observed at the other tested conditions should be noted here. Fig. 4 shows furfural yield versus reaction time observed at the highest yield operating condition. It is also important to note here that all formed side products are valuable chemicals and have wide industrial applications. Furfuryl alcohol, for instance, is considered an important ne chemical in the polymer industry, used for the production of tetrahydrofurfuryl alcohol, and various synthetic bers, rubbers, resins resistant to acids, bases and resins used for strengthening ceramics (Huang et al., 2007). It is also used as a chemical intermediate to manufacture lysine, vitamin C, lubricants and dispersing agents (Merlo et al., 2009). 5 Hydroxymethyl furfural (5HMF) is an important raw material for manufacturing plastics (Fujiki et al., 2008). Moreover, it is a versatile and key intermediate in biofuel chemistry and petrochemical industry (Tan et al., 2011). 5MF is also a valuable and important chemical intermediate (Yang and Sen, 2011). However it is desirable to limit its concentration to less than 1% of the nal furfural product (Zeitsch, 2000a). This should not be a major issue, since all of these valuable side products should be separated and utilized. Fig. 5 depicts the concentrations of side products versus time at the maximum furfural yield conditions. A sample of furfural yields reported by previous studies of sulfuric acid hydrolysis of different agriculture residues at different operating conditions are shown in Table 3. Aguilar et al. (2002) reported a furfural yield in the range of (13.339%) by sulfuric acid hydrolysis of sugar cane bagasse, which is similar to yield range obtained in this study at similar hydrolysis conditions. Montane et al. (2002) on the other hand, obtained higher furfural yields (5065%) than obtained in this study by a dilute sulfuric acid hydrolysis of olive stones, however, at a much higher temperature range of 220240 C. No furfural yield data are available in the

literature based on hydrolysis of agricultural wastes at high H2 SO4 acid concentrations similar to that employed in this study. 4.4. Kinetics Experimental kinetic data of the acid hydrolysis experiments to produce furfural from midribs of date-palm tree at different test conditions were tted to Eq. (10) using Polymath 5.1 software. Table 4 provides a summary of the outcome of the regression analysis for the best t values of k1 to k4 , and along with the corresponding regression coefcient, R2 values, for the kinetic data collected at different hydrolysis reaction conditions. All calculated k values shown in Table 4 exhibit plausible values with consistent dependence on both the hydrolysis reaction temperature and acid concentration. Moreover, the range of the calculated values (0.530.97), is similar to value range of (0.840.86) reported by Eken-Saracoglu et al. (1998) and (0.551) range reported by Aguilar et al. (2002). Moreover, the strong correlation of each set of kinetic data generated at the various test conditions with Eq. (10) is reected by the high values of the correlation coefcients calculated for each regression (R2 0.9), which is also evident by the excellent model t shown in Figs. 13. Data of Table 4 show that, depending on reaction conditions, k1 values are two to three orders of magnitude larger than the values of the other reaction rate constants k2 k4 . This clearly shows that the rate of conversion of pentosan to pentose is relatively quite fast and thus does not control the overall rate of furfural production or control the rate of the following consecutive or parallel reaction steps. Furthermore, the data also reect different degrees of increase in all k values with both the reaction temperature and the acid concentration. Thus, a modied Arrhenius equation similar to that used
60.00
5HMF

50.00 60

Furfuryl Alcohol 5MF 2 Acetyl Furan

Concentration, gm/m3

40.00 30.00 20.00 10.00 0.00

Furfural percent yield

50 40 30 20 10 0 0 50 100 150 200

50

100

150

200

Hydrolysis time, min


Fig. 5. Side products concentrations versus hydrolysis time in hydrolyzing with 15 wt.% H2 SO4 , at 140 C and a LSR of 50.

Hydrolysis time, min


Fig. 4. Furfural yield in hydrolyzing with 15 wt.% H2 SO4 , at 140 C and a LSR of 50.

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Table 3 Comparison of furfural yield by different studies using sulfuric acid. Ref Montane et al. (2002) Aguilar et al. (2002) Raw material Olive stone (18.5% pentosan) Sugar cane bagasse (xylan20.6 1.6 wt.%) LSR (ml/g) 11.1 10 Temp ( C) 220240 100128 Acid (wt.%) 0.050.25 mol/l (0.52.5 wt.%) 26 wt.% Furfural yield actual/theoretical 5065% 25.85 g/l reported (13.339%) calculated

Table 4 Regression best t values of k1 k4 and of Eq. (10). H2 SO4 (wt.%) 5 10 10 10 15 15 15 15 15 T ( C) 120 120 140 120 100 120 140 120 120 CP0 (mol/l) 0.0242 0.0242 0.0242 0.0169 0.0242 0.0242 0.0242 0.0169 0.0121 (g/g) 0.969 0.887 0.971 0.882 0.597 0.614 0.868 0.631 0.534 k1 (min1 ) 0.111 1.707 2.212 1.714 1.531 2.120 2.515 2.120 2.080 k2 (min1 ) 0.0022 0.0028 0.0097 0.0036 0.0018 0.0126 0.0570 0.0144 0.0159 k3 (min1 ) 0.0003 0.0015 0.0066 0.0020 0.0001 0.0035 0.0110 0.0005 0.0131 k4 (min1 ) 0.0022 0.0030 0.0186 0.0052 0.0066 0.0063 0.0191 0.0115 0.0051 R2 0.99 0.97 0.96 0.96 0.97 0.99 0.98 0.96 0.90

by other investigators (Romero et al., 2010; Rodrguez et al., 2008; Herrera et al., 2003; Aguilar et al., 2002; Tellez-Luiz et al., 2002) is used here to model the effect of both temperature and acid concentration on all reaction rate constants considered here. The modied Arrhenius equation assumes the following form ki = aC exp
b

reactions of corncob and sunower seed hulls using (0.20.6 N) H2 SO4 concentrations and (98130 C) temperature range: k1 = 1.486 1010 CH1.21 exp 0 k2 = 6.344 1014 CH0.78 exp 0 80.34 RT 133.7 RT (15) (16)

E RT

(11)

where a and b are regression parameters, C is the acid concentration in wt.%, E is the activation energy in kJ/mol, R is the universal gas constant in kJ/(mol K), and T is the reaction temperature in K. However, since our data revealed a quite sluggish furfural production rate and a very low furfural yield when the lower acid concentration of 5 wt.% is used albeit at the higher reaction temperatures employed, kinetic data generated at this low acid concentration in this study were not used in developing the modied Arrhenius equations for the rate constants. Nevertheless, data generated in our study at this lower acid concentration allowed for a comparison of our model predictions of the reaction rate constants with those predicted by models developed in other similar acid hydrolysis studies of different agricultural wastes at similar acid concentration levels and temperature range. Dunning and Lathrop (Zeitsch, 2000b) used Eqs. (12) and (13) below to predict the value of the reaction rate constants k1 and k2 , respectively of the hydrolysis reaction of corncobs using dilute sulfuric acid in the concentration range of (1.94.4 wt.%) and (100121 C) temperature range: k1 = 7.832 104 CH exp k2 = 9.306 1015 CH exp 5163 T 16, 894 T (12)

where CH0 is the normality of H2 SO4 used. Rahman et al. (2006) proposed the following correlations for the kinetic parameters k1 and k2 for the hydrolysis of oil palm empty fruit bunch ber using sulfuric acid at (26 wt.%) at 120 C. k1 = 0.013C 1.4217 k2 = 0.0005C 1.3849 (17) (18)

(13)

where CH is the initial hydrogen ion concentration in mol/l. Aguilar et al., 2002, used Eq. (14) below to predict the value of k1 as a function of temperature and acid concentration in the hydrolysis of sugar cane bagasse using dilute H2 SO4 concentration in the range of (26 wt.%) and a reaction temperature range of (100128 C). k1 = exp(30.7)C 0.734 exp 13, 080 T (14)

Table 5 shows a comparison of k1 and k2 values determined in this study at 5 wt.% H2 SO4 and 120 C with their predicted values at the same hydrolysis conditions by each of the correlations cited above of Dunning and Lathrop (Zeitsch, 2000a), Aguilar et al. (2002), Rahman et al. (2006) and Eken-Saracoglu et al. (1998). Although this comparison is made only at just one hydrolysis reaction condition, it nevertheless reects a general agreement of these models predictions of k1 and k2 with those determined by our model as well as with their relative order of magnitude. We could not nd similar correlations in the literature to predict these k values at higher acid concentrations (above 6 wt.%). Therefore, a set of correlations to predict k1 k4 as functions of temperature and higher acid concentration in the range of 1015 wt.% were developed based on data generated in this study. The proposed correlations along with corresponding values of the correlation coefcients are summarized in Table 6. Where C is H2 SO4 concentration in wt.%, T is the hydrolysis reaction temperature in Kelvin, and R is the universal gas constant in kJ/mol K. It should be noticed that Eqs. (19) and (20) indicate that the activation energies of these reaction steps at higher acid
Table 5 Predictions of different correlations of k1 and k2 obtained in this study at 5 wt.% H2 SO4 concentration and 120 C. Correlation Dunning and Lathrop (Zeitsch, 2000a,b) Aguilar et al. (2002) Rahman et al. (2006) Eken-Saracoglu et al. (1998) Current study k1 (min1 ) 0.157 0.246 0.128 0.319 0.111 k2 (min1 ) 0.0018 No correlation 0.0046 0.0011 0.0022

Eken-Saracoglu et al. (1998) developed the following correlations for the reaction rate constants k1 , and k2 of the hydrolysis

H.S. Bamueh et al. / Industrial Crops and Products 42 (2013) 421428 Table 6 Modied Arrhenius correlations of k1 k4 in H2 SO4 concentration range of 1015 wt.%. Correlation k1 k2 k3 k3 = 158.85 C exp(15.66/RT ) (19) = 4.53 108 C 4.345 exp(94.97/RT ) (20) = 3.848 1013 C 1.199 exp(127.6/RT )(21) = 4.14 105 C 0.462 exp(59.54/RT ) (22)
0.387

427

R2 0.98 0.99 0.98 0.86

was 53% at 140 C, 15 wt.% acid concentration, and a LSR of 50. Calculated yields were dependent on reaction temperature, acid concentrations and a LSR. Experimental data were successfully t with high accuracy a simple kinetic model of the reactions. The rate constants were also successfully correlated with the reaction conditions.

Acknowledgement
1.40 1.20 1.00

The authors are grateful to King Abdulaziz City for Science and Technology (KACST) for the nancial support of this project under grant no. AR 27-107.

ln (k1)

0.80 0.60 0.40 0.20 0.00 2.40 2.50 2.60 2.70

References
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(1/T) 103, 1/K


Fig. 6. ln k1 versus (1/T) at 15 wt.% H2 SO4 and LSR = 50.

12.00 10.00 8.00

-ln k2

-ln k3

-ln k4

-ln (k)

6.00 4.00 2.00 0.00 2.40

2.50

2.60

2.70

(1/T) 103, 1/K


Fig. 7. Natural log of each of k2 , k3 , and k4 versus (1/T) at 15 wt.% H2 SO4 and LSR = 50.

concentrations are lower than their corresponding values at lower acid concentrations reported by previously cited studies of Dunning and Lathrop (Zeitsch, 2000b), Aguilar et al. (2002) and EkenSaracoglu et al. (1998). This is obviously due to the fact that acid acts as a catalyst in such reactions and its catalytic activity increases with concentration. Rate constants of all reaction steps, except for that of furfural decomposition step k4 , exhibit a strong correlation with acid concentration and reaction temperature, as reected by the calculated values of the correlation coefcient R2 0.98. Figs. 6 and 7 show plots of the natural log of k1 versus 1/T and natural log of each of k2 , k3 , and k4 versus 1/T, respectively, based on kinetic data of the hydrolysis reactions with 15 wt.% acid concentration and a liquid to solid ratio of 50. These plots yield almost straight line t, and thus satisfying Arrhenius equation. 5. Conclusions Production of furfural from palm tree wastes can be achieved using H2 SO4 acid catalysis at high temperature, pressure and concentrations. Pentosan content of midribs is 14.6 wt.% so furfural production is feasible. The maximum furfural yield obtained

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