Fuel 97 (2012) 241244

Contents lists available at SciVerse ScienceDirect

Fuel
journal homepage: www.elsevier.com/locate/fuel

Comparison of batch aqueous-phase reforming of glycerol and lignocellulosic biomass hydrolysate

Bahar Meryemoglu, Burcak Kaya, Sibel Irmak , Arif Hesenov, Oktay Erbatur
Department of Chemistry, ukurova University, Arts and Sciences Faculty, Adana 01330, Turkey

a r t i c l e

i n f o

a b s t r a c t
The present study was designed to evaluate gasication performance of glycerol, overproduced from biodiesel fuel production, and lignocellulosic biomass hydrolysate for hydrogen gas production by aqueousphase reforming (APR) process. Lignocellulosic biomass hydrolysate was prepared by solubilization of wheat straw under subcritical water condition. APR experiments were performed in a batch type reactor at 250 and 300 C in the presence of various commercial reforming catalysts such as raney nickel and Pt doped on carbon and alumina supports. Although the gas composition was similar, lower amount of gas was produced when APR of glycerol performed at higher temperature in the presence of a Pt catalyst. Hydrogen production activity of Pt on alumina catalyst was same as Pt on carbon support at 250 C, however, the activity signicantly reduced at 300 C. The gasication performance of biomass hydrolysate was quite low compared to glycerol solution. The Pt on carbon was the most effective catalyst for total organic carbon (TOC) removal from glycerol while raney nickel was the most active one for TOC removal from wheat straw biomass hydrolysate. 2012 Elsevier Ltd. All rights reserved.

Article history: Received 27 April 2011 Received in revised form 3 February 2012 Accepted 6 February 2012 Available online 21 February 2012 Keywords: Aqueous-phase reforming Glycerol Lignocellulosic biomass Hydrogen Catalyst

1. Introduction Glycerol, a 1,2,3-propanetriol, is a simple alcohol also known as glycerin or glycerine. It is being overproduced as a result of biodiesel fuel production and 1 L of glycerol is made from every 10 L of biodiesel fuel produced [1]. Glycerol has been extensively used in liquefaction of biomass process to obtain less viscous tarry lump [25]. Utilization of lignocellulosic biomass, such as forest waste, energy crops and agricultural waste for biofuel production could reduce greenhouse gas emissions and dependence on fossil fuels since they have better CO2 and mass balances than rst generation biofuels and they limit the competition with food processing [6]. The use of renewable biomass as a major feedstock for hydrogen production has received considerable attention in recent years [7,8]. Hydrogen can be generated from biomass, but this technology needs further development. The aqueous-phase reforming (APR) has been considered as a promising way to produce hydrogen. APR takes place at lower temperatures that reduces the cost of the procedure. It is rather a new technology involving decomposition of the oxygenated hydrocarbons derived via solubilization of the carbohydrate rich lignocellulosics. APR is compatible with water-soluble feedstocks
Corresponding author. Tel.: +90 322 338 6081x24; fax: +90 322 338 6070.
E-mail address: sirmak@cu.edu.tr (S. Irmak). 0016-2361/$ - see front matter 2012 Elsevier Ltd. All rights reserved. doi:10.1016/j.fuel.2012.02.011

and it produces high yield of hydrogen gas with low CO byproduct due to facilitated watergas shift reaction [9]. Previous studies on hydrogen production by APR have been mainly focused on biomass model compounds or biomass-derived hydrocarbons [1012]. Hydrogen can be produced from APR of glycerol [10,1316], however, it is important to determine if the use of glycerol in APR has an advantage over biomass hydrolysate as a feedstock for efcient and cost-effective production of hydrogen. The present study was designed to evaluate batch aqueous phase reforming of glycerol solution and actual lignocellulosic biomass hydrolysate for hydrogen gas production. Wheat straw hydrolysate solubilized in subcritical water condition was used as a representative biomass hydrolysate. Since the aqueous phase reforming of polylols is very complex and many reaction pathways are possible, and some of them are seen to be very dependent on the properties of the catalyst used the gaseous products produced might differ [13,17]. Therefore, APR experiments in our study were performed in the presence of various commercial reforming catalysts such as raney nickel and Pt doped on carbon and alumina supports. 2. Experimental section 2.1. Materials Wheat straw used in this study was obtained from a local animal feed supplier. The ground wheat straw biomass was dried at

242

B. Meryemoglu et al. / Fuel 97 (2012) 241244

room temperature before use. The moisture content of ground samples was 8.67 0.40%. The CHN elemental analysis resulted in 46.48% carbon; 5.45% hydrogen; 0.33% nitrogen and 38.66% oxygen on dry basis of ground wheat samples. The ash content was 9.08%. Cellulose content of biomass material was determined as described by Foyle et al. [18] and found to be 48.65 0.70%. The percent of lignin fraction was 21.11 0.23% that was determined using the method described by Sluiter et al. [19]. Glycerol, raney nickel 2400 activated chromium catalyst in water solution and 5% Pt on alumina catalyst were obtained from Sigma-Aldrich (Sigma-Aldrich Corporation, St. Louis, MO). The 5% Pt on carbon catalyst was from Alfa Aesar (Alfa Aesar GmbH & Co. KG, Karlsruhe, Germany). All other chemicals used in this study were of either analytical or of reagent grade. 2.2. Preparation of wheat straw biomass hydrolysate The hydrolysis of wheat straw was performed in a 500 ml stainless steel high pressure reactor (Parr Model 4575 HP/HT, Parr Instrument Co., Moline, IL, USA) equipped with magnetic drive stirrer and temperature controller system. The 10 g ground wheat straw biomass and 350 ml water were placed in the reactor and the mixture was pretreated with 20 kHz 50 Hz high power ultrasound for 8 min by using an ultrasonic probe sonicator (Cole Parmer Ultrasonic Processor, IL, USA) before hydrolysis in subcritical water. The reactor was sealed after ultrasonication and air in the reactor was purged with CO2. The mixture was heated with a rate of 4.7 C/min until it reaches to desired temperature. After heating to a 250 C, the reactor was pressurized with CO2 using ISCO 260D pump (Isco Inc., Lincoln, Nebraska, USA) at 27.58 MPa. Following mixing (500 rpm) the reactor contents for 90 min continuously via the magne-drive at the desired temperature, the reactor was taken out of the heating system and quenched in ice-cold water. The hydrolysate solution was collected and ltered. The solid residue was dried in a vacuum oven and used for calculation of percent hydrolysis. The hydrolysate solution was ltered through 0.2 lm nylon lter and clear solution was analyzed for total organic carbon (TOC) content and polysaccharide molar mass fractions. All hydrolysis experiments were performed and analyzed in duplicate. Total organic carbon content, polysaccharide and monosugar analysis of the solutions were determined using the method and instrumentation as described by Irmak and ztrk [20]. 2.3. APR experiments The 50 ml of hydrolysate that obtained via solubilization of wheat straw biomass in subcritical water condition or 4000 mg/l carbon containing of glycerol solution was placed in a Parr 4590 model 100 ml stainless steel micro bench reactor equipped with magnetic drive stirrer and temperature controller system (Parr Instrument Co., Moline, IL, USA) and reforming catalyst (0.12 g of Pt on carbon/alumina whole catalyst corresponding to 6 mg of Pt

or 0.6 g of raney nickel based on dry weight) was added. The reactor was sealed and the air in the sealed reactor was purged with argon. The mixture was heated up to 250 C/300 C and reactor contents were mixed for 2 h via magnetic drive stirrer. After 2 h of reaction time, the reactor was taken out of the heating system and rapidly quenched in a water bath. The gases in the reactor were collected into gas burette and the volume was measured. All APR experiments were performed in triplicate. 2.4. Analysis of gaseous products The gaseous products were analyzed by a dual-channel gas chromatograph system equipped with two thermal conductivity detectors (Varian-450 GC). One channel was used with argon carrier to obtain good sensitivity and linearity for hydrogen and second one with helium carrier for detection of other gases (CO, CO2, alkanes, etc.). The columns used in hydrogen and other gas channels were MolSieve 5A 1 m 1/800 Ultimetal and Shincarbon 100/120 mesh 2 m 1/1600 1 mm, respectively. The triplicate gas mixture (250 ll) was injected into GC with 1:3 split injection mode via SSL injector in helium carrier gas channel. Oven temperature used was as follows: 3 min at 40 C; from 40 C to 230 C with 8 C/min heating rate and maintained at this temperature for 5 min. Inlet temperature was 230 C and lament was at 300 C. The standard gas mixture was obtained from Elite Gaz Teknolojileri (Istanbul, Turkey). The composition of gas mixture based on mole percent was 1.80 0.04 acetylene, 4.00 0.08 ethylene, 3.90 0.08 ethane, 4.90 0.10 methane, 16.00 0.32 carbon monoxide, 22.00 0.44 carbon dioxide and balance amount of hydrogen (47.40 0.47). 3. Results and discussion 3.1. APR of glycerol Gasication of glycerol solution in absence of a catalyst produced very low amount of gas that consisting entirely of carbon dioxide (Table 1). APR of glycerol in presence of a reforming catalyst caused an increase in the gas volume produced. The Pt catalysts produced more gas volume compared to raney nickel 2400 and activity of Pt catalyst was the same as each other for both catalyst supports (1.60 mol H2/g catalyst). The more hydrogen gas production was accompanied by a noticeable decrease in carbon monoxide production, which is attributed to the activation of the watergas shift reaction (CO + H2O M H2 + CO2) catalyzed by platinum. The performance of the catalyst was affected by type of support used for metal attachment and dispersion [10,21]. When APR experiments carried out at higher temperature (300 C) the amount of gas produced was signicantly differed (Table 2). The highest volume of gas was generated in APR carried out with raney nickel catalyst which is known as an inexpensive material and has catalytic properties for production of hydrogen

Table 1 Aqueous-phase reforming of glycerol at 250 C in the presence of various reforming catalysts. Catalyst Gas volume (ml) Gas composition (mol%) H2 No catalyst 5% Pt on carbon 5% Pt on alumina Raney Ni 2400
a b c

H2 mol/g catalystb, CO2 100 50.8 3.1 53.6 1.6 50.0 0.1 CH4 n.d. 13.2 0.3 12.2 0.1 19.0 0.8 C2H6 n.d. n.d. n.d. Under detection limit n.d. 1.60 1.60 0.01

CO n.d. n.d. n.d. 1.0 0.1

3.0 1.4 804.0 4.2 850.5 0.7 577.0 9.9

n.d.a 36.0 2.8 34.2 1.7 30.0 1.4

n.d.: not detected. The calculation made using ideal gas equation: ntotal = PV/RT. P = 1 atm, T = 300 K, V = volume of gas mixture produced. nhydrogen = ntotal hydrogen composition/100. Based on metals; Pt or NiAl according to catalyst types.

B. Meryemoglu et al. / Fuel 97 (2012) 241244 Table 2 Aqueous-phase reforming of glycerol at 300 C in the presence of various reforming catalysts.a Catalyst Gas volume (ml) Gas composition (mol%) H2 No catalyst 5% Pt on carbon 5% Pt on alumina Raney Ni 2400
a

243

H2 mol/g catalyst CO2 100 50.0 1.7 51.0 2.3 51.8 0.1 CH4 n.d. 15.0 3.8 13.4 3.0 17.0 0.5 C2H6 n.d. n.d. Under detection limit Under detection limit 1.60 1.20 0.02

CO n.d. 0.6 0.1 0.4 0.1 2.1 0.1

10.0 1.0 689.0 15.5 601.0 12.7 1026.0 2.8

n.d. 34.4 2.2 35.2 0.2 29.1 0.5

See Table 1 for abbreviations.

3.2. APR of wheat straw hydrolysate

800 700 600 500 400 300 200 100 0 5% Pt on carbon 5%Pt on alumina Raney Ni 2400 250C 300C

Fig. 1. Total organic carbon contents of glycerol after aqueous-phase reforming carried out 250 C and 300 C.

from small oxygenates, such as glycerol [22]. However, the composition of gas mixture was still better in Pt catalyst which is agreement with previous studies [13]. The 5% Pt on carbon catalyst produced more gas at 300 C compared to 250 C. Similar trend was observed in previously reported studies on aqueous phase reforming of oxygenates [9,23]. As can be seen in Table 2, increasing the APR processing temperature to 300 C, a decrease in hydrogen production was observed in alumina supported Pt catalyst. Hydrogen production was changed from 1.60 to 1.20 mol H2/g catalyst. Opposite trend was observed in case of using raney nickel as reforming catalyst. Fig. 1 represents decrease in total organic carbon content of glycerol solutions after APR experiments carried out at both 250 and 300 C temperatures with all catalysts tested. As can be seen, higher temperature was also effective on total organic carbon removal that indicates facilitation of CC bond cleavage that led to generation of smaller molecules of biomass components and therefore, release of more organic compounds into solution by solubilization. TOC removal was in the following descending order for 250 C: 5% Pt on carbon > raney nickel > 5% Pt alumina. The sequence was changed to following descending order for 300 C: 5% Pt on carbon > 5% Pt alumina > raney nickel. However, effect of temperature on TOC removal of glycerol in presence of 5% Pt on carbon was rather less contrast to alumina supported one in which large extent differences were observed in TOC removal between two temperatures studied.

The biomass hydrolysates obtained by solubilization of wheat straw in subcritical water found to contain 4964 8 mg/l of total organic carbon. Gel permeation chromatography (GPC) analysis showed that the hydrolysate had 50,104; 15,738; 7189 Da molecular weight of polysaccharide fractions in which 15,738 Da was the most concentrated one. Aqueous-phase reforming of biomass hydrolysate in the presence of Pt on carbon catalyst produced three times more gas which consisted of H2, CO, CO2, CH4 and C2H6 compared to that of performed in presence of alumina supported catalyst in which no aliphatic hydrocarbon products was formed (Table 3). The gas yield and hydrogen production were signicantly increased when the experiments performed in presence of raney nickel 2400 catalyst. No carbon monoxide was observed in that gas mixture. There were signicantly large differences on gas yields compared to glycerol and wheat straw hydrolysate feeds. For instance, 804 ml of gas produced from APR of glycerol in presence of 5% Pt on alumina catalyst while it was only 20.6 ml in case of wheat straw biomass hydrolysate. Since wheat straw hydrolysate composed of higher molecular weight of oxygenated hydrocarbons, the gasication yield was low comparing to glycerol, a simple compound, that is in agreement with previous ndings reported for glucose [20]. Hydrogen production and selectivity of Pt supported on carbon had best performance (0.40 mol H2/g catalyst) in APR of biomass hydrolysate, however, it was still quite low compared to APR of glycerol feed. Fig. 2 compares the reduction in total organic carbon content of wheat straw hydrolysate and glycerol after APR experiments for all catalysts tested. The solid residues left after APR were negligible for both feeds. As can be seen, the reductions in TOC were sharper in glycerol in presence of a reforming catalyst. The 5% Pt on carbon was the most effective catalyst on TOC removal when glycerol was used as a feed and almost 99% of organic carbon content of that solution was consumed during reforming process. On the other hand, raney nickel 2400 catalyst was the most active one in TOC removal for wheat straw hydrolysate feed and 52% of TOC of starting solution was consumed in APR process. The reductions in TOC among catalysts tested might also depend on very low amount of insoluble carbonous materials left after APR that was not quantied in our study.

Table 3 Aqueous-phase reforming of wheat straw hydrolysate at 250 C in the presence of various reforming catalysts.a Catalyst Gas volume (ml) Gas composition (mol%) H2 No catalyst 5% Pt on carbon 5% Pt on alumina Raney Ni 2400
a

TOC (mg/l)

H2 mol/g catalyst CO2 73.9 1.1 7.3 0.1 36.5 1.1 26.3 0.5 CH4 n.d. 23.2 1.6 n.d. 4.8 0.1 C2H6 n.d. 0.8 0.1 n.d. n.d. 0.40 0.08 0.02

CO 26.1 0.3 2.4 0.1 7.1 0.2 n.d.

14.6 1.6 62.8 4.8 20.6 1.1 450.7 6.1

n.d. 66.3 0.2 56.4 1.1 68.9 0.4

See Table 1 for abbreviations.

244

B. Meryemoglu et al. / Fuel 97 (2012) 241244

6000 5000

Glycerol Wheat straw

4000 3000 2000 1000 0 Original No catalyst 5% Pt on carbon 5% Pt on alumina Raney Ni 2400

Fig. 2. Comparison of total organic carbon contents of glycerol and wheat straw hydrolysate after aqueous-phase reforming at 250 C.

4. Conclusion The aim of this work was to evaluate aqueous phase reforming of renewable materials such as lignocellulosic biomass hydrolysate and glycerol for hydrogen gas production. The study conducted on liquid-phase reforming of those solutions in the presence of raney nickel, Pt on carbon and Pt on alumina catalysts. The results showed that gas yield and hydrogen selectivity was better in Pt catalysts. There were large differences between two feeds in terms of gas yields. The highest volume of gas was generated in APR carried out with raney nickel catalyst, however, gas composition was still better in case of Pt catalysts were used. Acknowledgment This study was funded by ukurova University Research Grant (Project number: FEF2007BAP11). References
[1] Selembo PA, Perez JM, Lloyd WA, Logan BE. High hydrogen production from glycerol or glucose by electrohydrogenesis using microbial electrolysis cells. Int J Hydrogen Energy 2009;34:537381. [2] Demirbas A. Conversion of wood to liquid products using alkaline glycerol. Fuel Sci Technol Int 1992;10:17384.

[3] Demirbas A. Liquefaction of biomass using glycerol. Energy Sources Part A 2008;30:11206. [4] Demirbas A. Aqueous glycerol delignication of wood chips and ground wood. Biores Technol 1998;63:17985. [5] Kucuk MM, Demirbas A. Kinetics study on hydrolysis of biomass (Ailanthus altissima chips) by using alkaline glycerol solution. Energy Convers Manage 1999;40:1397403. [6] Naik SN, Goud VV, Rout PK, Dalai AK. Production of rst and second generation biofuels: a comprehensive review. Renew Sustain Energy Rev 2010;14:57897. [7] Koroneos C, Dompros A, Roumbas G. Hydrogen production via biomass gasication a life cycle assessment approach. Chem Eng Process 2008;47: 12618. [8] Valenzuela MB, Jones CW, Agrawal PK. Batch aqueous-phase reforming of woody biomass. Energy Fuel 2006;20:174452. [9] Cortright RD, Davda RR, Dumesic JA. Hydrogen from catalytic reforming of biomass-derived hydrocarbons in liquid water. Nature 2002;418:9647. [10] Wen G, Xu Y, Ma H, Xu Z, Tian Z. Production of hydrogen by aqueous-phase reforming of glycerol. Int J Hydrogen Energy 2008;33:665766. [11] Davda RR, Dumesic JA. Renewable hydrogen by aqueous phase reforming of glucose. Chem Commun 2004;1:367. [12] Tanksale A, Wong Y, Beltramini JN, Lu GQ. Hydrogen generation from liquid phase catalytic reforming of sugar solutions using metal-supported catalysts. Int J Hydrogen Energy 2007;32:71724. [13] Luo N, Fu X, Cao F, Xiao T, Edwards PP. Glycerol aqueous phase reforming for hydrogen generation over Pt catalyst-effect of catalyst composition and reaction conditions. Fuel 2008;87:34839. [14] Menezes AO, Rodrigues MT, Zimmaro A, Borges LEP, Fraga MA. Production of renewable hydrogen from aqueous-phase reforming of glycerol over Pt catalysts supported on different oxides. Renew Energy 2011;36:5959. [15] Guo Y, Liu X, Azmat MU, Xu W, Ren J, Wang Y, et al. Hydrogen production by aqueous-phase reforming of glycerol over NiB catalysts. Int J Hydrogen Energy 2012;37:22734. [16] Guo Y, Azmat MU, Liu X, Wang Y, Lu G. Effect of supports basic properties on hydrogen production in aqueous-phase reforming of glycerol and correlation between WGS and APR. Appl Energy 2012;92:21823. [17] Shabaker JW, Huber GW, Davda RR, Cortright RD, Dumesic JA. Aqueous-phase reforming of ethylene glycol over supported platinum catalysts. Catal Lett 2003;88:18. [18] Foyle T, Jennings L, Mulcahy P. Compositional analysis of lignocellulosic materials: evaluation of methods used for sugar analysis of waste paper and straw. Biores Technol 2007;98:302636. [19] Sluiter A, Hames B, Ruiz R, Scarlata C, Sluiter J, Templeton D. Determination of structural carbohydrates and lignin in biomass. NREL Laboratory Analytical Procedures; 2004. <http://www.eere.energy.gov/biomass/analytical_ procedures.html>. _ [20] Irmak S, ztrk I. Hydrogen rich gas production by thermocatalytic decomposition of kenaf biomass. Int J Hydrogen Energy 2010;35:53127. [21] Lehnert K, Claus P. Inuence of Pt particle size and support type on the aqueous-phase reforming of glycerol. Catal Commun 2008;9:25436. [22] Shabaker JW, Huber GW, Dumesic JA. Aqueous-phase reforming of oxygenated hydrocarbons over Sn-modied Ni catalysts. J Catal 2004;222:18091. [23] Kruse A. Hydrothermal biomass gasication. J Supercrit Fluid 2009;47:3919.

TOC (mg/l)