Fuel 90 (2011) 16811688

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Hydrogen production via dry reforming of butanol: Thermodynamic analysis

Wenju Wang
Key Laboratory for Thermal Science and Power Engineering of Ministry of Education, Department of Thermal Engineering, Tsinghua University, Beijing 100084, PR China

a r t i c l e

i n f o

a b s t r a c t
Dry reforming of butanol for hydrogen production has been studied by Gibbs free energy minimization method. The calculation results showed that the formation of hydrogen and carbon monoxide was through a multi-step pathway via the dehydrogenation, dehydration, decomposition and carbon dioxide reforming of butanol. The optimum conditions for hydrogen production are identied: reaction temperatures between 1150 and 1200 K and carbon dioxide-to-butanol molar ratios between 3.5 and 4.0 at 1 atm. Under the above conditions, 100% conversion of butanol, 34.9137.98% concentration of hydrogen and 57.3457.87% concentration of carbon monoxide could be achieved in the absence of coke formation. The butanol dry reforming with carbon dioxide is suitable for providing fuels for Solid Oxide Fuel Cell (SOFC). The coke-formed and coke-free regions are found, which are useful in guiding the search for suitable catalysts for the reaction. 2010 Elsevier Ltd. All rights reserved.

Article history: Received 16 August 2010 Received in revised form 19 September 2010 Accepted 1 November 2010 Available online 12 November 2010 Keywords: Dry reforming Butanol Hydrogen Thermodynamic

1. Introduction Hydrogen is widely used in the production of pharmaceuticals, ne chemicals and bulk chemicals such as ammonia and methanol. It is also regarded as an energy carrier in the future because it can be produced from renewable sources such as biomass and solar energy is efciently converted to electricity by fuel cell, which provides high efciency with clean exhaust gas by consuming hydrogen and oxygen. However, effective generation of hydrogen from the primary energy carrier is the prerequisite for the commercialization of fuel cells [1]. Solid Oxide Fuel Cell (SOFC) is a good alternative for automotive application due to their high power density [1]. In order to commercialize this technology, economical sources and processes for the production of high-quality hydrogen need to be explored. Production of hydrogen from various renewable sources such as ethanol, dimethyl ether, bio-oil and glycerol (glycerine) is being widely researched [213]. Recently butanol (n-butanol/1-butanol, C4H10O), which is a higher member of the series of straight chain alcohols with each molecule of butanol containing four carbon atoms rather than two as in ethanol, has been proposed as a renewable raw material to produce hydrogen because butanol can be produced by fermentation process know as ABE, named such because it produced acetone, butanol and ethanol in roughly 6:3:1 ratios, and its feedstocks can include sugar beet, sugar cane, corn, wheat and potentially lignocellulosic biomass [1417]. In comparison with other fuels (e.g. ethanol and methanol), butanol (C4H10O) presents a series of advantages, including higher hydrogen content
E-mail address: wangwenju1982@gmail.com 0016-2361/$ - see front matter 2010 Elsevier Ltd. All rights reserved. doi:10.1016/j.fuel.2010.11.001

(13.51 wt.%) is higher compared to ethanol (13.04 wt.%) and methanol (12.50 wt.%), better safety because it is combustible but not dangerously ammable as is ethanol, lower vapor pressure, greater tolerance to water contamination, etc. [18]. Steam reforming of butanol for H2 production has been widely investigated [18,19], but little has been known for dry reforming of butanol (DRB). Butanol reforming with CO2 could be an attractive process. Firstly, since the bio-derived butanol is considered to be renewable and carbon dioxide neutral, it will not contribute to the greenhouse effect. Secondly, butanol reforming with CO2 is an interesting approach in converting CO2 into syngas, hydrogen or high value-added inert carbon and removing it from the carbon biosphere cycle. Recent investigations regarding ethanol reforming with CO2 have shown that CO2 can be sequestered and carbon deposits in the form of carbon nanolaments (CNF) which is a potential marketable byproduct [8,2024]. Butanol dry reforming is expected to show similar properties to that of ethanol. Furthermore, since butanol has more carbon atoms than ethanol, it may be more likely to produce CNF. Although thermodynamic analysis of ethanol and glycerol dry reforming have been extensively investigated [8,25], there are few reports about the thermodynamics of DRB in gaseous phase. Herein, for the rst time, this study on the thermodynamic equilibrium of DRB into hydrogen is investigated by Gibbs free energy minimization method. The novel aspects of the work are: (1) determining the inuences of the reforming conditions (including temperature, pressure, the adding of CO2) on the DRB; (2) determining the coke-formed and coke-free regions. The work provides the full thermodynamic data, useful to guide the study for the in situ DRB to supply fuels for SOFC.

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Nomenclature aik Ak fi fi GC(g) GC(s) Gi Gt G i G fi GCS f nC N number of atoms of the kth element present in each molecule of species i total mass of kth element in the feed the fugacity of species i in system the standard-state fugacity of species i partial molar Gibbs free energy of gas carbon partial molar Gibbs free energy of solid carbon partial molar Gibbs free energy of species i total Gibbs free energy standard Gibbs free energy of species i standard Gibbs function of formation of species i standard Gibbs function of formation of solid carbon mole of carbon number of species in the reaction system P P R T TC yi DH 298 pressure of system standard-state pressure of 101.3 kPa molar gas constant temperature of system temperature at which the rst disappearance of carbon was achieved gas phase mole fraction heat of reaction in temperature of 298 K, pressure of 101.3 kPa

Greek symbols kk Lagrange multiplier li chemical potential of species i ui fugacity coefcient of species i

2. Modeling and simulation methodology 2.1. Possible reactions The possible reactions of DRB can be described by Eqs. (1)(14), as shown in Table 1. The CO2 reforming process of C4H10O, Eq. (1), 1 is strongly endothermic (DH 298:15 681:74 kJ mol ) and produces H2 and CO if C4H10O reacts in the most desirable way. C4H10O can dehydrogenate to butanol (C4H8O) according to Eq. (2) [26], which 1 is exothermic (DH 298:15 86:47 kJ mol ). C4H10O can dehydrate to 1-butene (C4H8) according to Eq. (3) [27], which is exothermic 1 (DH 298:15 24:04 kJ mol ). C4H10O can also decompose to propane (C3H8), CO and H2 through Eq. (4), which is endothermic 1 (DH 298:15 11:98 kJ mol ). C3H8 can further decompose to C2H4 1 by Eq. (5) and even C2H2 by Eq. (6), which DH 298:15 is 81.65 kJ mol and 175.00 kJ mol1, respectively. In addition, CO and CO2 can transform into CH4 and H2O through methanation reactions [Eqs. (7) and (8)], CO can also react with H2O through water gas shift reaction [WGS, Eq. (9)], which is exothermic and reversible, and hence the equilibrium shifts to the

right and favors the formation of H2 and CO2 at lower temperatures. Solid carbon (coke) formation may occur through C2H4 decomposition reaction [Eq. (10)], CH4 thermal cracking reaction [Eq. (11)], Boudouard reaction [Eq. (12)] and carbon oxides reduction reactions [Eqs. (13) and (14)]. H2 may come from different reaction pathways according to the above discussion. In order to maximize H2 production, it is crucial to supply enough CO2 and minimize C4H10O dehydrogenation, dehydration and decomposition. In the present procedure, 12 species in DRB system were considered, including 11 gaseous species, i.e., C4H10O, CO2, H2, CO, CH4, H2O, C2H2, C2H4, C3H8, C4H8 and C4H8O and elemental carbon (coke) as a solid. In this work, the most occurring products are H2, CO, CH4, H2O and coke and they will be discussed in detail. 2.2. Minimization of Gibbs free energy The minimization of total Gibbs free energy is a method used commonly to calculate the equilibrium compositions of the reaction system [28,29]. The corresponding equations are summarized in Table 2. The total Gibbs free energy of a system is given by the sum of ith species, as shown in Eq. (15). For reaction equilibrium in gas-phase, fi = yiuiP, fi P , and G DG are assumed. By using i fi the Lagrange multiplier method, the minimum Gibbs free energy of each gaseous species and that of the total system without solid

Table 1 The reactions in DRB process. Reactions

1 DH  298:15 (kJ mol )

C4 H10 O 3CO2 ! 7CO 5H2 C4 H10 O ! C4 H8 O H2 C4 H10 O ! C4 H8 H2 O C4 H10 O ! C3 H8 CO H2 C3 H8 ! C2 H4 CH4 C2 H4 ! C2 H2 H2 CO 3H2 ! CH4 H2 O CO2 4H2 ! CH4 2H2 O CO H2 O ! CO2 H2 C2 H4 ! Polymers ! 2H2 2C CH4 ! 2H2 C CO ! 1 1 CO2 C 2 2

681.74 86.47 24.04 11.98 81.65 175.00 205.21 164.75 41.09 52.40 74.87 86.21 131.29 90.15

(1) (2) (3) (4) (5) (6) (7) (8) (9) (10) (11) (12) (13) (14) Table 2 Equations of Gibbs free energy minimization method.

Gt

N X i1

ni Gi

N X i1

ni li

ni G RT i

ni ln

fi fi

(15)

DG fi
N X i1

yuP X RT ln i i kk aik 0 P k yi ui P X kk aik P k ! 0

(16)

ni DG RT ln fi ni aik Ak

(17)

X
i

(18) (19) (20)

GCg GCs DG 0 fCs

N1 X i1

ni DG RT ln fi

yi ui P X kk aik nC DG 0 fCs P k Z

T

CO H2 ! C H2 O CO2 2H2 ! C 2H2 O

ln K P

DG 298:15 K 298:15R

298:15 K

DH T dT RT2

(21)

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ones can be expressed as Eqs. (16) and (17), respectively. Eq. (18) is the constraints of elemental balances. The vaporsolid phase equilibrium is applied to the Gibbs-energy of carbon, as shown in Eq. (19). Thus, the minimization function of Gibbs-energy Eq. (20) is obtained by substituting Eq. (15) by Eqs. (17) and (19). In addition, the reaction equilibrium constant can be obtained from Eq. (21). In this paper, the product distribution and coke formation were investigated by Gibbs free energy minimization, however, only the

equilibrium analysis of reactions in Section 3.1 was studied by equilibrium constant method. 2.3. Operating conditions of simulation The equilibrium calculations employing the Gibbs-energy minimization are capable to simulate a single phase or multiphase of multicomponents in equilibrium. In the simulation, the CO2/ C4H10O molar ratio (CBR), reaction temperature and pressure

Fig. 1. Equilibrium constants of Eqs. (1)(14) as a function of temperature.

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ranges were varied in the range of 05, 5001500 K and 1 100 atm, respectively. 3. Results and discussion 3.1. Equilibrium analysis of reactions Fig. 1 shows the equilibrium constant Kp of Eqs. (1)(14) as a function of temperatures, determined from the Vant Hoff reaction, as shown in Eq. (21). Eqs. (3), (4) and (10) play a key role in the DRB system due to high equilibrium constants in the temperature range of 5001500 K. The C4H10O dehydration and decomposition reactions [Eqs. (3) and (4)] can bring about the complete conversion of C4H10O in the absence of CO2. The addition of CO2 leads to CO2 reforming of C4H10O into the main reaction as well as C4H10O dehydration and decomposition reactions [Eqs. (3) and (4)]. Thus, high C4H10O conversion is dependent on CO2 reforming, dehydration and decomposition of C4H10O in DRB process. The effects of temperature, CBR and pressure on the product distribution are discussed as follows (Sections 3.2 and 3.3). 3.2. Temperature and CBR effect 3.2.1. Conversion of C4H10O In the temperature and CBR ranges analyzed, the conversion of C4H10O is always greater than 99.99% and it can be considered that the conversion is complete. It is attributed to the high equilibrium constants of Eqs. (3) and (4). 3.2.2. Main products The changes of the H2, CO, CH4 and H2O concentration with temperature and CBR in DRB at 1 atm are given in Fig. 2.

3.2.2.1. H2 production. At a given CBR, the concentration of H2 rst increases sharply with the increase of temperature. It approaches to 83.12% when the temperature is 1500 K and CBR is 0. This can be explained by the fact that equilibrium constants of Eqs. (1) and (2) increase with increasing temperature from 500 to 1500 K, as shown in Fig. 3(a). The increase of CBR rst sharply decreases the H2 concentration and then slightly decreases it at temperatures above 1000 K, but slightly decreases the H2 concentration at temperatures below 1000 K. For example, the concentration of H2 decreases from 80.58% to 30.41% with the increase of CBR from 0 to 5 at 1100 K, but it slightly decreases from 46.88% to 17.87% with the increase of CBR from 0 to 5 at 800 K. 3.2.2.2. CO production. The concentration of CO is close to 0.00 at 500 K and increases with increasing temperature at a given CBR. For example, the concentration of CO increases from 0.00% to 16.67% with increasing temperature from 500 to 1500 K when CBR is 0. This can be explained by the fact that equilibrium constants of Eqs. (1) and (4) increase with increasing temperature from 500 to 1500 K. The increase of CBR rst increases and then slightly decreases the CO concentration at a given temperature. For example, the CO concentration rst increases from 16.44% to 57.87% with increasing CBR from 0 to 3.5, and then decreases from 57.87% to 56.01% with increasing CBR from 3.5 to 5 at 1200 K. This is mainly due to the fact that Eq. (1) plays a more important role than others on the CO production at low CBRs, however, at higher CBRs (above 3.5), CO2 is in excess, which can dilute product. Because CO is also a fuel, the products from DRB can be used directly for Molten Carbonate Fuel Cell (MCFC) and Solid Oxide Fuel Cell (SOFC) [1]. However, CO has been known as the poisonous species for Pt electrode of low-temperature Polymer Electrolyte Fuel

Fig. 2. Equilibrium H2 (a), CO (b), CH4 (c) and H2O (d) concentration on a wet basis from DRB as a function of CBR and temperature at 1 atm (%).

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Cell (PEFC) [1]. For PEFC and Alkaline Fuel Cell (AFC) and Phosphoric Acid Fuel Cell (PAFC), CO in the gas feed should be removed through water gas shift and/or preferential oxidation reactions.

in a decrease of CH4 due to the reverse methanation [reverse of Eqs. (7) and (8)]. 3.2.2.4. H2O production. At a given CBR of 3, the increase of temperature decreases the H2O concentration due to the methanation [Eqs. (7) and (8)] and the temperatures below 1000 K lead to relatively high H2O concentration because exothermic Eq. (9) is dominant at low temperatures. Increasing CBR rst increase and then decrease the H2O concentration.

3.2.2.3. CH4 production. The CH4 concentration is between 0.00% and 66.52% in the temperature range of 5001500 K and CBR range of 05. The temperatures below 900 K lead to relatively high CH4 concentration. Increasing temperature or increasing CBR results

Fig. 3. Equilibrium C2H4 (a) and C2H2 (b) concentration on a wet basis from DRB as a function of CBR and temperature at 1 atm (ppm).

Fig. 4. Equilibrium H2 (a), CO (b), CH4 (c) and H2O (d) concentration on a wet basis from DRB as a function of pressure and temperature at CBR of 3 (%).

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Fig. 5. Equilibrium C2H4 (a) and C2H2 (b) concentration on a wet basis from DRB as a function of pressure and temperature at CBR of 3 (ppm).

3.2.3. Other thermodynamically plausible products Apart from H2, CO, CH4 and H2O, the concentrations of C3H8, C4H8 and C4H8O are essentially zero over the entire temperature and CBR ranges investigated. However, as shown in Fig. 4, C2H2 and C2H4 are found at high temperature and low CBR due to the high equilibrium constants of Eqs. (5) and (6) at high temperatures above 1200 K. 3.3. Pressure effect 3.3.1. Conversion of C4H10O In the temperature and pressure ranges analyzed, the pressure from 1 to 100 atm has no effect on the conversion of C4H10O, which is already attained 100%. It is attributed to the high equilibrium constants of Eqs. (1), (3), (4) and (10). 3.3.2. Main products The different tendencies are observed for the H2, CO, CH4 and H2O concentration as shown in Fig. 4. The increase of pressure de-

creases the H2 and CO concentration, but increase CH4 and H2O concentration, because the increase of pressure probably shifts the equilibrium to CH4 and H2O which is attributed to methanation [Eqs. (7) and (8)] and carbon oxides reduction [Eqs. (13) and (14)], respectively. For example, as shown in Fig. 4, the H2 concentration monotonously decrease from 41.14% to 23.54%, and the CH4 concentration monotonously increase from 0.27% to 8.86% with increasing pressure from 1 to 100 atm at CBR of 3 and 1200 K. 3.3.3. Other thermodynamically plausible products Apart from H2, CO, CH4 and H2O, the concentrations of C3H8 and C4H8 are essentially zero over the entire temperature and pressure ranges investigated. However, as shown in Figs. 5 and 6, C2H2, C2H4 and C4H8O are found at high temperatures above 1200 K and high pressures above 40 atm due to the high equilibrium constants of Eqs. (2), (5) and (6) at high temperature. 3.4. Coke-formed and coke-free regions Coke formation during the catalytic dry reforming of ethanol could lead to deactivation of catalysts, resulting in low durability and activity [8,2024]. It is well known that butanol, which has more carbon atoms than ethanol, is more reactive and shows a much greater propensity towards coke deposition than ethanol, i.e., according to thermodynamic calculation, 1.17 mol C/mol butanol was observed at 573 K and water-to-butanol molar ratio of 1 in the steam reforming of butanol [18], however, only 0.58 mol C/mol ethanol was observed at 573 K and water-to-ethanol molar ratio of 1 in the steam reforming of ethanol [3]. So, coke formation is considered in the thermodynamic calculation of DRB. The possible reactions in DRB that can attribute to coke formation are Eqs. (10)(14), which are list in Table 1. These reactions are easily inuenced by operational parameters due to their relatively lower equilibrium constants, which can be observed from Fig. 1. Coke-free regions at different pressures are shown in Fig. 7. The temperature, TC, at or above which coke is not formed, is plotted as a function of CBR. The regions above and below the lines are the coke-free and coke-formed regions, respectively. At the atmospheric pressure, coke is absent at temperatures above 1625 K and CBR of 3 and 1 atm. It is thermodynamically favored at low temperatures and low CBRs, whereas high temperatures and high CBRs obviously inhibit the coke formation. At

Fig. 6. Equilibrium C2H4O concentration on a wet basis from DRB as a function of pressure and temperature at CBR of 3 (ppm).

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Fig. 7. Coke-formed and coke-free regions in DRB at different pressure.

CBRs below 3.5, serious coke formation will occur at temperatures above 1110 K. With the increase of the CBR increases from 3.5 to 5.0, TC decreases slightly. The increase of pressure from 1 to 100 atm hardly affects the coke formation when CBR is below 3.0. But in the CBR range of 3.05.0, TC obviously increases with the increase of pressure, and high pressure obviously promotes the coke formation. The amount of coke determined from experiments is usually much larger than that from thermodynamical predication at/close to equilibrium. Because once coke is formed it is readily accumulated compared to other gaseous products. However, CNF, a high value product, will be produced if suitable catalysts are used. Recently, both stainless steel and carbon steel have been investigated in dry reforming and cracking of ethanol [8,2024]. The results revealed that they are active in these reactions and CNF can be produced. Since the properties of butanol dry reforming system would be similar to that of ethanol, problems regarding coke formation could be overcome by using proper catalysts. CNF will be produced even if coke formation takes place.

On the basis of the equilibrium calculation with hydrocarbon compounds included, the optimal operating conditions are 1150 1200 K, 1 atm and CBRs of 3.54.0 (see Table 3). Under these conditions, complete C4H10O conversion, 34.9137.98% concentration of H2 and 57.3457.87% concentration of CO are achieved. From the view point of application, DRB should be operated at temperatures as low as possible, which need less energy. However, at temperatures below the lowest one of the optimal ranges, coke tends to form, which may deactivate the catalysts used. On the other hand, operation at temperatures higher than the upper one of the optimal range means consuming more energy. At the optimal temperature ranges (11501200 K), equilibration of the reaction will be fast, while CH4 and carbon formation will be minimized. As CO2 is a co-reactant, its molar ratio to C4H10O is also of great signicance. Lower CBRs (<3.5) favor carbon formation, while higher CBRs (>4.0) lead to remarkable decrease of the H2 concentration, and larger volume reactor is required. Pressure, as expected, has a negative effect on the H2 content. The maximum H2 efciency is achieved at atmospheric pressure. The products are directly suitable for SOFC. But for PEFC, AFC and PAFC, CO level in the gas feed should be further removed. 4. Conclusions Thermodynamic analysis for the dry reforming of C4H10O via Gibbs free energy minimization method to evaluate the effect of reaction temperatures, CBRs and pressures has been studied. The principal set of compounds involved in the calculation are C4H10O, CO2, H2, CO, CH4, H2O, C2H2, C2H4, C3H8, C4H8 and C4H8O and C. Based on the thermodynamic calculations, the following conclusions are drawn:  Almost complete conversion, 34.9137.98% concentration of H2 and 57.3457.87% concentration of CO could be achieved at the optimized conditions in DRB, i.e., 11501200 K, CBRs of 3.54.0, and 1 atm. These conditions are suitable for in situ dry reforming of C4H10O to supply fuels for SOFC.  Within the ranges of CBR (from 0 to 5), reaction temperature (from 500 to 1500 K) and pressure (from 1 to 100 atm), only C thermodynamically coexist with H2, CO, CH4 and H2O, while C2H2, C2H4, C3H8, C4H8 and C4H8O are suppressed at essentially zero.  Higher pressures have a negative effect on the H2 concentration. The maximum H2 efciency is achieved at atmospheric pressure.  Coke tends to form at low temperatures and low CBRs. The reaction should be carried out in the coke-free regions. Otherwise, the catalysts selected must be able to resist coke formation.

3.5. The optimal operating conditions The operating conditions for hydrogen production from DRB are optimized to obtain the maximum H2 formation with complete conversion of C4H10O. These include the CBRs, pressures, and temperatures. Under the above conditions, high H2 content could be achieved with the lower reaction temperature and the smallest size of reactor. The difference in H2 and CO production calculated as a function of CBR and temperature at 1 atm is evaluated.

Acknowledgment The nancial support of this work by China Postdoctoral Science Foundation Funded Project (20090460021) is gratefully acknowledged. References
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Table 3 Optimal operating conditions and corresponding results of DRB. Optimal conditions Temperature (K) Pressure (atm) CBR Results of DRB C4H10O conversion (%) H2 concentration (%)a CO concentration (%)a CH4 concentration (%)a
a

11501200 1 3.54.0 100 34.9137.98 57.3457.87 0.010.20

On a wet basis.

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