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Thermodynamic study of the supercritical water reforming of glycerol

rrez Ortiz*, P. Ollero, A. Serrera, A. Sanz F.J. Gutie
Departamento de Ingenier a Qu mica y Ambiental, Universidad de Sevilla, Camino de los Descubrimientos, s/n, 41092 Sevilla, Spain

article info
Article history: Received 15 March 2011 Accepted 14 April 2011 Available online 18 May 2011 Keywords: Reforming Supercritical water Thermodynamic analysis Equation of state Glycerol Biodiesel

abstract
Hydrogen can be produced by steam reforming, partial oxidation, autothermal, or aqueousphase reforming processes using various noble metal based catalysts, but also by supercritical water (SCW) reforming. Using AspenPlus, a systematic thermodynamic analysis of glycerol reforming using supercritical water has been carried out by the total Gibbs free energy minimization method, which computes the equilibrium composition of synthesis gas (syngas). The predictive SoaveeRedlicheKwong equation of state (EOS) has been used as thermodynamic method in the simulation of the supercritical region, after evaluating it against other EOS methods. A sensitivity analysis has been conducted on supercritical water reforming of pure and pretreated crude glycerol, as obtained from biodiesel production. The effect of the main operating parameters (temperature, concentration of glycerol feed, glycerol purity in the feed of crude glycerol, and pressure) aimed to the hydrogen production has been investigated in the reforming process, by obtaining the mole fraction and molar ow-rate of components in syngas, as well as the hydrogen yield. Selectivity to the different compounds has been also calculated. By this way, the thermodynamic favorable operating conditions at which glycerol may be converted into hydrogen by SCW reforming have been identied. The simulation results agree well with some few experimental data from the literature. This study is the rst of a series addressed to glycerol reforming using SCW. Copyright 2011, Hydrogen Energy Publications, LLC. Published by Elsevier Ltd. All rights reserved.

1.

Introduction

In recent years there have been intensive efforts toward the development of novel technologies for the production of hydrogen from renewable resources, mainly biomass. Among the various biomass-derived compounds proposed as feedstock for hydrogen production, glycerol (C3H5(OH)3) is of special interest because it is produced in large amounts (10 wt %) as by-product of the chemical reaction (transesterication) in which vegetable oil is processed into biodiesel. By-product glycerol comprises a mixture of several other constituents, such as methanol, water, inorganic salts, free fatty acids,

unreacted mono-, di-, and triglycerides, and methyl esters. Conventional options for crude glycerol consist of rening it to a higher purity. Unfortunately, the rapidly expanding market for biodiesel cannot accommodate the excess amounts of glycerol generated altering thus the cost and availability of glycerol. However, glycerol production and utilization has a great impact on both the economic stability and sustainability of biodiesel production that will continue to increase as the industry grows. As such, for utilizing the glycerol byproduct it is crucial to develop innovative processes. The valorization of the crude glycerol, while avoiding the application of expensive purication processes, will allow

* Corresponding author. Tel.: 34 95 448 72 68; fax: 34 95 446 17 75. rrez Ortiz). E-mail address: fjgo@esi.us.es (F.J. Gutie 0360-3199/$ e see front matter Copyright 2011, Hydrogen Energy Publications, LLC. Published by Elsevier Ltd. All rights reserved. doi:10.1016/j.ijhydene.2011.04.095

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augmented protability of the biodiesel plants. One promising and economical alternative is the transformation of glycerol into an energy derivative as, for instance, to use it as a renewable source of hydrogen, which is often dened as the future energy carrier. This can be done with the use of several methods including some reforming processes. Besides, establishing a technology for hydrogen production from this waste is desirable from the perspective of reduction of fossil fuel consumption for power generation. By now, glycerol reforming has been extensively studied and an evaluation of these studies appears attractive. Three types of glycerol reforming processes e steam reforming [1,2], aqueous-phase reforming [3], and autothermal reforming [4] e have primarily been investigated, but the glycerol reforming by using supercritical water (SCW) has been barely studied from a thermodynamic point of view, and even less using not pure but crude glycerol. Reforming reactions are generally endothermic, and a reforming process may be characterized depending on the source of heat and types of reactants. A general equation to describe glycerol reforming is shown in reaction (1). C3 H8 O3 xH2 O aCO2 bCO cH2 O dH2 eCH4 . (1)

The equilibrium composition depends upon the reactant ratios as well as the reaction temperature and pressure. Reforming products include hydrogen and carbon monoxide in addition to carbon dioxide and methane. A catalyst is normally used to accelerate the reactions in the reforming process. Ni, Co, Ni/Cu, and noble metal (Pd, Pt, Rh) based catalysts all favor hydrogen production, with Ni being the most commonly used [5]. Catalysts boost the reforming reaction rates at the molecular level and many thorough discussions of the topic are available in the literature. Glycerol steam reforming is the more popular reforming process, and it can be represented by the overall reaction (2): C3 H8 O3 3H2 O 3CO2 7H2 (2)

allows the product of SCWG to leave the system free from the salt. More details are available in the literature [9]. Supercritical water is characterized by its high ion product, which implies high [H] or [OH] concentration in supercritical water. This allows SCW act like an acid or base catalyst in the reactions. Many organic chemicals that do not react in water without the presence of strong acid or base catalyst may readily react under the hydrothermal condition of SCW. Reactivity of water increases in the neighborhood of the critical point with or without a catalyst. Thus, the reforming of glycerol to synthesis gas or syngas (SG) using supercritical water under a catalyst-free process arises as a very interesting alternative and it will be studied in a future experimental work. Due to the unique properties of SCW, thermodynamic equilibrium and high chemical reaction rates are possible. In fact, using SWC may be an excellent means for extraction of energy from biomass, and allows high hydrogen concentration in the product gas with suppression of char and tar formation [10]. At temperature higher than 600  C and pressure higher than that of its critical point, water becomes a strong oxidant. As a result, carbon is preferentially oxidized into CO2 although low concentrations of CO are also formed. The hydrogen atoms of water and glycerol, as biomass, are set free and form H2. The gas product (syngas) consists of H2, CO2, CH4 and CO. Thus, for the design of the reactor and separators, the knowledge of phase equilibria is very important.

2.

Aims and scope

Thus, 7 mol of H2 are produced per mol of glycerol on the reaction stoichiometry. Major concerns are by-product formation (e.g., CO), catalyst deactivation, and high energy consumption. There are more reforming processes and this work is focused on reforming using supercritical water (SCW), which is dened as water that is heated and compressed over its critical temperature (374  C) and pressure (22.1 MPa). Supercritical water (SCW) has properties very different from those of liquid water. The dielectric constant of SCW is much lower, the number of hydrogen bonds is much lower and their strength is much weaker. As a result, SCW behaves like many organic solvents so that organic compounds have complete miscibility with SCW. Moreover, gases are also soluble in SCW, thus an SCW reaction environment provides an opportunity to conduct chemistry in a single uid phase that would otherwise occur in a multiphase system under conventional conditions [6]. Gases like CO2, CH4, H2, and CO are completely miscible in supercritical water [7,8]. The polar inorganic compounds like KCl, NaCl, CaSO4 etc., which have high solubility in subcritical water, shows very low solubility in supercritical water. Thus, it is relatively easy to separate them from the product. This

The objective of a reforming process of crude glycerol is to produce hydrogen; however selectivity to hydrogen remains challenging due to subsequent reactions in the gas. Thermodynamic studies are very important because they provide information on conditions that are advantageous for hydrogen production. Thus, the aim of this study is to examine hydrogen production by SCW reforming of pure and crude glycerol, which comprises impurities that cause catalyst deactivation. Firstly, a discussion about the most suitable thermodynamic method to be used for the simulation of the supercritical state is carried out. Then, by predicting the synthesis gas composition (hydrogen, carbon monoxide and others) at equilibrium condition in the reforming reactor, a sensitivity analysis is performed to know the effect of the main operating parameters on hydrogen yield, so as to achieve optimal conditions for glycerol SCW reforming that maximize hydrogen production.

3. Equations of state and simulation of the supercritical state

When the operating temperature is beyond the critical point, the simulation tool used in this work, AspenPlus, considers a gaseous behavior for the stream. Likewise, for lower temperatures the properties taken by this software corresponds to a liquid. Therefore, in the supercritical region, the error of some thermodynamic properties, like enthalpy and entropy, should be quoted depending on their reference to the liquid or vapor state, as considered by AspenPlus. By checking

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and comparing the results provided by different thermodynamic methods, previously discriminated based on their rightness of use in supercritical state, the most suitable one to be chosen is that providing minima deviations in properties from liquid and vapor state. Besides, this is also essential as a prior step for achieving a conceptual design of the process to be studied with condence, by carrying out energy analysis and using a heat exchangers network for recovering the process heat [11]. The most computationally straightforward and thermodynamically consistent method for calculating high pressure phase behavior is to select an equation of state (EOS) to model both the liquid and vapor or supercritical uid phases, in opposition to those thermodynamic methods based on activity coefcients, which cannot be used for phase equilibrium with supercritical uids due to the different manner that they treat each phase, and hence they cannot represent the changes that occur in the critical region in continuous form. The thermodynamic method nally chosen for fugacity calculation was the predictive SoaveeRedlicheKwong (PSRK) equation of state [12,13], which is an extension of the SRK equation of state, and uses the generalized MathiaseCopeman a-function. This model uses the HolderbaumeGemehling mixing rules, which can predict the binary interactions at any pressure. Using UNIFAC, the PSRK method is predictive for any interaction that can be predicted by UNIFAC at low pressure. The main advantage of using PSRK equation of state is that it is more accurate in the prediction of the binary interaction parameters and it gives more satisfactory results for mixtures of non-polar and polar components, as the case of the crude/pure glycerol and water mixture. This choice has been weighed against other thermodynamic methods such as the original SoaveeRedlicheKwong (SRK), Peng-Robinson (PR) and Peng-Robinson with the BostonMathias afunction (PR-BM). The PSRK method represents quite accurately the supercritical state for the glycerol and the CO2 (taking as a reference since it is probably the uid more studied in supercritical

state), as shown in Fig. 1, although 240 atm is a pressure much higher than critical pressure of glycerol (74.02 atm) and CO2 (72.86 atm). PR and PR-BM also give a very good t and the SRK shows small deviations, although these are not shown. On the other hand, for the water, the PSRK method shows the minimum deviation between the liquid and vapor curves in the supercritical state (Fig. 2) of all the thermodynamic methods tested. The absolute error for specic enthalpy (difference between liquid and vapor curves) has been quoted between 3 and 6 kJ/mol in the critical region, showing the maximum deviation around 565  C. Although 6 kJ/mol may not be considered as a large difference, it should be noted that the glycerol should be very dilute in the reforming with SCW, as after explained, so an error of 6 kJ/mol could become a signicant divergence from the energy standpoint. The PR and PR-BM methods showed behaviors similar to that depicted in Fig. 2 for PRSK, but the deviations are slightly higher. Then, these methods could be also used with relative condence. However, the SRK method showed large errors. For the glycerol, it has been veried that in the supercritical state, the vaporization heat is saved, which is a very signicant energy saving and agrees well with data from literature [14,15]. This is illustrated in Fig. 3, where a specic energy saving of 47.3 kJ/mol is obtained when operating at 600  C and 240 atm, which is lower than the glycerol vaporization heat (58.2 kJ/mol) at its boiling point (1 atm, 290  C). However, the energy saving continuously decreases as the temperature rises. In the case of water, depicted in Fig. 4, there is an uncertainty relative to the error due to the mismatch between the enthalpies referred to vapor and liquid states for temperatures higher than the critical temperature. This inconvenient may be overcome by an average curve between the vapor and liquid curves, with a maximum error of 3 kJ/mol, or by directly taking the vapor curve as the valid one, since this option corresponds to the minimum energy saving. The increase in enthalpy is huge when changing from liquid to vapor at atmospheric pressure. However, for the liquid at

Fig. 1 e Simulation of the supercritical state for glycerol and CO2 at 240 atm (PSRK method).

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Fig. 2 e Evolution of the water trend in liquid and vapor state at 240 atm (PSRK method) - each enthalpy interval is 2 kJ/mol.

240 atm, it can be seen that when temperature rises to the critical value, the slope of the curve rapidly increases. Beyond this zone, the specic energy saving becomes 10.7 kJ/mol at 400  C (Fig. 4). Although this value is quite lower than that for glycerol, there will be a signicant energy saving due to the heat up of the large amount of water required for the SCW reforming of glycerol to maximize hydrogen yield, as below exposed. However, by increasing the temperature from 400 to 800  C, the specic energy saving would decrease from 10.7 to 4.5 kJ/mol. Therefore, the energy saving is lower for temperatures much higher than 374  C. Besides, the energy analysis should account for the mechanical energy necessary to raise the pressure from atmospheric to supercritical values.

Fig. 5 illustrates the effect of pressure on simulation of the supercritical state for the water, it can be seen that when the pressure increases over the critical value, the vapor curve exhibits a decrease in enthalpy at temperatures slightly under the critical one in such a way that the liquid and vapor enthalpies matches just in the critical point. Besides, when the pressure is twoethree times higher than critical pressure, the vapor and liquid states match well for supercritical temperatures. In Fig. 6 a more narrow range of temperatures has been used in order to get better accuracy in the cited vapor behavior around the critical point under different pressures. Thus, it was carried out an analysis between 350 and 400  C using temperature increments of 0.10  C (500 point data versus the

Fig. 3 e Vaporization heat (l) and energy saving for the glycerol at 240 atm. The blue curve represents the vapor state at atmospheric pressure and it is taken as a reference in the computation of the energy saving. (For interpretation of the references to colour in this gure legend, the reader is referred to the web version of this article.)

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Fig. 4 e Vaporization heat (l) and energy saving for the water (supercritical pressure of 240 atm).

previous gures that is 100 point data). These analyses were done for both subcritical and supercritical conditions. At 210 and 215 atm, the enthalpy curves for liquid and vapor phases are not still concurrent. At 218 atm, the curves match each other just at 374  C. At pressures higher than the critical one, the enthalpy curve tends to abruptly diminish just at 374  C, where it matches with the liquid curve. Next, a unique curve is shown. The sudden enthalpy drop of the vapor curve at the critical temperature for pressures higher than the critical is quite sound. The reason is because the thermodynamic

method used is based on an EOS where, by denition, the fugacity of liquid and vapor in the critical point must be equal. This implies that all the properties must be equal in this point, and so the enthalpy. By this way, it has been obtained a decrease in enthalpy as the temperature increases inside a given range just before reaching the critical point, which is not thermodynamically reasonable. The explanation of this simulated behavior is due to the vapor curve for water is not real at temperatures lower than the critical under pressures higher than the critical. That is, at pressures as high as those

Fig. 5 e Enthalpy variation for water in liquid and vapor phase at 220, 300, 600 and 800 atm.

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Fig. 6 e Enthalpy variation between 350 and 400  C for water in liquid and vapor phase at 210 and 215 atm (subcritical conditions), 218 atm (critical conditions), and 220, 240, 400 and 600 atm (supercritical conditions). computation has been made with the aid of AspenPlus version 2006.5 [16]. In this study, an R-Gibbs reactor has been used to calculate the products composition and the heat of overall reaction in a system under the conditions that minimize of Gibbs free energy. This is a non stoichiometric approach, where a selection of the possible set of reactions is not necessary and does not require any initial estimation of the equilibrium. Indeed, the method of minimizing the Gibbs free energy is normally preferred in fuel-reforming analysis, especially when the reaction temperature and pressure are specied. The R-Gibbs reactor does not take reaction kinetics into account and allows individual reactions to be at a restricted equilibrium. The thermodynamic analysis ignores and does not provide kinetics effects of reactions taking place, and it assumes equilibrium. Although a practical situation may diverge, the results of the analysis provide a valuable reference on optimal conditions for hydrogen production so as to design experimental tests and compare the results from these.

used in these analyses, the water must be in liquid phase. As a consequence, although AspenPlus provides results for the vapor curve in any interval of temperatures, the part of the vapor curve to be rightly used is that just over the critical point, i.e., the part relative to the supercritical region. Likewise, the rapid increase of the liquid enthalpy around the critical temperature found for pressures around the critical pressure becomes negligible at pressures higher than 400 atm, where supercritical state is more clearly distinguished from the subcritical state. Finally, a sensitivity analysis for the case of water was carried out to study the transition from the subcritical to supercritical state starting at a given pressure. Results are shown in Fig. 7, in an HeP diagram, where it can be seen that there is a decrease in the enthalpy corresponding to the vaporization heat due to phase change from vapor to liquid for all the isothermal curves, except at 400 and 500  C (values higher than the critical temperature). This vaporization heat decreases when temperature approaches to the critical one (374  C), where becomes null. Beyond the critical point, enthalpy slightly decreases as pressure rises.

4.1.

Process simulated

4. Methodology of the thermodynamic analysis

For given operating conditions, the equilibrium compositions in the reforming reactor have been calculated. The

The simulated process is illustrated in Fig. 8. The ow-sheet consists of a high pressure pump for the glycerol-water mixture, obtained in a mixer and a heater in order to respectively get the pressure and temperature specied for the reforming reactor. It is assumed that reactor also operates by providing the energy needed to hold the endothermic

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Fig. 7 e Enthalpy of water as function of pressure at constant temperature (100, 200, 300, 350, 400 and 500  C).

reactions so as to operate at the specied temperature. Hydrogen, carbon monoxide, carbon dioxide, methane, ethane, propane, water, methanol, ethanol and glycerol as well as pure carbon were manually added for being considered as the possible species in SCW reforming of glycerol. The simulation did not predict coke formation for any of the experimental conditions in this paper, and it did not add any other compound (mole fractions lower than 1020). Next, an expander (turbine) is included to reduce the pressure in an efcient way. Downstream from the expander, a cooler diminishes the temperature to 200  C. Then, an Equilibrium reactor (Requil) is used to model the wateregas shift reaction to increase the conversion to hydrogen in the syngas and to reduce the CO content, which poisons the anode of proton exchange membrane fuel cells (PEMFC). Requil operates withdrawing the energy released from the exothermic reaction so as to operate at the specied temperature. The outlet stream is after cooled to 60  C in another cooler to drive, e.g., the gas to a PEMFC where hydrogen would be converted into electrical energy. Finally, a ash separator is included to separate liquid

condensates from the gaseous phase. Pressure reduction should not be made after cooling to 200  C because another separator should be added, prior to expansion, where there would be a signicant fraction of hydrogen removed in the liquid outlet stream and, hence, an important yield lost. Specications of elements used in the simulation are shown in Table 1. As aforementioned, the thermodynamic method used has been the predictive SoaveeRedlicheKwonge(PSRK). This method was contrasted against UNIFAC and Ideal methods for the low pressure zone of ow-sheet downstream from the expander (operating at about atmospheric pressure), but results are undisturbed, so for the sake of simplicity, PSRK method was used for all the simulation.

4.2.

Crude glycerol simulated

Two feeds have been considered: pure and pretreated crude glycerol. Normally, 1:6e1:9 M ratios of oil-to-methanol are used in the transesterication of vegetable oil to biodiesel with catalyst NaOH. After the reaction is nished, large amount of

W B1 01 PUMP 02

HEAT1 03

R1

04 B2 C OOL2 C OOL1 05 SG1 W2 8 R2 SG2 SG3 SEP SG4

GLY

Fig. 8 e Flow-sheet of the simulated process.

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Table 1 e Specications of the components for the simulation. Code

B1 PUMP HEAT1 R1

Equipment
Mixer Pump Heat exchanger Reactor

Specications
Outlet pressure: Variable Pressure drop: 0.2 atm. Outlet temperature Variable Inlet temperature: Variable Outlet temperature Inlet temperature Pressure drop: 0.22 Pa Isentropic turbine Outlet Pressure: 1.4 atm. Outlet temperature: 200  C Pressure drop: 0.2 atm. Inlet temperature: 200  C Outlet temperature Inlet temperature Reaction: H2O CO H2 CO2 Outlet temperature: 60  C Pressure drop: 0.2 atm. Outlet temperature Inlet temperature 60  C

B2 COOL1 R2

Expander Heat exchanger Reactor

COOL2 SEP

Heat exchanger GaseLiquid separator

the methanol is unreacted. Since methanol and glycerol both have carbon-to-alcohol ratios of 1:1 with associated high degrees of hydrogen bonding, the methanol preferentially distributes into glycerol phase, and only a relatively small amount dissolves in biodiesel, as experimentally veried [17]. Indeed, the main components of crude glycerol are glycerol and methanol [18], and also water [19], which is used to reduce its viscosity and allow the crude glycerol to be pumped. Anyway, in order to better perform the reforming process, an economic solution for the partial purication of crude glycerol stream should be done, especially to reduce the negative impact on catalyst and reactor material under supercritical conditions. Thus, in this study it is assumed that de crude glycerol is pretreated to remove high salt (it may be very corrosive) and free fatty acid content as well as methyl esters impurities (these two latter may be converted into undesired tar and coke [10]), e.g., by neutralization. The salt formed during this phase may be recovered for use as fertilizer, after precipitation and ltration. Furthermore, the methanol may be stripped from this stream to be recovered and reused. Thus, this pre-treatment would produce a stream with >80 wt% pure glycerol. Therefore, a pretreated crude glycerol consists of glycerol (80 wt%), methanol (20 wt%) and no water has been considered in this study. The possible water content in the pretreated crude glycerol feed is included inside the water stream, and thus an anhydrous crude glycerol feed is referred in this work. The upper concentration of MeOH has been limited to 30 wt % in the crude glycerol, as a realistic value, since the MeOH recovery is essential for the economy of a biodiesel production plant.

concentration for both the pure and the pretreated crude glycerol. In addition, for this latter, a sensitivity analysis has been performed for the MeOH content in the crude glycerol, as a measure of the glycerol purity of crude feed. The total molar ow-rate fed to the system is always 1000 mol/h. The analyses were carried out over the following variable ranges: temperature of 400e1000  C, glycerol to feed (glycerol plus water) mole ratio of 1e16 (990 mol/h water and 10 mol/h glycerol e 840 mol/h water and 160 mol/h glycerol) and pressure ranging from 200 to 300 atm, for both pure and pretreated crude glycerol. MeOH content in the crude glycerol was changed from 10 to 30 wt%. Selectivity results are analyzed for the reactor outlet stream (4) and the hydrogen yield is referred to this stream as well as to the outlet stream of the WGS reactor (stream SG2), so as to include the global process. In the simulation results, the contents of ethane, propane and ethanol have been grouped as the content in organic carbon different of methane (namely Others), due to in all the cases the concentration of those compounds at the reactor outlet are quite lower than those corresponding to the other compounds. In addition, at glycerol to feed mole ratios used from 1 to 16, carbon formation is predicted to be thermodynamically inhibited at any temperature analyzed in this study, due to the high proportion of water, and so the carbon (graphite) production is insignicant and not shown.

5.1.

Effect of the reaction temperature

5.

Results and discussion

A sensitivity analysis has been carried by varying operating pressure and temperature as well as the glycerol feed

Reaction temperature is perhaps the most important parameter that inuences the performance of SCW reforming of glycerol. It is expected to have a signicant effect on the process yield, especially in absence of catalyst [15]. To avoid the use of a catalyst, which becomes essential for low temperature processes, the present study only considers high temperatures. So, the uncatalyzed reforming will need high temperature (500e800  C, and even more), although it is less efcient than that at low temperature from the energy and exergy point of view, since external energy may be needed to sustain the process. The overall reforming yield depends on chemical reactions involved and their rate. The product gas composition would be governed by the chemical equilibrium of the reactions involved. Since the reaction rate constant would increase with temperature, the overall reforming yield would be higher and its rate of increase with time would also increase as temperature does so. On the other hand, the reaction of complete conversion of glycerol to hydrogen is endothermic while the reaction that completely converts glycerol to methane is slightly exothermic. Thus, on equilibrium conditions and according to the Le Chatelier principle, the methane formation increases at lower temperature. CH4 competes against H2, and obviously, CH4 is not a desirable product if the ultimate goal is hydrogen production. As a consequence, it is clear that high reforming temperatures are recommended. Since the minimum operating temperature is the critical (374  C), the effect of the temperature has been analyzed on the equilibrium of the different reactions taking place in the reactor by varying in increments of 50  C, between 400 and

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1000  C. The pressure was kept at 240 atm and the glycerol concentration in the feed was always 1 mol % (5 wt%). Results are shown in Figs. 9 and10 relative to streams 4 and SG2 (outlet of the reformer and WGS reactor respectively) for both pure and pretreated crude glycerol. These gures represent the equilibrium mole fraction of the gaseous products in dry basis as a function of temperature. For the pure glycerol, it is depicted that the mole fraction of hydrogen increases with the increase in the temperature up to a maximum value and then it is approximately constant (about 0.689) in R1, and 0.696 at the outlet of R2, very next to maximum value according to the stoichiometry of the reaction (3), as CH4 and CO are insignicant, due to the operating conditions that does not promote the methane production and to the huge excess of water, which consumes near all of carbon monoxide. In addition, the reaction (3) is endothermic, so it is very shifted to the right side at high temperatures. overall glycerol reforming: C3 H5 OH3 3H2 O 3CO2 7H2 glycerol decomposition: C3 H5 OH3 3CO 4H2 wateregas shift: CO H2 O CO2 H2 (3b) (3a) (3)

The reactions of methanol reforming (6) and decomposition (7) are the following: methanol reforming: CH3 OH H2 O CO2 3H2 methanol decomposition: CH3 OH CO 2H2 (7) (6)

For pretreated crude glycerol reforming the results are very similar to those obtained for pure glycerol, especially relative to the mole fraction of hydrogen, although the mole ow-rates are lower according to reactions (3) and (6). On reactions (3) and (6), hydrogen yield are computed for pure and pretreated crude glycerol as follows (Eq. (8) and (9)): hpure mol=h H2 1 mol=h C3 H5 OH3 7 mol=h H2 mol=h C3 H5 OH3 7 mol=h CH3 OH 3 (8)

hcrude

(9)

As expressed by reactions (3a) and (3b), overall glycerol reforming may be represented as a rst stage of glycerol decomposition followed by a wateregas shift reaction. In Figs. 9 and 10, it can be also observed that the mole fraction of CH4 decreases with the increase in the temperature, mainly because the high temperatures favors its thermal decomposition forming hydrogen and CO2 in the presence of water, as it can be seen in the reaction (4). methane steam reforming: CH4 H2 O 3H2 CO (4)

Likewise, the mole fraction of CO2 decreases with the increase in the temperature because at high temperature the reaction between CO2 and CH4 is promoted thus producing CO and H2, on the reaction (5). methane dry reforming: CO2 CH4 2H2 2CO (5)

Thus, Figs. 9 and 10 also illustrate the hydrogen yield in the reforming reactor (R1) and for the overall process. The glycerol and methanol conversion were always 100%, at equilibrium condition. Between 750 and 800  C, the hydrogen yield becomes approximately constant and equal to 95%, at the R1 outlet, achieving 99% in the WGS reactor at 200  C and 1 atm. Likewise, a maximum value is reached for 900  C in R1 (95.9%), and the hydrogen content scarcely changes for temperatures greater than 900  C. Anyway, for a practical purpose, beyond 800  C the yield can be considered as constant, and thus a temperature higher than 800  C would be unnecessary. For the pretreated crude glycerol, the hydrogen yield should be referred to the sum of glycerol and methanol, so as to avoid to get efciencies higher than 100%. With respect to the pure glycerol, for pretreated crude glycerol relatively higher hydrogen yields are obtained although hydrogen production (molar ow-rate) is lower, due to the methanol presence, which reforms better but produces less hydrogen than glycerol. A case study was performed (but not shown) by considering a feed with a 16 mol % of pretreated crude glycerol with a 10 wt% methanol, and very low mole fraction of hydrogen as well as very high increase in methane production were obtained. Moreover, it was veried that at temperatures lower than 750  C, hydrogen yield is lower than 20%, and almost the main production is methane and carbon dioxide.

At higher temperatures, this endothermic reaction is favored and therefore CO2 produced is after consumed. Indeed, reactions (3)e(5) are endothermic so an increase in temperature will provide a shift of the equilibrium toward the products (right side of reactions). Table 2 shows the reaction enthalpy for these three reactions (3)e(5), obtained for both standard conditions (298 K and 1 atm) and nominal operating conditions (800  C and 240 atm). The rest of organic compounds (grouped in Others) present a concentration much lower than 0.01 mol %, so these compounds can be considered as insignicant and be neglected. As a result, the more likely expected products are CO, CO2, CH4 and H2. In addition, CO will practically disappear in the wateregas shift (WGS) reactor (R2).

5.2.

Effect of glycerol concentration in the feed

An interval from 1 to 16 mol % (about 5e50 wt%) of glycerol concentration in the feed, with water being the rest, has been studied at 240 atm and 800  C. For the pretreated crude glycerol, 20 wt% is methanol. Results are represented in Fig. 11 and 12, which depict gas concentration at the outlet of the reforming reactor (R1) and the WGS reactor (R2) as a function of glycerol feed concentration for pure and pretreated crude glycerol. It can be observed that the mole fraction and the molar ow-rate of methane increase as well as the mole fraction of hydrogen decreases and its molar ow-rate increases as the glycerol feed concentration rises. This is an expected result since a higher

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Fig. 9 e Mole fraction (a), molar ow-rate (b) of the outlet gases and hydrogen yield (c) for a pure glycerol concentration in the feed of 1 mol % at 240 atm. Streams 4 and SG2.

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Fig. 10 e Mole fraction (a), molar ow-rate (b) of the outlet gases and hydrogen yield (c) for a crude glycerol (20 wt% MeOH, 80 wt% C3H8O3) concentration in the feed of 1 mol % crude glycerol at 240 atm. Streams 4 and SG2.

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glycerol concentration lessens the shift toward the right side of reaction (3) due to the lower water surplus. Accordingly, the reforming reaction to produce hydrogen compete against the methanation reactions, in such a way that the produced hydrogen is partially consumed by reacting with CO and CO2 to produce CH4, as shown in reactions (10) and (11): methanation of CO: CO 3H2 CH4 H2 O methanation of CO2: CO2 4H2 CH4 2H2 O (11) (10)

issues should be further inspected for an energy analysis of the process, as it will be done in the next work. Because of the high CO2 content in the syngas produced, the dry reforming of methane (reaction (5)) will also proceed. Dependent upon the water to methane ratio and CO2 content in the syngas, CH4 is more or less reformed with H2O or CO2. Thereby, the equilibrium of the wateregas shift reaction and H2 and CO mole fraction in the synthesis gas are affected.

5.3. Effect of the methanol concentration in the crude glycerol

Fig. 13 shows how the increase in MeOH concentration (decrease in C3H5(OH)3 purity) of the crude glycerol leads to a reduction of the molar ow-rate of hydrogen and carbon dioxide for streams 4 and SG2. This effect is stronger if the crude glycerol feed concentration was higher, in such a way that hydrogen produced from the reforming of methanol is less than that obtained from glycerol reforming, on reactions (3) and (6). Fractions of MeOH in the crude glycerol should be controlled at low values, not because of inefcient methanol reforming, but to save it thus recovering and returning to the biodiesel production process. An increase of methanol fraction in crude glycerol makes the concentration of CO and CO2 decrease very slightly as well as does with the molar ow-rates of those compounds. Therefore, the concentrations of carbon monoxide and carbon dioxide are not practically affected by the variation of MeOH in the feed concentration. The simulation results showed good agreement with the theoretical results obtained by previous studies regarding with the SCW reforming of methanol [20,21]. Moreover, in order to contrast the effect of methanol by minimizing the effect of the high water dilution, another simulation was also performed (but not illustrated in a gure) using 16 mol % pretreated crude glycerol with variable MeOH content at 800  C and 240 atm. Apart from the low mole fraction and yields of hydrogen as well as high production of methane, as expected, the effect of MeOH as such was disclosed as insignicant (at curves) for the range tested (10e30 wt% MeOH).

The temperature also affects these two equilibria, moving them to the left side when the temperature increases, because of reactions (10) and (11) are exothermic. Thus, CH4 production is inhibited by operating at high temperatures, as aforementioned. Mole fractions of CO and CO2 increase as glycerol concentration increases in the feed, although not as much as CH4. Anyway, CO2 mole fraction is quite higher than that of CO due the wateregas shift reaction, which promotes the reaction (3b) leading thus to CO2 production. Results for pretreated crude glycerol are qualitatively similar to those obtained for pure glycerol, and values of mole fraction for the product gases are practically the same. The difference is found in the molar owrate that is lower for a crude glycerol with higher content in MeOH, since the number of carbon, hydrogen and oxygen atoms is lower in the methanol for a given total feed molar ow-rate. Moreover, Figs. 11 and 12 also illustrate that higher methanol content in the crude glycerol relatively enhances the hydrogen yield dened by Eq. (9), although hydrogen production (molar ow-rate) is lower. If instead of using Eq. (8) and (9), the hydrogen yield is expressed by the produced H2 molar ow-rate to (pure or crude) glycerol feed molar owrate ratio, the values obtained for pure glycerol would be higher than those for pretreated crude glycerol. Thus, with regarding to R1 reactor, and in case of feeding pure glycerol, 6.66 mol of H2 are produced per mol of glycerol for a glycerol concentration of 1 mol % (5 wt%), while at 16 mol % (49 wt%) glycerol, the number of H2 moles produced per mol of glycerol decreases to 1.44. For the crude glycerol with 20 wt% methanol, the ratios are 5.17 and 1.39 mol of H2 are produced per mol of pretreated crude glycerol, respectively. When the yields are referred to R2 reactor, the ratios are 6.86 and 1.99 for pure glycerol; 5.90 and 1.66 for crude glycerol, respectively. Therefore, the process moves far from the optimum for hydrogen production as the glycerol feed concentration increases, but for low glycerol feed concentration the unreacted water (as steam) dilutes hydrogen product. These

5.4.

Effect of the reaction pressure

According to some authors, the effect of pressure is negligible in the supercritical region [14,21,22]. However, when the pressure is below the critical pressure, the special physical and chemical properties of water disappear. Likewise, higher pressure causes trouble for the design and maintenance of the system and also increases the operating and investment costs. For it, a pressure range from 200 to 300 atm has been considered by taking increments of 20 atm. By this way, the process is

Table 2 e Reaction enthalpies for the main reactions taking place inside the reforming reactor under standard (298.15 K, 1 atm) and operating (1073.15 K, 240 atm) conditions. Reaction
C3 H8 O3 3H2 O43CO2 7H2 CH4 2H2 O44H2 CO2 CO2 CH4 42H2 2CO

Enthalpy standard cond. (kJ/mol) (25  C, 1 atm)

358.01 252.85 247.00

Enthalpy operating cond. (kJ/mol) (800  C, 240 atm)

192.42 197.64 260.87

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compared under subcritical conditions and the possible advantages of increasing the operating pressure are evaluated, from the thermodynamic point of view. The temperature was kept in 800  C and the glycerol concentration in the feed has been of 1 mol%. The simulation for crude glycerol is almost

equal to that of pure glycerol, and it has not been included in this paper. Fig. 14 depicts the results of the simulation, for the pure glycerol. In general, it can be observed that the pressure barely affects the gas composition at the reformer outlet, even for subcritical region. H2, CO2, CO and CH4 change all of them

Fig. 11 e Mole fraction (a), molar ow-rate (b) of the outlet gases and hydrogen yield (c) as a function of the glycerol concentration in the feed (pure glycerol) at 800  C and 240 atm. Streams 4 and SG2.

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very slightly. Consequently, hydrogen yield and glycerol conversion are almost constant for the overall range of pressures tested. Thus, 240 atm can be considered as a suitable pressure, taking into account that it is convenient to have

a margin over the critical pressure (218 atm) thus accounting for pressure drops in the equipment and through the pipes. However, values slightly lower than 240 atm should be experimentally inspected.

Fig. 12 e Mole fraction (a) and molar ow-rate (b) of the outlet gases and hydrogen yield (c) as a function of the glycerol concentration in the feed (crude glycerol, 20 wt% MeOH and 80 wt% C3H8O3) at 800  C and 240 atm. Streams 4 and SG2.

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5.5.

Selectivity computation

Finally, in order to assess the reactions taking place inside the reforming reactor (R1), selectivity to main compounds

(H2, CO, CO2 and CH4) were computed, for both pure and pretreated crude glycerol, just at the reforming reactor outlet (stream 4). For the pure glycerol, the selectivity computation to component x was made by using Eq. (12), where the

Fig. 13 e Mole fraction (a) and molar ow-rate (b) of the outlet gases and hydrogen yield (c) as a function of the methanol concentration (wt%) in the feed (crude glycerol, 1 mol %) at 800  C and 240 atm. Streams 4 and SG2.

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Fig. 14 e Mole fraction of the outlet gases for a glycerol concentration in the feed (pure glycerol) of1 mol% glycerol at 240 atm and an operating temperature of 800  C. Stream 4.   nH2 xC3 H8 O3 xCH3 OH 100 nCO nCO2 nCH4 7=3 3=1

calculation for H2 and CO2 are shown as examples (Eq. (13)). This equation was modied for hydrogen by referring it to CO2 in reaction (3) that produces 7 mol of H2 per each 3 mol of CO2. Sx  no: C atoms in x no: total C atoms stream 4 nCO2 100 and SH2 nCO nCO2 nCH4 nH2 1 100 nCO nCO2 nCH4 7=3 (12)

SH2

(14)

SCO2

(13)

For a crude glycerol, a revised equation of selectivity to hydrogen was derived from reactions (3) and (6) and then used, as follows (Eq. (14)):

where xC3H8O3 and xCH3OHare the mole fraction of glycerol and methanol in the feed, respectively. Thus, it is weighted the mole ratio between H2 and CO2 in the reforming of glycerol (7/ 3) and methanol (3/1), on reactions (3) and (6). First, the selectivity analysis was performed for a nominal glycerol feed concentration of 1 mol% at 240 atm, and temperature was changed from 400 to 1000  C. Then, the glycerol concentration was changed from 1 to 16 mol %, at 800  C and 240 atm. In Fig. 15, it can be observed as, for a pure glycerol feed, hydrogen selectivity increases with the increase in the reaction temperature, and the methane selectivity decreases.

Fig. 15 e Selectivity of H2, CO, CO2 and CH4 as a function of the temperature for a glycerol concentration in the feed (pure glycerol) of 1 mol% glycerol at 240 atm and an operating pressure of 240 atm.

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Fig. 16 e Selectivity of H2, CO, CO2 and CH4 as a function of the temperature for a glycerol concentration in the feed (crude glycerol, 20 wt% MeOH and 80 wt% C3H8O3) of 1 mol % crude glycerol at 240 atm.

Beyond 800  C, CH4 production is insignicant. For a temperature higher than 750  C, CO2 selectivity begins to decrease, probably due to the reformation of CH4 with CO2 following the reaction (5). Similar trends are observed for pretreated crude glycerol (Fig. 16), and main differences between this latter and pure glycerol are in selectivity to hydrogen, about 850e900  C: 93.1 and 95.9%, respectively. Fig. 17 and 18 illustrate the decrease in selectivity to hydrogen as well as the rapid increase of selectivity to methane when the glycerol feed concentration is increased. Beyond the glycerol concentration of 8 mol %, CH4 selectivity becomes higher than H2 selectivity, for pure glycerol. So, if the product desired is hydrogen the glycerol feed concentration should be reduced as much as possible. Likewise, CO2

selectivity decreases as glycerol feed concentration rises while CO selectivity increases to reach a maximum at about 2e3 mol % pure glycerol and then decreases to 20%, remaining constant in this value from about 6 to 16 mol %, due to the reforming reaction is inhibited and promoted the methanation reactions (8) and (9). For pretreated crude glycerol, selectivity to CO rises to maximum (12.3%) at 2.8 mol % pure glycerol, remaining constant for higher concentration of glycerol. Finally, selectivity evolution versus pressure was also studied but it was veried a lack of dependence between both variables, and so the simulation results are not shown. Fig. 19 depicts a very weak effect of the methanol concentration in the crude glycerol for all the compounds. Although

Fig. 17 e Selectivity of H2, CO, CO2 and CH4 as a function of the glycerol concentration in the feed (pure glycerol) at 800  C and 240 atm.

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Fig. 18 e Selectivity of H2, CO, CO2 and CH4 as a function of the glycerol concentration in the feed (crude glycerol, 20 wt% MeOH and 80 wt% C3H8O3) at 800  C and 240 atm.

this gure shows the simulation results obtained by using 1 mol % crude glycerol, this is not due to the high proportion of water because another simulation for 16 mol % glycerol feed concentration was performed (but not shown) where the concentration of MeOH was changed from 10 to 30 wt% and no noticeable effect due to MeOH concentration was observed.

5.6. Optimal conditions for maximum hydrogen production

The maximum hydrogen yield is achieved at 900  C and for a glycerol feed concentration of 1 mol %, combining thus low

carbon monoxide and methane yields. Carbon monoxide and methane are considered undesirable products. CO affects the overall size of the reforming process, especially the wateregas shift reactors, and CH4 contains hydrogen, decreasing thus the overall hydrogen production. The higher the mole ratio of water to glycerol, the higher mole fraction of hydrogen (in dry basis) is. The carbon monoxide is nearly converted in the WGS reactor. However, the energy consumption and the size of the units increase as water owrate increases. All the thermodynamic analyses agree well with the few experimental results found in the literature [22], where at dilute feed concentration (5 wt% glycerol), 6.5 mol of hydrogen/

Fig. 19 e Selectivity of H2, CO, CO2 and CH4 as a function of the methanol concentration (wt%) in the feed (crude glycerol, 1 mol %) at 800  C and 240 atm.

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mol of glycerol was obtained at a temperature of 800  C and pressure of 241 bar, over Ru/Al2O3 catalysts in a tubular xedbed ow reactor. Therefore, if the real yields come close to those calculated assuming equilibrium is because of a right approach to equilibrium in real reactors is achieved.

In addition, it will be assessed the effect of reaction time by changing the feed ow-rate and performed studies on chemistry kinetics.

Acknowledgment 6. Conclusions
This research is supported by the Science and Technology Ministry of Spain under the research project ENE2009-13755, as a Project of Fundamental Research inside the framework of the National Plan of Scientic Research, Development and Technological Innovation 2008e2011.

Thermodynamic equilibrium calculations were done by minimizing Gibbs free energy using the predictive SoaveeRedlicheKwong method in AspenPlus, after evaluating against other equation of state based methods and discussing about the simulation of the supercritical state. The aim was to identify the operating conditions that maximize hydrogen production from a mixture of water and glycerol. The effects of reaction temperature and pressure as well as the glycerol feed concentration have been studied for pure glycerol and pretreated crude glycerol consisting mainly of glycerol and methanol, by varying this latter from 10 to 30 wt%. The reforming reactor and the wateregas shift reactor work at isothermal condition. From a thermodynamic point of view, and under equilibrium conditions, the best conditions to optimize hydrogen production are 900  C and 1 mol % glycerol in the feed. By this way, a hydrogen yield of about 95% for the pure glycerol and 97.2% for pretreated crude (20 wt% methanol) glycerol in the reforming reactor are achieved. These values rise to 99.7% and 99.9% in the wateregas shift reactor, respectively. However, compared to pure glycerol, the use of crude glycerol to produce hydrogen gives a lower performance regarding with the molar ow-rate of hydrogen produced in the reforming reactor due to the lower number of atoms present in methanol, i.e., the hydrogen production per mol of (pure or crude) glycerol is higher for pure glycerol. The water to crude glycerol ratio is a key factor to reduce the CO content in the WGS reactor, and the hydrogen yield decreases and methane production rises as the glycerol feed concentration increases, so a high water owrate is required. The operating pressure does not affect the results in the studied range (200e300 atm), and the analysis shows that a suitable operation pressure may be about 240 atm. For practical purposes, it is recommended to operate at temperatures from 750 to 800  C, depending on the hydrogen yield specied, since the glycerol conversion is total in all the range. Operating at not too high temperatures reduces the energy cost and extends the durability of materials. This is very important since under operating conditions so severe (combination of high pressure and temperatures) the special materials required signicantly increase the cost of the plant. The next work will consist of a conceptual design of the overall process including an energy and exergy analysis of the SCW reforming of glycerol. Likewise, a facility is being assembled to test the performance of this process. One of the foreseeable features is that the catalyst will not be strictly necessary. This is an important issue to be checked since, so far, it is crucial to identify catalysts and design reactors that maximize the yields of desired products and minimize undesired by-products formed in series and/or parallel reaction pathways. Thus, next the process will be tested by a tubular reactor with and without using catalyst.

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