Glycerol and bioglycerol conversion in supercritical water

Qian Wu1, Hlne Boucard1, Elsa Weiss-Hortala*1, Radu Barna1

1

Universit de Toulouse; Mines Albi; CNRS; Centre RAPSODEE, Campus Jarlard, F- 81013 Albi, France Corresponding author: elsa.weiss@mines-albi.fr; Phone: +33563493145; Fax: +33563493243

ABSTRACT
Catalytic transesterification of vegetable oils leads to biodiesel and an alkaline feed (bioglycerol and organic residues such as esters, alcohols...). The conversion of bioglycerol into valuable organic molecules represents a sustainable industrial process leading to the valorization of a renewable organic resource. The physicochemical properties in the supercritical domain (T>374C, P>22.1 MPa) transforms water in a solvent for organics and a reactant favoring radical reactions. In this context, conversion of bioglycerol in supercritical water into platform molecules and/or high energetic gases (hydrogen, hydrocarbons) could represent an interesting valorization process. The reported research results concern the conversion of bioglycerol compared to pure glycerol. The experiments have been done in batch autoclaves (5 mL and 500 mL stirred). Solutions of pure (5 or 10 wt%) and crude (3.5 wt%) glycerol have been processed with or without catalyst (K2CO3 1.5 wt%) in the range of 450600C. The molecular formula of bioglycerol was determined as C4.3H9.7O1.8Na0.1Si0.08. Glycerol was partially decomposed in the batch systems during the heating (42% before reaching 420C) and some intermediates (propanediol, ethylene glycol...) were quantified leading to a proposition of a reaction pathway. Acrolein, a valuable platform molecule, was mainly produced in absence of catalyst. No solid phase was recovered after SCW conversion of pure and bioglycerol in batch reactors. The optimal parameters for gasification were 600C, 25 MPa for bioglycerol and 525C, 25 MPa, for pure glycerol. In these operating conditions, 1 kg of pure or bioglycerol leads to 15 and 10 mol of hydrogen. SCW conversion of glycerol (pure and crude) allows to obtain simultaneously energetic gases (respectively 2600 and 4000kcal/kg glycerol) and valuable platform molecules.

INTRODUCTION
The increase of energy consumption in the world asks for the exploitation of new resources in the context of the limitation of new oil sources and global oil production. In parallel, the high consumption of fossil fuels is considered as one of the major factors responsible for the climate change, because of the generation and accumulation of more and more important quantities of CO2, one of the significant GHG. It is an urgent need for the development of new renewable energy sources, in parallel with the implementation of new processes. Biorefinery concept is considered very promising, making good economic sense open to interesting markets, characterized by high environmental performance, low impact and technically sophisticated. This concept agrees very well with the idea of sustainable development. Its application facilitates the reduction of biomass residues and their valorization in a more circular economy, by production of bio-fuels, chemicals (platform molecules), polymers and materials. One of the biorefinery major applications is oilseed processing. The extracted vegetable oil, a complex mixture of glycerol esters is industrially transesterificated with production of biodiesel that can be used in addition/replacement of transportation fuel (diesel). The process leads to a byproduct, called also bioglycerol or crude glycerol, a mixture composed mainly of glycerol that needs to be better valorized. Among the different industrial processes proposed to be applied, hydrothermal conversion of bioglycerol in supercritical water presents interesting advantages. In fact, the process can be performed without addition of chemical reagents and leads to partial gasification of the organics into high valuable gases: H2, low hydrocarbons, CO2. Obtained at high pressure, after cooling the gas components can be separated based on their different water solubilities: it could be possible to separate a gas phase with high H2 content at high pressure from a liquid phase containing predominantly dissolved CO2, issued from biomass processing. Valuable platform molecules can be separated from the liquid phase and the solid could be reused as combustible. The hydrothermal conversion of glycerol in supercritical water is a complex physicochemical process performed at temperatures higher than 374C and pressures up to 22.1 MPa. In the supercritical region, water becomes an interesting solvent and reactant, known for its particular properties [1, 2]. In fact, water has a behavior close to a gas: low density, high diffusivity, low viscosity. Its dielectric constant decreases dramatically towards the critical point leading water to be an excellent solvent for organics and in contrary to precipitate salts [3, 4]. Ionic product

of water increases towards the critical point (about thousand times) and decreases more significantly after. Consequently, the water reactivity changes and the role played in the reaction mechanisms also: in the (P,T) domain before the critical point water favors ionic reactions while after the critical point water promotes radical mechanisms. Fine tuning of the (P,T) couple of the hydrothermal system should allow to orient the reaction system toward gasification or to reactions producing platform molecules. The behavior of glycerol solutions in the domain of supercritical water represents the main goal of our research program. Literature data pointed out the influence of temperature on glycerol degradation [5-9]. Therefore we investigated the thermal stability of glycerol solutions with and without catalyst at normal pressure using calorimetric methods. Because of the observed glycerol ability to partial degrade during the autoclave heating towards the critical temperature; the composition of the contained solution has been also investigated. A comparison between the hydrothermal supercritical conversion of solutions containing pure and crude glycerol has been also done. The processes have been performed in batch reactors at two scales, 5 and 500 mL. Preliminary experiments have been done to study the influence of operating parameters. The effect of temperature (450-600C) and catalyst (K2CO3) is presented here keeping concentrations of glycerol (5wt% for pure and 3.5 wt% for crude glycerol) and pressure (25 MPa) and reaction time (60 min) constant. In fact, the analysis of gas composition as function of time showed [10] that hydrogen content is quasi constant after 20 min of reaction time whatever the raw material. The increase of the total amount of gas is essentially due to the production of light hydrocarbons, in accordance with the thermodynamic equilibrium [11], since the kinetics improves hydrogen production at the beginning of the reaction. The decrease of hydrogen amount 60 min could be explained by its consumption towards methanation reaction. The collected gaseous and liquid phases have been characterized using specific analytical methods.

MATERIALS AND METHODS

Reagents Pure glycerol (C3H8O3, 100%) was purchased from Fisher Scientific while crude glycerol (pH=11.4) was produced in a biodiesel pilot plant at Ecole des Mines de Nantes. Obtained by alkaline transesterification, it was mainly composed of glycerol, Na glycerate, methanol and Na salts of carboxylic acids etc. and its equivalent molecular formula C4.3H9.7O1.8Na0.1Si0.08, has been obtained by total elemental analysis. The hydrothermal experiments have been conducted with solutions containing pure glycerol (5 or 10 wt%) or crude glycerol (3.5 wt%). An alkaline catalyst, K2CO3 (99.0-100.0%, Prolabo), was also used at 1.5 wt%. Ultrapure water has been used in all experiments. Batch reactors Experiments were carried out in two kinds of batch reactors: 5 and 500 mL. The autoclaves are filled with a precise volume of liquid to be processed. Final reaction temperature was reached after heating with a known heating rate. As consequence, temperature, conversion and initial load factor (volume solution/volume of reactor) control pressure in the autoclave. The 500 mL stirred autoclave was used to study the effect of the heating process on the composition of a pure glycerol solution. This reactor is composed of an Inconel 718 shell, in which a reaction shell in stainless steel 316 was installed. The reactor is designed to reach 500C, 30 MPa with a maximum heating rate of 20C min-1. An electric resistance insured the heating and the cooling was achieved by injecting cold air around the autoclave. Stirring and temperature are controlled. Continuous monitoring and time dependent recording of temperature, pressure and heating power are carried out. A valve allows sampling the reaction media by efficient down cooling and recovering of the liquid. This device was used during the system heating: every 20C, between 120 and 450C, the inner reaction media was sampled to monitor glycerol concentration. The mini-autoclaves (5 mL) were in stainless steel 316, with inner and outer diameters of 8.5 and 31.4 mm respectively. The copper seal ensures tightness between the two parts of the autoclave. The volume being low, each experiment was carried out with 5 mini-autoclaves, running simultaneously; the reported results are mean values. The mass of initial solution varied from 0.362 (T=600C) to 0.558 g (T=450C). The estimated final pressure in the autoclaves was in a range from 20 to 28 MPa. The process was conducted by placing the 5 miniautoclaves in the preheated oven (Nabertherm L5/11/P320). After introduction, a heating time of 10 min was necessary to attempt the desired temperature in the system. We consider that reaction time is the residence time of the autoclaves in the oven at steady temperature. At the end of the desired reaction time (5-120 min), autoclaves were removed and cooled down to room temperature (25 2C) for about 26 minutes. Then the autoclaves were placed in the sampling system for phase separation. A manometer measured the overpressure in the system, which was used to calculate the produced gas volume. Finally, gaseous and liquid phases were collected and analyzed. For all the experiments, no solid was recovered from the 5 mL autoclaves.

Liquid phase analysis Pure glycerol (C3H8O3) concentration was measured by 1H-NMR (Bruker Avance 500 MHz, Top Spin software). The quantification with internal calibration was realized by mixing 500 L of TSPd4 (2.43 mg L-1 in D2O) and 100 L of sample solutions. The single proton used for quantification (in the CH) was referenced at 3.78 ppm. Liquid samples were also analyzed by GC (Agilent 6890N, FID detector) with a HP-INNOVAX column to quantify intermediates of the reaction: acetaldehyde, propionaldehyde, acrolein, ethanol, allyl alcohol, hydroxyacetone, 1,2-propanediol, methanol, 1-propanol, 2-propanol and ethylene glycol. The internal calibration was also realized using dimethylformamide and butanol. The total amount of carbon (organic and inorganic) in the liquid phase after the reaction was measured with a TOC analyzer (Shimadzu TOC-5050). TGA measurements of glycerol solution were performed under N2 at a heating rate of 1C min-1 from 30C to 320C using a TGA-DSC B111 SETARAM instrument in a platinum crucible. Gas phase analysis The collected gas was analyzed in a micro-gas chromatograph (Agilent GC-3000) with 4 columns and 4 TCD detectors. It is composed of H2, CO2, CO, CH4, C2H6, C2H4 and C3H8. The results presented are the average of the 5 mini-autoclaves gas analysis. Presentation of experimental data The main objective of our research is to identify the conditions to improve the global gasification efficiency of the process, i.e. the conversion of initial organic matter from the liquid phase to the gas phase. The gasification efficiency (GE) is defined as followed and expressed in percentage:
GE = the mass of gas product the mass of organic reagent 100%

(1)

The carbon and hydrogen conversion from glucose to gas (H2, CO2, CO, CH4, ) was expressed as: 100%

(2) (3)

100%

The lower calorific value (LCV) of the gas produced was also calculated following Eq. 4 and using LCV values of each gas (Table 1). 100% (4)

Table 1. Lower Calorific Values of some gas recovered in the gaseous phase and glycerol. Pouvoir calorifique infrieur (kcal mol-1) C2H6 340.5 C2H4 315.6 H2 57.1 CH4 191.1 C3H8 487.5 CO 67.5 glycerol 348.1

RESULTS
Pure glycerol decomposition during the heating phase Prior to the proposed batch hydrothermal experiments (under pressure), the thermal sensibility of glycerol was investigated at ambient pressure using a TGA instrument. At ambient pressure, the thermal decomposition of glycerol occurs at 170C and the vaporization starts at 290C. The thermograms (Figure 2) have been realized under inert atmosphere (nitrogen) at 1C min-1 heating rate using a glycerol solution at 10 wt% with or without catalyst. The first mass loss (100C) corresponds to the water evaporation which represents 90% of the solution. A second low mass loss starts at 130C and finishes at 150 for both solutions; the third one starts some C after. We can combine the two mass losses in one corresponding to the decomposition/volatilization of organic compounds. This mass loss occurs at a lower temperature than expected (170C) [9]. A similar behavior was observed by Dou et al. [9] for mixtures of glycerol and water or methanol. In this temperature region the profile is modified in presence of catalyst. In fact the end of the decomposition is abrupt without catalyst while the derivative mass loss is parabolic with catalyst. The catalyst modifies the thermal behavior of the solution at ambient pressure despite of the role of the catalyst, chosen to improve the water gas shift reaction in the supercritical process. Solutions at various concentration of glycerol in presence of catalyst were treated and the same profiles have been observed. Second remark concerns the value of the second mass loss. In the presence of catalyst, the mass loss is lower than for the solution with catalyst. This slight difference is probably due to an

interaction between glycerol molecules and catalyst. An FTIR was coupled to the TGA apparatus for the detection of the various organic functions in the gas phase during this experiment. Unfortunately, no specific composition was revealed and the behavior in this temperature region cannot be explained through modifications in gas composition. 0 -0,2 -20 Mass loss (%) -40 -60 -2,2 -80 -100 0 100 200 300 Temperature (C) -2,7 -3,2 with catalyst without catalyst -0,7 -1,2 -1,7 Derivative mass loss (%/min) Pressure (MPa)

Figure 1. Mass loss (full lines) and derivative mass loss (dotted lines) of glycerol solutions with or without catalyst. Glycerol: 10 wt%, K2CO3: 1 wt%, N2 atmosphere, 1C min-1, aluminum crucible. In conclusion, glycerol decomposition has been observed at relatively low temperature (130-230C) under ambient pressure and the reactivity of glycerol should not be neglected during the heating phase of its hydrothermal conversion. Moreover, the presence of catalyst seems to play a role in the decomposition of glycerol molecules by enlarging the temperature region of the process. Literature data showed that glycerol decomposition occurred rapidly in supercritical water. In fact, May et al. obtained a complete conversion in a short time (8 s) in a continuous reactor at 550C and 35 MPa using a Rubased catalyst [5]. The main intermediates of glycerol decomposition are propionaldehyde, acrolein, hydroxyacetone, methanol, formaldehyde [5-8]. In a batch process, the glycerol decomposition can occur during the heating process and the catalyst can affect the kinetics. Two experiments were carried out in the batch autoclave of 500 mL with or without catalyst. The contained glycerol solution at 10 wt% was submitted to the normal process: continuous stirring and heating of the closed vessel. Liquid aliquots, sampled every 20C during heating from 120C to 450C were analyzed by NMR, GC and TOC to determine the dynamics of the solution composition. Figure 2 presents the profiles of temperature and pressure in the autoclave during the heating. The heating rate varies from 13C min-1 (until 170C) to 4C min-1. The pressure increases more significantly when the temperature exceeds 150C. According to the results at ambient pressure, some reactions can start at this temperature with or without catalyst. The samples have been analyzed for the glycerol concentration, the TOC in liquid phase and the intermediates. The results of glycerol concentration and TOC are resumed, for selected temperatures, in Table 2. 500 Temperature (C) 400 300 200 100 0 0 20 Time (min) Figure 2. Profile of temperature (full line) and pressure (dotted line) in the reactor versus time during the heating step in the 500 mL autoclave. 40 60 T P 50 40 30 20 10 0

Table 2. Glycerol and TOC conversion of samples from the heating step. Glycerol concentration measured by NMR with internal calibration. TOC measured with TOC-analyzer. Glycerol solution at 10 wt% (1.0875 M), with catalyst (K2CO3). Sample 120C 380C 420C 450C % of glycerol converted to liquid, % of TOC converted to liquid solid and/or gaseous phase and/or solid phases 0 0 33 42 92 25.6 33.1 46.5

Glycerol concentration (Table 2) decreases appreciably at 380C and 92% of glycerol molecules are removed at the target temperature of 450C. The successive NMR spectra show the dynamics of formation/disappearance of various intermediates. The TOC content in the liquid decreases simultaneously during heating. The same process realized without catalyst leads to a slower decrease in glycerol concentration and TOC. In both cases, TOC removal is lower than glycerol disappearance, meaning that intermediates are formed in liquid phase and their amounts are not negligible. All the intermediates cited previously were quantified (acetaldehyde, propionaldehyde, acrolein, hydroxyacetone, methanol, 1-propanol, ethylene glycol, allyl alcohol and 1,2 propanediol) in total concordance with the literature [5-8]. Figure 3 presents the temperature depending concentration for four of them, selected because of the influence of the catalyst. The catalyst allows the formation of the selected intermediates (excepting acrolein) to lower temperature, before the critical temperature. Concentration (mmol L-1) Concentration (mmol L-1)
30 25 20 15 10 5 0 100 200 300

methanol

16 14 12 10 8 6 4 2 0 100 200

hydroxyacetone

Tc
400 500

Tc
300 400 500

Temperature (C)
18

(a)
40

Temperature (C)

(b)

1, 2 propanediol
Concentration (mmol L-1)

acrolein

Concentraiton (mmol L-1)

16 14 12 10 8 6 4 2 0 100 200 300

35 30 25 20 15 10 5 0 100 200 300

Tc

Tc
400 500

400

500

Temperature (C) (c) Temperature (C) (d) Figure 3. Evolution of the concentration of 4 intermediates versus temperature during the heating step of a glycerol solution (10 w%, 1.0875 M). Sampling every 20C in the 500 mL batch autoclave. Black full lines referred to solution with catalyst while red dotted lines corresponded to solutions without catalyst. Figure 3 shows that methanol was formed at lower temperature in presence of catalyst (280C instead of 400C). The gap of appearance temperature of the other intermediates is lower (20-30C). Although the intermediates have been formed below the critical point, the glycerol concentration decreased slowly. The first intermediates

formed are hydroxyacetone and 1,2 propanediol and their amounts are higher in presence of catalyst. Acrolein, valuable platform molecule, appears as a main intermediate of glycerol non-catalytic conversion in supercritical water while methanol is particularly produced in presence of catalyst. Methanol is supposed to be mainly produced by radical reactions [6]. As consequence, the presence of alkaline catalyst seems steer the mechanism pathway towards a radical reaction instead of an ionic one. May et al. [5] consider that acrolein is also produced by a radical reaction. In conclusion, it seems to be difficult to separate between the domain of ionic and radical reactions. It is obvious that the catalyst decreases the activation temperature of the reactions. In fact, radical reactions are supposed to be improved under supercritical conditions in the accompanying of the variation of ionic product of water. Kw increases from 10-14 to 10-11 towards the critical point and then decreases dramatically, e.g. to 10-22 in supercritical conditions. The various compositions of the samples were in accordance with the color variation of the solutions (not shown). Without catalyst, the solution takes a slight yellow color only at 450C. In catalytic conversion, the solution takes a slight brown color in the region of the hydroxyacetone and 1,2 propanediol peaks, returns colorless and takes an intense and trouble yellow color at 440C. In conclusion, the glycerol solutions processed in a batch autoclave towards the supercritical domain conducts to the dynamic modification of the liquid composition during the heating. The heating rate is supposed to strongly influence the glycerol decomposition. The next section will present the comparison of gasification efficiency of pure and crude glycerol, based on the gas produced. Comparison of pure and crude glycerol gasification: effect of crude glycerol composition The gasification efficiency (Eq. 1) was compared for solutions containing crude and pure glycerol with the same initial total organic carbon content. The processes (25 MPa, 5 wt% of pure or 3.5 wt% of crude glycerol, 1 h) have been conducted at different temperatures without catalyst. The gasification efficiency increases with the process temperature (Figure 4 a). Complete gasification of crude glycerol is achieved at 600C (hydrogen represents 25 mol% in the gas) while GE reaches only 85% for pure glycerol. Two reasons can explain this behavior. On one hand, the crude glycerol contains naturally some alkaline salts from the transesterification process of the oil, particularly Na salts. These alkaline components can act as catalyst e.g. for water gas shift reaction during the supercritical process. On the other hand, the equivalent molecular formula of crude glycerol presents different ratios of C/O and C/H compared to pure glycerol (C3H8O3). In fact, in the crude glycerol molecule (C4.3H9.7O1.8Na0.1Si0.08) H/O and C/O molar ratios are 5.4 and respectively 2.4, compared to the pure glycerol: 2.7 and respectively 1. Crude glycerol contains more carbon and hydrogen than pure glycerol.
100%

100%

(a)
GE (g gas/g crude glycerol )
80%

(b)
80% 60% 40% 20% 0% 400 500 600 Temperature (C) crude without catalyst glycrol brut sans cat crude with glycrol brut catalyst avec cat

GE (g gas/g glycerol)

Crude
60%

40%

Pure
20%

0% 400 450 500 550 600 650

Temperature (C)

Figure 4. Gasification efficiency obtained during SCWG of glycerol solution versus reaction temperature (batch reactor of 5 mL, 25 MPa, 1 h). (a): crude (3.5 wt%) and pure (5 wt%) glycerol solutions with similar TOC content, without catalyst. (b): crude glycerol solution (3.5 wt%) with (0.5 wt%) or without catalyst. The following equations represent the total conversion of pure (Eq. 5) and crude (Eq. 6) glycerol in water:

C3 H 3O8 + 3H 2O 7 H 2 + 3CO2

(5)

(6) C 4.3 H 9.7 O1.8 + 3.4H 2 O 8.25H 2 + 4.3CO2 As consequence, the amount of gas produced from crude glycerol should be higher, in accordance with the values of gasification efficiency. However, the H2 gas fraction should be lower in the case of crude glycerol gasification.

Figure 4 b shows the effect of K2CO3 (catalyst) on the gasification efficiency of crude glycerol solutions. Taking into account the error bars, the catalytic effect is minimal. The salts content of the raw material seems to catalyze the reaction and as consequence, the catalyst added has no significant influence on gasification. The next section is dedicated to the analyses of the gas composition. Comparison of pure and crude glycerol gasification: effect of temperature on gas composition Figure 5 (a to d) shows the production efficiency (mol/kg glycerol) of the main gases (H2, CO2, CH4, C2H6) during the gasification process. Experiments are performed in parallel series under the same conditions (25 MPa, 5 wt% of pure or 3.5 wt% of crude glycerol, 1 h) but at different reaction temperatures: 450, 500, 525, 550 and 600C. The yields of each gas are following similar profiles with temperature for the two glycerols. The maximum hydrogen yield is obtained at 525C for both reactants. The amount of gaseous hydrocarbons increases with the increasing temperature, indicating that temperature controls the kinetics and reactions equilibrium. The yield of light hydrocarbons is higher for crude glycerol, probably due to its composition. In fact the ratios of C, H and O indicates a lower proportion of hydroxyl groups in the crude glycerol compared to pure glycerol, explained by a probably incomplete extraction of the fatty acids/esters at the end of the transesterification.
Yield (mol H2/kg glycerol) Yield (mol CO2/kg glycerol)
20 15 10 5 0 450 500 550 600 Temperature (C)

H2

20 15 10 5 0 450

CO2

500

550

600

Temperature (C)

Yield (mol CH4/kg glycerol)

10 8 6 4 2 0 450

Yield (mol C2H6/kg glycerol)

CH4

8 6 4 2 0 450

C2H6

500

550

600

500

550

600

Temperature (C)

Temperature (C)

Figure 5. Variation of the gases yields (H2, CO2, CH4 and C2H6) versus temperature for pure and crude glycerol gasification in supercritical water (batch autoclaves of 5 mL). Pure (5 wt %), crude (3.5 wt%), 25 MPa, 1 h and catalyst (1.5 wt% K2CO3). To resume, for a given temperature, gasification of pure glycerol preferentially produces hydrogen while crude glycerol favors the generation of light hydrocarbons. The differences in gas yields can be attributed to mineral and organic impurities. A temperature of 525C conducts to the higher hydrogen yield. Energetic comparison of the gas phase Finally, a brief energetic comparison of the gas produced by the gasification of glycerol and crude glycerol at different temperatures is proposed in Figure 6. Crude glycerol led to a more energetic gas than pure glycerol. This difference is not only due to the volume of gas but also to its composition. In fact, hydrocarbons have significant higher lower calorific value (LCV) than hydrogen as reported in Table 1. Taking into account the previous results, the gas produced by crude glycerol is richer in hydrocarbons while the gas issued from pure glycerol gasification contains relatively more hydrogen. The optimal temperature as regards to the highest LCV is 600C for crude and 550C for pure glycerol, which is not related to the highest H2 production (525C).

5000 4000 LCV (kcal kg-1)

Crude glycerol
3000 2000 1000 0 400 450 500 550 600 650

Pure glycerol

Temperature (C) Figure 6. Variation of LCV of gas produced versus temperature during SCWG of for pure and crude glycerol solutions (batch autoclaves of 5 mL). Pure (5 wt %), crude (3.5 wt%), 25 MPa, 1 h and 1.5 wt% K2CO3.

CONCLUSION
Our research concerns the supercritical water gasification of solutions containing pure or crude glycerol. On the one hand, the thermal stability of glycerol was studied at atmospheric pressure. The glycerol conversion occurs at relatively low temperature and the catalyst enlarged the temperature region of the decomposition. On the other hand, the reaction media was sampled through the heating process in a batch reactor that highlighted the severe decomposition of glycerol (92% in presence of catalyst) and total organic carbon before reaching the reaction temperature. Among the intermediates formed, acrolein was favored in the non-catalytic process while methanol was preferentially produced in presence of catalyst. The gasification behavior and the composition of the gaseous products were compared between both glycerols. The gasification efficiency increases with temperature for both, while being upper for crude glycerol. For bioglycerol the contribution of the catalyst is low because it naturally contains some salts that act as catalyst. These organic and mineral impurities favored production of more light hydrocarbons than hydrogen. Hydrogen production yield is higher for pure glycerol: 15 mol of H2 per kg of glycerol versus 10 mol of H2 per kg of glycerol for crude glycerol. Finally, 1 kg of pure or crude glycerol generates a gas with a total LCV of respectively 4000 kcal (at 600C) and 2600 kcal (at 550C).

REFERENCES
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ACKNOWLEDGMENT
The authors thank Ms Maria PARASCHIV, Energy Engineering department of Ecole des Mines Nantes who furnished the investigated crude glycerol. The authors thank Mr Stphane Massou, who analyzed the glycerol by NMR at INSA Toulouse.