SUPERCRITICAL WATER GASIFICATION OF MODEL COMPOUNDS: INTERACTIONS BETWEEN GLUCOSE AND GLYCEROL

Q. WU*, E. WEISS-HORTALA*, S. BULZA** AND R. BARNA* * Universit de Toulouse, Mines Albi CNRS, ALBI, France ** Universitatea Politehnica Timisoara, Romania

SUMMARY: Super Critical Water Gasification (SCWG: P>22.1 MPa, T>374C) converts organic compounds in species with high chemical energy (hydrogen, light hydrocarbons) with a largely neutral CO2 balance. To observe interactions between two model molecules representing the main organic byproducts: glucose and glycerol, batch experiments have been carried out with 5 mL autoclaves. The experiments have been performed in similar conditions with the pure components and in mixture: 0.5 mol L-1 of organic matter and 0.025 to 0.1 mol L-1 of K2CO3 as catalyst. The range temperature and pressure were 450-600C and 20-28 MPa. The reaction time varied from 15 to 240 min. H2, CO2, CH4 and C2H6 were the main gas products. The interaction between glycerol and glucose in a mixed solution was very weak. A high temperature and the use of K2CO3 allowed to improve the gasification efficiency and the hydrogen production. The highest gasification efficiency of 70% and hydrogen yield of 1.5 mol/mol mixture was obtained by using 0.1 mol L-1 of catalyst at 600C and 25 MPa. 1. INTRODUCTION Wet biomass or comparable residues can be considered as renewable resources for sustainable energy systems. Super Critical Water Gasification (SCWG: P>22.1 MPa, T>374C) is a novel way of treatment, where water acts as solvent and reactant (Clifford, 1993; Kruse and Dinjus, 2007). Supercritical water converts biomass into species with high chemical energy (hydrogen, light hydrocarbons) with a largely neutral CO2 balance. The process is considered interesting for biomass or organic residues with high water content (>30%). It allows the separation at high pressure of H2 from the solution containing dissolved CO2, favouring sustainable solutions for its use/storage. SCWG process is under research, large scale industrial applications are not known (Kruse, 2009). Physico-chemichal properties of supercritical water are different from liquid water, implying a high reactivity with organic compounds. The global reaction expected for glucose is as follow: C 6 H 12 O6 + 6 H 2 O 12 H 2 + 6CO2 (1)

However this reaction is not complete and some concurrent reactions could conduct to methane and/or carbon monoxide production or lights hydrocarbons. Particularly, in presence of water,

Proceedings Venice 2010, Third International Symposium on Energy from Biomass and Waste Venice, Italy; 8-11 November 2010 2010 by CISA, Environmental Sanitary Engineering Centre, Italy

Venice 2010, Third International Symposium on Energy from Biomass and Waste

carbon monoxide can react at high temperature and in presence of catalyst and produce hydrogen and carbon dioxide (water gas shift reaction). Biomass has a complex and variable composition of organic compounds and salts. The particular properties of water in the region of its critical point lead (including salt precipitation) to the quantitative hydrolysis and decomposition of biomass or organic residues in more simple molecules which react forming different products distributed in gas, liquid or solid phases (Kruse and Dinjus, 2007). A large part of the experiments developed in laboratories replace biomass/organic waste by model components. So glucose, hydrolysis product of cellulose, often replaces cellulose/hemicelluloses (Matsumura et al., 2007) or syrupy residues. Glycerol is also interesting because it is a sub product (residue) of the industrial process of biodiesel, which has an important improve (Bhler et al., 2002). Moreover, glycerol composes also vinasses. In view to model SCWG of syrupy residues, the interaction between glucose and glycerol should be studied. The literature shows that glucose gasification is efficient in batch and continuous process (Holgate et al., 1995; Lee et al., 2002; Kruse and Gawlik, 2003; Yoshida et al., 2007; WeissHortala et al., 2010) in presence of catalyst. Watanabe et al. (2007) studied the conversion of glycerol into acrolein and observed its low degradation for long reaction times in their operating conditions (close to supercritical point). They showed that H2SO4 addition enhanced the conversion efficiency into acrolein. A more complete study of reaction mechanisms showed that a long reaction time disfavors acrolein production and favors gasification (Bhler et al., 2002). Antal et al. (1999) were interested by the gasification process with carbon-based catalyst and obtained a quasi-total conversion of glycerol. They noted the important catalytic effect of the reactor surface. Other studies were carried out with Ru/Al2O3 catalyst (Byrd et al., 2008), Na2CO3 catalyst (Xu et al., 2009) or Ru/ZrO2 catalyst (May et al., 2010); Ru-based catalysts are efficient to convert glycerol and produce hydrogen in a short reaction time, while catalytic effect is not significant. In the present study, the choice of catalyst is oriented towards alkaline instead of metallic ones. Alkali salts are used to promote the water gas shift reaction (Sutton et al., 2001; Matsumura et al., 2005; Yanik et al., 2008) and to model inorganic compounds of a real biomass. We have chosen an experimental SCWG approach in batch reactor to observe interactions between the two model molecules representing in our experiment main organic components of organic byproducts: glucose and glycerol.

2. EXPERIMENTAL STUDY 2.1 Reactor and reagents The batch reaction was conducted in stainless steel 316 mini-autoclaves (V = 5 mL). The inner diameter was 8.5 mm and the outer diameter was 31.4 mm. Two parts composed the miniautoclaves and a cupper joint was used in order to improve the watertight quality. The volume being low, each experiment was carried out with 5 mini-autoclaves, running simultaneously. The pressure was kept constant by adjusting the solution quantity as function of reaction temperature. The mass of initial solution varied from 0.362 g (T=600C) to 0.558 g (T=600C). The pressures varied from 20 to 28 MPa. The reaction, at the desired temperature, was conducted by placing simultaneously 5 mini-autoclaves in the preheated muffle oven (Nabertherm L5/11/P320). A heating time (about 10 min) is necessary to reach the desired temperature in the system. After the reaction time, the autoclaves were cooled down in air jet to room temperature (25 2C) during about 26 min. Then the autoclaves were placed in the sampling system and the volume was scanned by nitrogen at atmospheric pressure. The overpressure obtained by opening the autoclave was

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measured by a manometer. The volume of the system was 16.7 mL. The total mol number of the gas recovered in the system by the mini autoclave openening was calculated (P, V and T known). The gas was collected in a sampling bag under nitrogen flush. The liquid phase was collected with a filtering syringe. The reactor was washed (by water) and the solid phase recovered by filtration. Glucose powder (C6H12O6, water free, Prolabo), glycerol solution (C3H8O3, 86-88%, Fluka) and ultra-pure water were used as raw materials to prepare the initial solutions. The solutions of pure compounds, glucose or glycerol, were prepared at a concentration of 0.5 mol L-1. The mixture solutions were composed by 0.25 mol L-1 of glucose and 0.25 mol L-1 of glycerol. K2CO3 (99.0-100.0%, Prolabo) was employed as catalyst, the molar ratio between organic reactant and K2CO3 varies from 1:1 to 20:1. 2.2 Experimental procedure The gas product was analyzed by a gas chromatograph (Agilent GC-3000 with 4 columns and 4 TCD detectors). The gases analysed are H2, CO2, CO, CH4, C2H6, C2H4 and C3H8. The gas phase of each autoclave was analysed, but the results presented in this study are an average of the 5 mini-autoclaves analyses. A TOC analyser (Shimadzu TOC-5050) measured the total amount of carbon (organic and inorganic) in the liquid phase after reaction. 2.3 Presentation of experimental datas The main objective of the work is to determine the 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 follow and expressed in percentage: GE =

mass of
i

gas i 100 (2)

initial mass of organic reagent

The second goal is to increase the part of hydrogen into the gas phase, particularly by promoting the water gas shift reaction. So, the yield of each gas (Yi) is defined such as: Yi = mol number of gas i 100 initial mol number of organic reagent (3)

3. RESULTS AND DISCUSSION To study the interaction between glycerol and glucose, experiments were realized with pure substances and with mixture of the two compounds. At first, the interaction was studied comparing the gasification efficiency of pure component and mixture. Then, the influences of temperature, catalyst on the gasification of mixture solution were investigated. 3.1 Study of interactions between glucose and glycerol As it was mentioned previously, glucose and glycerol are obtained in different waste and particularly vinasses. As regards to lignin or its model compounds (Yoshida and Matsumura,

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2001; Weiss-Hortala et al., 2010), which influence glucose degradation, a similar method was employed. Gas amounts of solutions containing separately glucose or glycerol, obtained under the same operating conditions, were theoretically summed. This theoretical sum was compared to the experimental value obtained for the mixture of the both molecules. If glucose and glycerol interact during SCWG, the theoretical sum should be different from the experimental value. In order to verify the possible effect of glycerol on the gasification of glucose, three experiments were conducted with a solution of glucose (0.54 mol L-1), a solution of glycerol (0.54 mol L-1) and a solution containing glucose (0.54 mol L-1) and glycerol (0.54 mol L-1) at 525C and 25 MPa. The comparison, illustrated in Figure 1, concerns the experimental amounts of the main gas (CH4, CO2, H2, C2H6 and C2H4) and the total gas value. Theoretical value represents the theoretical sum of gas production from glucose solution and glycerol solution. Experimental value is the experimental gas amount obtained with the mixture solution. Previous experiments using only glucose were realized with a concentration up to 1 M. In this range, the glucose concentration was not a limitative factor of the gasification (proportionality between gas produced and concentration), so the upper concentration of each compound employed in this study was 0.54 mol L-1. Taking into account Equation 1, the total gasification of 1 mol of glucose conducts to 18 mol of gas whose 12 mol of hydrogen. A similar equation written for glycerol (C3H8O3) conducts to 7 mol of hydrogen and 3 mol of carbon dioxide. The experiments presented on Figure 1 were realized with 0.432 g of solution (= 0.23 mmol of each organic compound). The gas amount of experiment conducted with glucose (4.1 mmol) should be higher than with glycerol (2.3 mmol), but results in Figure 1 show that gasification is more efficient for glycerol than glucose. It could be due to the higher polymerisation ability of glucose: Sina et al., (2004) explained this behavior by favoring phenol formation and furfurals after a long reaction time (1 h). The gas production from glucose is lower than that expected, indicating that the reaction is not complete. For glucose, a ratio of about 2 mol of gas per mol of glucose is obtained being in accordance with literature (Hao et al., 2003; Matsumura et al., 2005).

Figure 1. Comparison of gas production as function of kind of solutions under the same operating conditions: glucose at 0.54 M; glycerol at 0.54 M; theoretical sum of the two previous values; solution containing glucose and glycerol each at 0.54 M. T = 525C, P = 25 MPa, without catalyst and during 1 h.

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The hydrogen quantity is lower than that of some published results, but operating conditions, catalyst and process (batch or continuous) have a great influence on the process results. The experiments presented were carried out without added catalyst. Hao et al. (2003) obtained also a CO2 amount 3 times higher than H2. For glycerol, the ratio is close to 3 mol of gas per mol or glycerol. This result is also in accordance with the ratio obtained by Antal et al. (1999) in batch experiments with similar operating conditions. Moreover, the molar ratios of hydrogen and carbon dioxide are also close to those obtained by Antal et al. (1999). The part of methan is higher with glycerol than glucose and it strongly depends from the catalyst (Sina et al., 2004). The experimental value of gas production obtained with a mixture solution (1.02 mmol) is close to the theoretical sum obtained with the pure compounds (0.97 mmol). This behavior indicates that there are few interactions between glucose and glycerol molecules during the gasification process. Concerning each gas produced: H2, CO2, CH4, the experimental values of gas production are also close to the theoretical values. At this stage, the modeling of SCWG of glucose and glycerol solutions seems to be a simple sum of each pure component under the same operating conditions. However, literature indicates that the effect of temperature has opposite effects on the gas production. In fact, experimental datas of Byrd et al. (2008) and a thermodynamic analysis of Voll et al. (2009) indicates that an increase of temperature conducts to: a decrease of H2 and CO2 proportion and an increase of CH4 for glycerol solutions an increase of H2 and CO proportion and a decrease of CH4 and CO2 for glucose solutions. As regards theses informations, the gasification performance of a mixed glycerol / glucose solution should be studied as function of different operating conditions. In this part of our research, the effects of temperature and catalyst were investigated. 3.2 Influence of operating conditions In this part, solutions were prepared with glucose and glycerol. The total concentration of organic compound was 0.5 mol L-1 such as 0.25 mol L-1 of each pure compound. K2CO3 was used as catalyst and the moles ratio between [mixture]/[catalyst] varies from 5:1 to 20:1 and the temperature varies from 450 to 600C. 3.2.1 Influence of temperature Figure 2 shows the comparison of gasification efficiency (GE, Equation 2) as function of reaction temperature. Results are presented also with or without catalyst. At moderated temperature (450C and 500C) gasification efficiency is low (33% and 35%), but catalyst improves the conversion into gas (54% and 59%). At the highest temperature (600C), the gasification efficiency is higher (close to 70%) and the effect of catalyst is weak. According to the literature, an increase of the temperature and the presence of an alkaline catalyst favor the gasification of organic compounds (Kruse and Dinjus, 2007). Under the operating conditions, the total conversion is not reached for the initial organic matter; we suppose that the catalytic effect of the reactor influences also the reaction (Antal et al., 1999). Figure 3 presents the variation of gas yield (Yi, Equation 3) as function of temperature for solutions with and without catalyst. As shown in Figure 3 (a) and (b), carbon monoxide is not a final product of the process. In conclusion, CO is not a main gas obtained during the gasification process under the tested operating conditions. Without catalyst (Figure 3 a) the yields of CH4 and CO2 increase significantly with the temperature, those of H2 and C2H6 also increase while those of C2H4 and C3H8 stay constant.

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Figure 2. Influence of temperature on gasification efficiency of glucose and glycerol solutions in batch reactor (1 h). [glucose] = [glycerol] = 0.25 M, 25 MPa, [K2CO3] = 0.025 M. As regards thermodynamic behavior of glucose and glycerol, an increase of temperature has opposite effects on H2 and CH4 generation but should decrease the part of CO2. Results from Figure 3 (a) do not confirm a decrease of carbon dioxide production. This difference could be attributed to the rate of the competitive reactions and the role of catalysts (alkaline and reactor inner surface). At 600C, the gasification is more efficient but the hydrogen amount is comparable to the value obtained with lower temperatures. With catalyst (Figure 3 b) the yields of CH4 and CO2 increase almost linearly with the temperature while H2 present a fluctuation. Results from Figure 3 (b) indicate also that combined thermodynamic and kinetic can explain the increase of CO2 production. However, the profile obtained for hydrogen could be the result of the opposite thermodynamic behavior. Under the operating conditions, it seems that thermodynamic of glucose degradation determine the gasification profile between 500 and 550C. This point should be developed in the future using solutions at various concentrations of glucose and glycerol. Maximum yield of CH4, CO2 and H2 are obtained for samples with and without catalyst at 600C, which is in accordance with the maximum gasification efficiency.

(a)

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(b) Figure 3. Influence of temperature on gas yield of glucose and glycerol solutions in batch reactor, without (a) or with (b) catalyst. T varies from 450-600C, P = 25 MPa, [glucose] = [glycerol] = 0.25 M, [K2CO3] = 0.025 M, time = 1 h. (a) (b)

(c)

(d)

Figure 4. Influence of temperature on gas fraction of various solutions treated by batch SCWG process, during 1 h. (a): glycerol solution; (b): glucose solution; (c): theoretical sum of a and b; (d): experimental value of a glucose and glycerol solution. [glucose] = [glycerol] = 0.54 M, 25 MPa, [K2CO3] = 0.025 M.

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In order to explain the previous results and study the possible interactions between glucose and glycerol, gas composition (only CO2, H2 and CH4) as function of temperature was compared for solutions of glucose and glycerol or either of them. Figure 4 (a) and (b) shows the molar fraction of gas produced from glycerol solution and glucose solution. For the glycerol solution (Figure 4 a), gas fraction of CO2 changes slightly from 45% to 43%, while H2 fraction decreases from 51 to 35%, with an important jump in the range of 500-550C. The methan fraction increases quasi linearly. Only the increase of methan fraction is in accordance with the thermodynamic model. Concerning H2 and CO2, a cumulative effect of thermodynamics and kinetics may explain the profiles. For glucose solution (Figure 4 b, only 3 experiments), gas fraction of CO2 drops linearly from 88% to 48% and that of H2 increasse linearly from 11% to 28%. The part of methan stays constant. The decrease of CO2 fraction and the increase of H2 fraction in the gas phase is in accordance with the thermodynamic prediction. The results of glucose and glycerol solutions are combined to build a theoretical profile of the gas fraction (Figure 4 c) and to be compared with the experimental dats (Figure 4 d). The graphs present the same temperature dependence shapes and quasi the same fluctuations, even if the number of points is different. The strong resemblance of CO2, H2 and CH4 repartition between the theoretical values and the experimental values further proves that there are no major interactions between glucose and glycerol during the gasification in supercritical water. However, influences on H2 and CH4 gas fractions can be observed. To conclude this part, the high gasification temperature enhances the gasification of glucose and glycerol solution. The catalyst role is more efficient at lower temperatures (450-500C) for the gasification efficiency and the catalyst favors the generation of H2. The best gasification efficiency and the highest yields of CH4, CO2 and H2 are obtained at 600C for samples with catalyst. Under the operating conditions, gasification of glucose and glycerol solutions seems to be the combination of behaviors of each pure substance. Therefore, the influence of catalyst concentration on gasification will be studied at 600C. 3.2.2 Influence of catalyst concentration Figure 5 illustrates the influence of catalyst concentration on gasification efficiency (a) and gas yield (b) for mixture solutions at 600C. The molar ratio between K2CO3 (catalyst) and mixture varies from 0 to 1:5. Figure 5 (a) shows that gasification efficiency rises slightly from 62% to about 69% at 600C (maximum at a ratio of 1:20). No real influence on gasification efficiency can be observerd by increase of the catalyst ratio beyond 1:20. The molar proportion of catalyst compared to amount of organic compounds is not a limitative factor of the gasification efficiency. This observation indicates that the catalyst does not play an important role directly on the substrate at this temperature. K2CO3 is a catalyst of the water gas shift reaction, meaning that the reaction between CO and H2O is favored. The variation of gas composition is presented on Figure 5 (b). The yield of H2 increases significantly from 0.54 to 0.86 mol/mol mixture while the yields of CO2, CH4 and C2H6 keep stable with the increase of the catalyst concentration. The fluctuation of H2 proportion obtained at a ratio of 1:10 seems to be linked to the slight decrease of the gasification efficiency. Only a complete study of other ratio arond this value could confirm the presence of this decrease. However, the general profile indicates that K2CO3 plays an important role to improve the H2 production. The total organic carbon content (TOC) of the solutions confirms that the TOC removal increases as function of catalyst concentration increase (not shown). According to the previous results, K2CO3 favors slightly the gasification at 600C, and the increase of its concentration improves the generation of H2.

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(a)

(b)

Figure 5. Influence of catalyst concentration on gasification efficiency (a) and gas yield (b) of glucose and glycerol solutions during 1 h of batch SCWG process. [glucose] = [glycerol] = 0.25 M, 25 MPa, T = 600C.

4. CONCLUSIONS Glucose and glycerol, model molecules of parts of biomass, have been widely studied in SCWG process, but not the interaction between those two substances. The aim of the work was to investigate the supercritical water gasification of mixed glucose and glycerol solution in a batch reactor. With a concentration of organic substances at 0.5 mol L-1 and K2CO3 used as catalyst, the influences of gasification temperature (450-600C) and catalyst concentration (K2CO3) have been studied. The main conclusions are: the interaction between glycerol and glucose during SCWG of an equimolar in a mixed solution is very weak. A mixed solution produces more gas than solution of pure substances, close to the theoretical prediction. high temperature (600C) enhances the gasification of mixed glucose and glycerol solution compared to relatively lower temperatures (450-500C).

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catalyst (K2CO3) improves hardly the gasification efficiency at 450 and 500C but the effect is less important at 600C: it favors H2 generation. In the future researches, the influence of concentration of mixed solution, reaction time and pressure will be investigated.

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degradation during supercritical water gasification. J. Supercrit. Fluids, 53, 42-47. Xu D., Wang S., Hu X., Chen C., Zhang Q. and Gong Y. (2009) Catalytic gasification of glycine and glycerol in supercritical water. Int. J. Hydrogen Energy, 34, 5357-5364. Yanik J., Ebale S., Kruse A., Saglam M. and Yksel M. (2008) Biomass gasification in supercritical water: II. Effect of catalyst. Int. J. Hydrogen Energy, 33, 4520-4526. Yoshida T. and Matsumura Y. (2001) Gasification of cellulose, xylan and lignin mixtures in supercritical water. Ind. Eng. Chem. Res., 40, 5469-5474. Yoshida T., Yanachi S. and Matsumura Y. (2007) Glucose Decomposition in Water under Supercritical Pressure at 448-498 K. J. Japan Institute of Energy, 86, 700-706.