Progress of Cryogenics and Isotopes Separation

Volume 13, issue 1/2010

FUEL GAS FROM BIOMASS WASTES GASIFICATION IN A FREE-FALL REACTOR E. David*, S. Preda1, C. Ducu2
*

National Research and Development Institute for Cryogenics and Isotope Technologies ICIT Rm. Valcea, Uzinei Street no.4, O.P Rureni, P.O.Box 7, Code 240050, Rm.Vlcea, Romania, phone: 0250/732744, fax: 0250/732746,

ABSTRACT
Renewable biomass and biomass-derived fuels could be readily gasified to produce a fuel gas rich in hydrogen. Among the biomass energy conversion schemes gasification produces a product gas, which based on its properties could be used either to co-produce value-added byproducts or hydrogen. As a readily renewable fuel, biomass may become a significant component in the global sustainable energy mix as fossil fuel resources begin to deplete. In addition, biomass utilization can expedite mitigation of greenhouse gas emissions and carbon sequestration cycles and promote "green" industries. Hydrogen or fuel gas produced from biomass could be readily used in most of the present natural gas or petroleum derived hydrogen energy conversion devices and also in advanced systems such as fuel cells. The main objective pursued in this work is to investigate the fuel gas(rich in hydrogen) production from biomass wastes by applying the steam gasification technique. Characteristics of steam gasification of two kinds of biomass (rapeseed oil cakes and walnut shells) at different heating rate (in the order of 10-20C s1) and different metal oxide catalysts (CaO, MgO and a mixture 50% CaO and 50% MgO) in a gassolid concurrent down flow free-fall reactor were investigated. The effects of steam/biomass (S/B) mass ratio (0.01.0 g/g) and reactor temperature (750850C) on the product yields and the compositions of product gas were determined. The experimental results show that the gas yields and the content of H2 in the gas increase with reactor temperature, while the yields of tar, char and the content of CO and CH4 in the product gas decrease. The presence of steam increases the gas yield and reduces the tar and char yields. It is inferred that an in situ steam reforming reaction of tar takes place even in a short gas residence time in the free-fall reactor. Water-gas shift reaction determines greatly the gas compositions and H2 production at higher temperature. The effects of different occurring catalysts, CaO, MgO and a mixture 50% CaO and 50% MgO, were also investigated in the same unit. The mixt catalyst reveals a comparably good performance in terms of catalytic activity of tar destruction and the consequential increase in the production of gases in thus a short vapor-catalyst contact time. The results verify that the presence of steam and catalyst favors the tar decomposition and lead to increasing of hydrogen content in gas yield. The present gasification process could be generally used to produce fuel gas for heat and power. KEYWORDS: fuel gas, biomass wastes, gasification, catalyst

*Corresponding author: e-mail: david@icsi.ro 1 Research Station for Fruit Growing Valcea, Calea lui Traian, no. 464, 240263, Rm.Valcea, Romania, predasilvia@yahoo.com 2 University of Pitesti-Research Centre for Advanced Materials, Trgu din Vale no.1, RO-110040, Pitesti, Romania, catalin.ducu@upit.ro 95

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1. INTRODUCTION Agricultural residues are potentially an attractive feedstock for producing energy as their use contributes little or no net carbon dioxide to the atmosphere. The processing of this wastes has become a technological issue that has attracted the attention of numerous researchers [1,2]. Presently, the most conventional way of handling these waste streams is to burn them with energy recovery or for landfilling. However, both combustion and landfill use cause secondary pollution problems. Novel disposal technologies are in high demand to provide for more energy efficient and environmentally and economically sound solutions. An alternative to these combustion and landfill uses is gasification. Thermochemical gasification of biomass is a well-known technology that seems to be a feasible application and has been developed for industrial applications [3-6]. This technology has been identified as a possible system for producing renewable hydrogen. The transformation of biomass into hydrogen-rich gas is a suitable source for energy production due to the advantages typical biomass (renewable character, net below zero CO2 emissions, possibility of using residues generated from agriculture activities). The gas produced from biomass gasification can be directly used as fuel in internal combustion engines or gas turbines [7]. As is well known, during biomass gasification process, the products distribution and the yield of hydrogen-rich gas depend on the fuel type, reactor configuration, gassolid residence time, reaction temperature, pressure, gasifying agent and catalyst [8-11]. Among these factors, the type of reactor and gasifying agent play a key role in determining products distribution and gas compositions of biomass gasification. The addition of steam as gasifying agent and catalyst in gasification process makes it possible to obtain high-grade and nearly N2-free product gas. Steam gasification of biomass has been studied in various reactors including bubbling fluidized bed reactor and circulating fluidized bed reactor [11 17] in recent years. The significant advantage of these fast reaction reactors is a much higher heating rate. Hence, the mechanisms and behaviors of steam gasification of biomass at higher rate should be comprehensively studied. The freefall reactor has the advantages of constant reaction temperature in the reactor, a higher heating rate and a short but narrowly distributed residence time (in the order of seconds) of both solids and gas. It is a good approach to investigate the mechanisms and behaviors of steam gasification of biomass at high heating rate in a freefall reactor. It was reported [18] that the secondary gas phase reactions between primary pyrolysates of a brown coal and water proceeded within the vapor residence time (< 2 s) in a drop tube reactor. However, no data on the roles of steam and catalyst during biomass thermoconversion in a short residence time at higher heating rate in a free-fall reactor have been reported to our knowledge. In this paper, a free-fall reactor was used to study the characteristics of biomass steam gasification. The primary objective of this work was to experimentally examine the effects of steam and catalyst in a short residence time at high heating rate and the factors, which determine the gas compositions and tar yields in the initial step of steam gasification. This study would enhance our understandings of gasification process, and be beneficial to developing a new
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process for to obtain hydrogen-rich gas. Steam gasification of two kinds of biomass (rapeseed oil cakes and walnut shells) was conducted in the temperature region from 750 to 850C. The effects of reactor temperature, steam/biomass (S/B) mass ratio, fuel type and catalyst on the products distribution and product gas composition were investigated.

2. EXPERIMENTAL PART 2.1. Materials and methods Biomass wastes (rapeseed oil cakes and walnut shells) are employed as raw materials in this process. Rape seed oil cakes were in extrudates form and raw walnut shells were in hemispherical shape with about 25 mm diameter and 3 mm thickness that were grinding at a size of about 3-5 mm (Figure 1).

Figure 1. Raw waste biomass: (a)- extrudates of rapeseed oil cakes; b)-walnut shells;

The rapeseed oil cakes and walnut shells were dried at 105C, for 4 h to remove the moisture and kept in desiccator before test. The proximate analyses of rapeseed oil cake and walnut shells were done according to ASTM D3174-04 for ash analysis and ASTM D3175-89a for volatile matter. The ultimate analysis to determine the amounts of carbon, hydrogen, nitrogen, sulphur and oxygen (by calculated from difference) were made in according to ASTM D5291-96. The gross calorific values were determined in according to ASTM D240-02. The proximate, ultimate and component analyses of rapeseed oil cakes and walnut shells are shown in Table 1 and 2. All chemicals used in the investigation were of analytical grade.

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Table 1. Proximate, ultimate and component analyses of reapseed oil cakes. Proximate analysis (raw wt%) Moisture 10.62 Volatile matter 67.71 Fixed carbon 15.40 Ash 6.27 Ultimate analysis (dry wt%) C 45.91 H 6.19 N 6.89 S 0.88 Oa 40.13 H/C molar ratio 1.62 O/C molar ratio 0.65 Component analysis (dry wt%) Extractivesb 19.42 Cellulose 28.56 Hemicellulose 41.50 Lignin 4.89

Empirical formula CH 1.62 O 0.65 N 0.128 S 0.007 GCVc , MJkg-11 19.38

a

Calculated from difference; bToluene/alcohol (2/1, v/v); cGross calorific value

Table 2. Proximate, ultimate and component analyses of walnut shells. Proximate analysis (raw wt%) Moisture 11.59 Volatile matter 65.31 Fixed carbon 14.80 Ash 7.30 Ultimate analysis (dry wt%) C 47.67 H 5.67 N 0.34 S 0.73 Oa 45.59 H/C molar ratio 1.42 O/C molar ratio 0.72 Component analysis (dry wt%) Extractivesb 14.40 Cellulose 32.58 Hemicellulose 40.38 Lignin 6.25

Empirical formula CH 1.42 O 0.63 N 0.006 S 0.0057 GCVc , MJkg-11 18.89

a

Calculated from difference; bToluene/alcohol (2/1, v/v); cGross calorific value

For pyrolysis and steam gasification the nitrogen was used as inert gas, while for catalytic gasification three kinds of catalysts (CaO, MgO and a mixture 50% CaO and 50% MgO) were used. 2.2. Experimental system The experimental system used in this study includes a free-fall reactor that is a gas-solid concurrent down flow reactor. This is schematically shown in Fig. 2.

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Figure 2. Experimental system with the free-fall reactor (1) hopper; (2) electrical furnace; (3) thermal couple; (4) reactor tube; (5) char collector; (6) cyclone; (7) condensor; (8) tar trap; (9) glass wool and CaCl2 filters; (10) gas flowmeter; (11) gas tank; (12) steam generator. The reactor tube made of stainless steel has a length of 1000 mm and an i.d. of 55 mm and was independently heated by electrical furnaces to ensure reaction region isothermal. Three thermocouples were inserted in heater outside the wall of the reactor tube, respectively. Biomass and catalysts (as additives) were, respectively, fed into the reactor on the tope of the reactor at a prefixed and constant flow rate. The mass of the biomass was calculated on dry basis. Water was provided by a vaporizer heated for steam generation before injection into the reactor. The steam/biomass (S/B) mass ratio could be varied by changing the biomass feeding rate while keeping the steam flow rate constant or vice versa, which ensured a more constant residence time for all the runs. The system was controlled at atmospheric pressure with N2 as a balance gas. The reactor temperature was set at 750, 800 and 850C, respectively. After the temperature reached, the fast gasification took place by feeding into the biomass, catalyst and steam. The volatiles passed through a metallic sieve to remove solid particles and were further passed in a cyclone and cooled in water condensor to separate the condensable components. The obtained liquids were collected in tar traps. The remaining aerosol was captured in filters filled with glass wool and CaCl2. CaCl2
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from filters dried the gaseous product before it was collected. The gases were collected in a gas tank and off-line analyzed by a chromatograph type Varian CP3800 with TCD and FID detectors. The concentrations of H2, CO, CO2, N2, CH4 and hydrocarbons up to C7 were determined. The char was accumulated in the char collector. The quantity of the char was obtained by weighing the collector inventory before and at the end of each run. Repeated experiments were carried out to get mass balance data and the results were between 97% and 100%. The tar samples were dissolved in hexamethylene to produce insoluble part, asphalt and soluble part composed of alkanes, aromatics, and non-hydrocarbons and these parts were calculated.

3. RESULTS AND DISCUSSIONS The yield of hydrogen from biomass varies according to the technology used, the operating parameters, and the composition of fuel used. In general the biomass thermochemical reaction can be written:
Biomass + Energy Bio - oil + Char + Gas
Biomass + Energy CO + H 2 + CH 4 + + Bio - oil + Char

(1) (2)

The biomass gasification reaction can be written:

nC x H y O z + mH 2O + w O 2 x1CO + x 2 H 2 + x 3CO 2 + x 4 CH 4 + x 5 H 2O + x 6 O 2 (3)

If is considered that the fractions of CO2, O2 and H2O formed in the gasification are mainly products of the combustion to get the necessary energy to perform the gasification and cover the energy losses included in the efficiency of the gasification reactor, and also that the CH4 production is negligible, the reaction to obtain hydrogen from biomass can be reduced to:

nC x H y Oz + mH 2 O x1CO + x 2 H2

(4)

which is the general equation for biomass gasification and could be followed by the shift reaction:

x1CO + x 3 H 2 O x 4 CO 2 + x 5 H 2

(5)

These general equations are similar to those proposed by Turn et. al. in [19], to obtain the theoretical hydrogen production. To obtain the theoretical production of hydrogen by the steam gasification of wet biomass it was used the general equation for biomass gasification (3) and according to the percentage of C, H and O of the biomass composition included in Tables 1 and 2 After gasification of the biomass it was considered the water gas shift reaction based on equation (5), where
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the CO reacts with water molecules to produce more hydrogen. The reactions that would be carried out by the steam gasification process and shift reaction for the different biomass feedstock used in this experiment are included in equations (6) and (7). from rapeseed oil cake:

CH1.62 O 0.65 + 1.35 H 2 O 2.16H 2 + CO 2

from walnut shells:

(6)

CH1.42 O0.63 + 1.37 H 2O 2.08H 2 + CO 2

(7)

In case of steam gasification, the presence of air could be limited so the risk of reaching the flammability limits could be lower than the air gasification, so the process could be considered safer than air gasification process. 3.1. Effect of S/B mass ratio Biomass gasification is a very complex process and occurs by three steps: the initial pyrolysis step, which produces volatile matter and the char residues, the secondary reactions involving the volatile products and the gasification reactions of the char with steam and carbon dioxide [21,22]. The influences of steam/biomass mass ratio ( S/B) on product yields of rapeseed oil cake and walnut shells: at 800C were studied. As shown in Fig. 3, in the case of rapeseed oil cake , the gas yield smoothly increases with the increase of S/B mass ratio, while the tar and char yield slightly decreases.

Figure 3. Effect of S/B mass ratio at 800C on the product yields.

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The similar trend is presented in the case of walnut shells. With an increase of S/B mass ratio from 0.0 to 0.6 g/g, the tar yield from rapeseed oil cake decreases from 5.8 wt% to 4.1 wt%, while the char yield decreases from 7.4 to 4.8 wt% at the same time, the tar yield from walnut shells decreases from 3.9 wt% to 2.1 wt% ,while the char yield decreases from 6.4 to 3.0 wt% . It can be inferred that steam reforming of tar and gasification reactions of char may simultaneously occur at high heating rate with biomass pyrolysis in the free-fall reactor. The addition of steam favors tar and char reduction and the increase of the gas yields mainly result from tar steam reforming, cracking and char gasification. At higher S/B ratio from 0.8 to 1.0 g/g, the product yields keep nearly constant, which is consistent with those reported in literatures [23]. The effects of S/B mass ratio on the product gas compositions are shown in Fig. 4.

Figure 4. Effect of S/B mass ratio at 800C on the product gas compositions. It is found that the CO and CH4 concentrations decrease with an increase of S/B mass ratio from 0.0 to 0.6 g/g, whereas the CO2 and H2 concentrations increase. There is a clear increase in the H2 concentration at S/B mass ratio between 0.20.6 g/g, and at higher S/B mass ratio, no significant changes are detected. It can be inferred that the addition of steam favor H2 formation. The H2 concentration of gas produced from rapeseed oil cake reaches the maximum 41 mol% at S/B mass ratio
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of 0.6 g/g, while that from walnut shells is 35 mol%. As shown in Fig. 4, for both kinds of biomass, the H2/CO molar ratio increases with the increase of S/B mass ratio Fig 5. It can be inferred that the watergas shift reaction plays an important role in determining the dry gas compositions and H2 production even in thus a short gas residence in the free-fall reactor. The difference of the dry gas compositions between both kinds of biomass could clearly be seen in Fig. 4. The H2/CO molar ratio in dry gas from rapeseed oil cake is higher than that from walnut shells. The fuel/nonfuel gases ( H2+CH4+C2-7 / CO+CO2) molar ratio increased to S / B 0.6 and 0.8 for rapeseed oil cake and walnut shells respectively and then slightly decreases This behavior is explained by increasing of the decomposition reaction of liquid and char products to a value after the reverse phenomenon occurs (Fig.6)

Figure 5. Effect of S/B mass ratio at 800C on the H2 / CO molar ratio

Figure 6. Effect of S/B mass ratio at 800C on the and H2+CH4+C2-7 /CO+CO2 molar ratio
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Also this maybe due to the difference in the inorganic matter contents of biomass such as CaO, K2O, and so on, which may act as a catalyst for the water gas shift reaction . According to the data obtained in our experiments and literatures [23], it could be concluded that the optimal gas yields and compositions are to be obtained at S/B ratio of 0.60.8 g/g in biomass steam gasification process. This result would favor the scale-up and system optimization of biomass gasification process. 3.2. Effect of reactor temperature The effects of reactor temperature on product distributions from rapeseed oil cake and walnut shells at S/B mass ratio of 0.6 g/g are shown in Fig. 7. The yields can be expressed as nearly the identical functions of the temperature.

Figure 7. Effect of reactor temperature on the product yields. A clear increase of the gas yields with reactor temperature is observed, which can result from various reasons: the higher temperature favors the higher heating rate, so the greater production of gas can be obtained in the initial pyrolysis step; the increase of gas yield is due to the endothermic steam reforming, cracking reactions of the tar and gasification reactions of the char, which are favorable at elevated temperatures. In the temperature region from 750 to 850C, the gas yields of walnut shells are a little more than that of rapeseed oil cake, which may be attributed to more volatiles from walnut shells. The effects of temperature on the gas compositions for both kinds of biomass are plotted in Fig. 8. It can be found that an increase in H2 and a decrease
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in CO concentration of product gas take place at elevated temperature. A product gas with H2 concentration of 51 mol% and CO concentration of 21 mol% can be produced from rapeseed oil cake at the highest temperature of 850C, while that with H2 concentration of 45 mol% and CO concentration of 30.02 mol% can be obtained from walnut shells at the same reactor temperature.

Figure 8. Effect of reactor temperature on the product gas compositions As shown in Fig.9 and Fig.10 the H2/CO and the fuel/nonfuel gases (H2+CH4+C2-7/CO+CO2) molar ratio increases with an increase of reactor temperature. Some of H2 formation is obtained due to further reactions of heavier hydrocarbons and tars. Another reason is the presence of the inorganic matters in the char produced from pyrolysis, which are to catalyze the watergas shift reaction.

Figure 9. Effect of reactor temperature on the H2/CO molar ratio(mol/mol)

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The fuel / nonfuel gases (H2 + CH4 + C2-7 / CO + CO2) molar ratio is much higher for rapeseed oil cake than walnut shells (Fig. 10). This could be explained by the difference in chemical composition of the two types of biomass.

Figure 10. Effect of reactor temperature on the H2+CH4+C2-7 / CO+CO2 molar ratio(mol/mol) Rapeseed oil cake contains a greater quantity of organic matter that by decomposition increases the amount of combustible gases, while walnut shells have a higher content in anorganic matter ,as results from the empirical formula (Table 1 and 2). Fuel gas arising from both species of biomass has a high content in H2 and can be a source from which it can be recovered. 3.3. Effect of catalyst One of the major issues in biomass gasification is to deal with the tar formation that occurs during the process. The unwanted tar may cause the formation of tar aerosols and polymerization to a more complex structure, which are not favorable for hydrogen production through steam reforming. Currently, three methods are available to minimize tar formation: (i) proper design of gasifier, (ii) proper control and operation and (iii) additives/catalysts. Catalysts not only reduce the tar content, but also improve the gas product quality and conversion efficiency. In this work CaO, MgO and mixture consisting of 50%CaO and 50% MgO catalytic substances were employed in biomass steam gasification processes to enhance the yield and quality of product gas and to decrease tar production by cracking and reforming the high molecular weight organic components. The catalytic activity on tar conversion was extensively investigated in different reactors such as fixed bed and fluidized bed reactors [15, 24, 25, 26]. Few data have been found on catalytic behaviors of catalysts in the initial stage of gasification as in the case of a free-fall reactor, although they should be very
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essential to develop and scale-up a novel gasification process. The data obtained in our experiments for CaO, MgO and mixture consisting of 50%CaO and 50%MgO catalysts are presented in Fig. 11. The diagrams present the influence of catalyst on product yields (800C, S/B mass ratio=0.6g/g).
Rapeseed oil cake 100 99 98 97 Gas(wt%) 96 95 94 93 92 CaO MgO Catalyst CaO+MgO Walnut shells

Rapeseed oil cake 3 2.5 2 Tar(wt%) 1.5 1 0.5 0 CaO

Walnut shells

MgO Catalyst

CaO+MgO

Rapeseed oil cake 4 3.5 3 2.5 Char(wt%) 2 1.5 1 0.5 0 CaO

Walnut shells

MgO Catalyst

CaO+MgO

Figure 11. Effect of catalyst on the product yields.

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For the mixt catalyst (50%CaO + 50% MgO) the gas yields are clearly higher while the tar yields lower than that of the CaO and MgO. The tar content resulted from rapeseed oil cake is higher than from walnut shells in presence of mixt catalyst, which is clearly lower than that in presence of the CaO and MgO additives. The effects of catalyst on dry gas compositions are shown in Fig.12.
CaO 50 45 40 35 Gas 30 composition 25 20 (wt%) 15 10 5 0 H2 CH4 CO CO2 C2-7 Mixture components (rapeseed oil cake) MgO CaO+MgO

CaO 45 40 35 30 Gas 25 composition 20 (wt%) 15 10 5 0 H2

MgO

CaO+MgO

CH4

CO

CO2

C2-7

Mixture components (walnut shells)

Figure 12. Effect of catalyst on the product gas compositions The H2 concentration increases notably in presence of mixt catalyst for both kinds of biomass. In the case of mixt catalyst the H2 concentration in product gas from rapeseed oil cake is 10% more than that in the case of CaO or MgO, while that from walnut shells is 15%. The increase of the H2 concentration is mainly attributed to catalytic steam reforming and cracking of the tar. In terms of catalytic activity, mixt catalyst (50%CaO + 50% MgO) reveals a comparably good performance of the tar destruction and the consequential H2 increase in the production of gases. The addition of CaO and MgO seems to play no significant role in tar conversion and H2 formation in the free-fall reactor. It may be due to that the mixture of oxides calcined before would create some degree of distortion in the array of the Ca or Mg atoms generating more active catalytic sites, which lead to
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the fact that the catalytic activity of mixt catalyst is better than CaO and MgO. The experimental results show that calcined mixt catalyst is more suitable to fast conversion process of biomass than calcined CaO and MgO. The asphalt fractions of the tars from rapeseed oil cake were determined to indicate the effects of steam and catalyst on the properties of tars. The reactor temperature was fixed at 800C and S/B mass ratio is 0.6 g/g. The yield of the asphalt indicates the tar conversion degree as shown in Fig. 13. The addition of steam and catalyst leads to more sufficient conversion of tars.
Walnut shells 0.25 0.2 Asphalt 0.15 fraction 0.1 (wt%) 0.05 0 Pyrolysis Steam Catalyst Thermochemical process Rapeseed cake

Figure 13. Asphalt fraction yield in different condition (pyrolysis, steam gasification and catalytic steam gasification) As Figure 13 shows the fraction of asphalt falls to about half when is used catalyst compared to that obtained in the simple process of pyrolysis. Utilization of the catalyst also varied the main gas composition by converting hydrocarbons and water vapor to CO and H2. The gasification efficiency was improved by increasing gas yield, which was probably due to tar cracking in presence of catalyst.

4. CONCLUSIONS Biomass is potentially a reliable energy resource for hydrogen production. Biomass is renewable, abundant and easy to use. Over the life cycle, net CO2 emission is nearly zero due to the photosynthesis of green plants. The technologies of pyrolysis and gasification of biomass can be used for the production of H2 in a sustainable way, giving an energy use of the biomass residues. Of these two technologies, the gasification technology is more suitable for gas production, although both of them are still in process of improvement and investigation. Steam gasification of two kinds of biomass (rapeseed oil cake and walnut shells) was carried out at high heating rate in a gassolid concurrent down flow
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free-fall reactor. The experimental results show that the in situ steam reforming of nascent volatiles and steam gasification of char occur instantaneously with fast pyrolysis of biomass in a short gas residence time in reactor. The gas yields increase and the tar and char yields decrease with the increase of S/B mass ratio. The maximum of the gas yield and the H2 concentration in dry gas can be obtained at about S/B ratio of 0.6 g/g to 0.8 g/g. The gas yield and the H2 concentration in product gas increase with the reactor temperature, while the yield of tar, char and CO and CH4 concentrations in dry gas decrease. The catalytic activity of CaO, MgO and mixture consisting of 50%CaO and 50% MgO catalysts were investigated. Mixt catalyst reveals a comparably good performance of tar destruction and the consequential increase of gas production in a short vapor catalyst contact time. Asphalt fraction of tar samples indicate the presence of steam and catalyst favors the tar decomposition and small molecules production. These results will contribue to developing a new approach of biomass gasification for hydrogen-rich gas as a source as renewable energy. Acknowledgments The authors gratefully acknowledges the financial support provided by research project no. 21-013/2007 of National Plan II for R & D in energy field.

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