International Journal of Hydrogen Energy 32 (2007) 2803 2808 www.elsevier.

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An experimental study of hydrogen production by gasication of biomass in the presence of a CO2 sorbent
Madhukar R. Mahishi a , , D.Y. Goswami b
a Mechanical & Aerospace Engineering, University of Florida, PO Box 116300, Gainesville, FL 32611, USA b Clean Energy Research Center, University of South Florida, 4202 E. Fowler Avenue, Tampa, FL 33620, USA

Received 10 June 2006; received in revised form 18 December 2006; accepted 19 March 2007 Available online 10 May 2007

Abstract The paper presents a novel technique that enhances the hydrogen yield of conventional biomass steam gasication. This is done by integrating the gasication and absorption reactions. The method involves steam gasication of a carbonaceous fuel (biomass) in presence of a CO2 sorbent. Experiments were conducted by gasifying pine bark in presence of calcium oxide. The gasication was carried out at atmospheric pressure in the temperature range 500.700 C. The hydrogen yield, total gas yield and carbon conversion efciency increased by 48.6%, 62.2% and 83.5%, respectively, in the presence of sorbent at a gasication temperature of 600 C. This was attributed to the reforming of tars and hydrocarbons in the raw product gas in presence of calcium oxide. The CO and CH4 concentrations in the product gas were lower while using the sorbent. The calcium oxide played the dual role of sorbent and catalyst. 2007 International Association for Hydrogen Energy. Published by Elsevier Ltd. All rights reserved.
Keywords: Biomass; Calcium oxide; CO2 ; Gasication; Hydrogen; Sorbent

1. Introduction Presently, hydrogen is produced mainly by catalytic steam reforming of natural gas [1]. However, in order to have environment friendly hydrogen, it must be produced by renewable methods. A number of ways and a variety of resources for producing renewable hydrogen are being investigated [2]. Of all the renewable resources, biomass holds the greatest promise for hydrogen production in the near future [2,3]. Thermochemical biomass gasication has been identied as a potential technology for producing renewable hydrogen [46]. Balasubramanian et al. [7] have proposed the use of a CO2 sorbent for enhancing the hydrogen yield of conventional steam methane reforming. This innovative method could be applied to any carbonaceous material such as coal, hydrocarbons or biomass [8,9]. A theoretical study of using sorbents during thermochemical gasication of biomass was conducted by
Corresponding author. Tel: +1 352 328 4109; fax: +1 763 528 7226.

the authors in a previous work [10]. Conventional biomass steam gasication consists of two main reactionsa biomass reforming reaction: CH1.43 O0.62 + 0.38H2 O CO + 1.1H2 HR = 112.7 kJ/mol. (1)

(biomass chemical formula obtained from the elemental analysis: Table 1). This is followed by the watergas shift reaction: CO + H2 O CO2 + H2 , HR = 41.2 kJ/mol. (2)

A sorbent, such as calcium oxide absorbs the product CO2 and releases heat as per the following reaction: CaO + CO2 CaCO3 , HR = 178.3 kJ/mol. (3)

The concept of using sorbents combines the biomass reforming, watergas shift and CO2 absorption reactions into a single step: CH1.43 O0.62 + 1.38H2 O + CaO CaCO3 + 2.2H2 , HR = 106.8 kJ/mol. (4)

E-mail addresses: mahishi@u.edu (M.R. Mahishi), goswami@eng.usf.edu (D.Y. Goswami).

0360-3199/$ - see front matter 2007 International Association for Hydrogen Energy. Published by Elsevier Ltd. All rights reserved. doi:10.1016/j.ijhydene.2007.03.030

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Nomenclature M P T moles () pressure (atm) temperature (K) subscript/abbreviation prod bio C.T. product gas biomass constant temperature

Greek letters
cc

carbon conversion efciency (%)

The objective of the present work is to experimentally determine the effect of adding sorbent on the hydrogen yield during biomass gasication. For this purpose, tests were carried out by steam gasifying Southern pine bark (a popular biomass resource found in Southeastern United States) in the presence of calcium oxide at different temperatures. The output variables studied were gas composition, total gas yield, individual yields of important gases (H2 , CO, CO2 and CH4 ) and the carbon conversion efciency. 2. Experimental set-up Southern pine bark was used as the model biomass compound. The elemental composition of biomass was determined by ultimate and proximate analysis and is given in Table 1. The experimental set-up is shown in Fig. 1. It consists of (1) a primary reactor, (2) a secondary reactor, (3) steam generator sub-system, (4) gas cooling sub-system, (5) gas analysis facility. The primary reactor (also called gasier) was a simple batch-type reactor which was heated by a radiant ceramic cylindrical heater. The primary reactor holds the biomass bed on a quartz wool support. The secondary reactor is similar to the primary reactor, except that it holds the calcium oxide bed. Both the reactors were made from SS-316 tubing. About 5 g of pine bark (in the form of pellets) were fed to the gasier during each experiment. Calcium oxide reagent (Fisher scientic, particle size 0.045 mm) was used as the sorbent. The temperatures of the biomass and sorbent beds were measured by K-type thermocouples. Two temperature controllers controlled the heaters individually. The steam generator sub-system consisted of a peristaltic pump which sent water through a coiled 1 4 SS-316 tubing heated by another radiant ceramic heater. Superheated steam at a maximum temperature of 700 C and 1 atm pressure was produced. The steam ow rate was set at 5 g/min for all the experiments. The ow rate was based on practical considerations. In order to have a uniform ow of steam around the biomass bed, it was necessary to send the steam at a ow rate that was neither too high nor too low. High ow rates would blow the bed and low ow rates would not generate sufciently high steam temperatures. Based on these considerations, the steam ow rate was set at 5 g/min. The system was purged using inert gas (Argon) before the start of each experiment. All experiments were carried out at atmospheric pressure. The gas cooling subsystem consisted of a concentric tube heat exchanger and condensate traps. The concentric tube heat exchanger was made of SS-316 tubing.

Table 1 Composition of Southern pine bark

Ultimate analysis C H O N S 51.13% 6.10% 41.96% 0.14% 0.04% Proximate analysis Fixed carbon Volatiles Moisture Ash 26.94% 63.21% 9.22% 0.63%

The hot gas and steam mixture owed through the inner tube and ethylene glycol coolant owed through the outer tube. The ethylene glycol coolant was further cooled by a refrigerant in a constant temperature bath. The gas passed through a condensate trap where the condensed steam and tars were collected. The gas further passed through another condensate trap via a quartz wool packing which absorbed any moisture still left in the gas. The dry, clean gas was then fed to a gas chromatograph (SRI 8610C) where sampling was done every 15 min. The gas ow rate was measured using a mass ow controller (Omega FMA 2610A) in conjunction with a soap bubble lm ow meter (Alltech make). The gas composition varied with time, however, after about 45 min it reached a quasi-steady state. An average of the different samples gave the representative product composition for each run. The product composition and gas volume data (obtained using the ow meter) were used to determine the gas yield (ml/g) for each run. The GC had a Molecular Sieve 13X column (for separating H2 , O2 , N2 , CO, CH4 ) and a Hayesep D column (for separating CO2 and C1 C6 ) and TCD detector was used. The carbon conversion efciency quanties the effectiveness of gasication. The carbon conversion efciency is dened in terms of the moles of carbon in the solid biomass that are converted to carbon-containing gases:
cc

Mprod 100, Mbio

(5)

where Mprod is the moles of C in product gas (CO, CO2 , CH4 1 ), Mbio the moles of C in pine bark. 3. Test variables and thermodynamic considerations Experimental studies were conducted to determine the effect of adding sorbents on the hydrogen yield of biomass
1 Moles of higher hydrocarbons were not considered as their proportion was small as compared to CO, CO2 and CH4 .

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T1 : Thermocouple (biomass bed) T2 : Thermocouple (sorbent bed) P: Pressure Biomass Bed

Primary reactor

Secondary reactor

Sorbent Bed

Steam Generator Subsystem Peristaltic pump Steam Generator Gas Cooling Subsystem Dry clean gas to GC Heat Exchanger Water Steam T1 Heaters T2 Hot Gases Eth glycol To CT bath
Fig. 1. Schematic of experimental set-up.

Gas Analysis Facility

Eth glycol From CT bath

gasication. The temperature of the gasier was varied from 500 to 700 C and the total gas yield and hydrogen yield of plain biomass gasication were determined. Later on, experiments were conducted by gasifying the biomass in the same temperature range but, in the presence of calcium oxide sorbent. Since temperature is an important variable that signicantly affects the product gas composition, the experimental studies focused rst on the effect of temperature and later, on the combined effects of adding sorbent and varying the temperature. Pressure, too, has considerable inuence on the hydrogen yield of biomass gasication. Basic thermodynamic studies on the effect of pressure on the hydrogen yield of biomass gasication were conducted in the past and are reported in an earlier work [10]. It was observed in that work that increasing the pressure reduced the hydrogen yield of biomass gasication. The highest hydrogen yield occurred at atmospheric pressure. Hence, in the present work, all the experiments were carried out at one atmosphere. In any biomass gasication system for hydrogen production, there are many reactors which absorb heat (such as gasier and steam generator) and there are other reactors which reject heat. From reaction 1, it is clear that 112.7 kJ of energy is required to produce 1.1 moles of hydrogen. An additional mole of hydrogen is produced by the watergas shift reaction (reaction 2). The shift reaction also consumes a mole of steam. Hence, in total, 1.38 moles of steam are consumed and 2.1 moles of hydrogen are produced. The amount of heat energy required by the boiler to produce 1.38 moles of steam (say at 1 atm and a temperature of 600 C) is about 90 kJ. Hence a total of 202.7 kJ (112.7 + 90) of heat energy is consumed by the boiler and gasier combined. In the process, the sorbent gets saturated and should be regenerated for further use. The regeneration typically takes place at 850 C and consumes about 168 kJ/mol of CO2 absorbed [11]. This heat needs to be continuously supplied to the system in order to ensure continuous hydrogen production. Hence a total of 370.7 kJ of heat must be supplied to

the system for producing 2.1 moles of hydrogen. Theoretically, this comes to 176 kJ of heat energy input per mole of hydrogen produced. In actual practice, more heat must be supplied to take care of the equipment inefciencies and heat losses to the surrounding. This however does not consider any internal heat integration which is possible by optimizing the system. In the laboratory scale experimental set-up the necessary heat is provided by electric heaters. However, for actual gasication systems external heat needs to be supplied by appropriate means. Some reactors (such as gasier and steam generator) consume large amounts of heat. In actual systems, heat can be supplied by combusting part of the biomass feedstock. Alternately, a fraction of the syngas produced by the gasier can be oxidized to supply the necessary heat. Another method would be to use the hydrogen produced by the gasier in a Solid Oxide Fuel Cell (SOFC) and use the high temperature SOFC exhaust to supply the necessary heat. SOFCs do not require ultra pure hydrogen and hence some impurity (CO) in the product gas is acceptable. The hydrogen in the nal product stream can also be combusted to produce power using a gas turbine and the waste heat from the exhaust stream of turbine can be used to supply heat to the gasier. Hence there are many alternatives by which heat can be supplied and the most appropriate method will depend on the end use of the product hydrogen and system optimization. 4. Results and discussion 4.1. Effect of temperature Baseline experiments were carried out by steam gasifying pine bark (without sorbent) at various temperatures from 500 C to 700 C. It took about 75 min to completely gasify 5 g of biomass. The experiment was considered complete when gas stopped bubbling out of the condensate trap. The baseline data of total gas yield and yields of H2 , CO, CO2 and CH4 were

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Table 3 Gas composition (vol%) and total gas yield (ml/g) and carbon conversion efciency for sorbent enhanced case
T ( C) Gas composition (%) H2 549.9 874.8 1111.0 22.9 30.3 40.3 500 600 700 58.9 64.5 65.5 CH4 5.9 2.8 3.6 CO 9.0 5.9 4.2 CO2 26.2 26.8 26.7 1360.0 1418.1 1235.7 63.8 55.6 49.0 Yield (ml/g)
cc

Table 2 Gas composition (vol%), total gas yield (ml/g) and carbon conversion efciency for no sorbent case
T ( C) Gas composition (%) H2 500 600 700 51.8 60 62 CH4 8.4 3.2 1.5 CO 12.8 9.1 8.1 CO2 27.0 27.7 28.4 Yield (ml/g)
cc

(%)

(%)

Gas yield (ml/g) for plain biomass gasification - no sorbent 900 800 700 600 Yield (ml/g) 500 400 300 200 100 0 H2 CH4 Gas 500 deg C 600 deg C 700 deg C CO CO2

Gas yield (ml/g) - biomass gasified with sorbent 900 800 700 Yield (ml/g) 600 500 400 300 200 100 0 H2 CH4 Gas 500 deg C 600 deg C 700 deg C CO CO2

Fig. 3. Effect of sorbent addition on gas yield.

Fig. 2. Effect of temperature on gas yield (no CaO).

Watergas shift: CO + H2 O CO2 + H2 , HR = 41.2 kJ/mol. (8)

obtained from these experiments (total gas yield (in ml/g) refers to sum of the yields (ml/g) of the four important gases that are produced in the highest proportion namely: H2 , CO, CO2 and CH4 ). The gas composition (vol%) for each test including the main constituents (H2 , CO, CO2 and CH4 ) and the total gas yield are given in Table 2. Fig. 2 shows the effect of temperature on the gas yield. The total gas and hydrogen yields were found to increase monotonically with temperature. The carbon conversion efciency (Table 2) was also found to increase steadily with temperature. This is attributed to the reforming of tars and higher hydrocarbons in the presence of steam at high temperatures to produce more gas. In general, it was observed that the amount of hydrogen and carbon dioxide in the product gas was high as compared to the other constituents. This is due to reforming of the hydrocarbons in the presence of steam and also due to the watergas shift reaction. The important reactions taking place during the biomass steam gasication process are as follows: Biomass steam reforming: Biomass + steam H2 + CO + CO2 + CH4 + Cn Hm + Tars + , HR > 0. Hydrocarbon reforming: Cn Hm + 2nH2 O nCO2 + (2n + m/2)H2 , HR > 0. (7)

In all the above reactions, hydrogen is produced. 4.2. Effect of sorbent Experiments were conducted by steam gasifying pine bark in the presence of calcium oxide. The pine and the calcium oxide beds were maintained at the same temperature. The sorbent to biomass molar ratio was maintained at one for all the experiments. This was based on thermodynamic considerations. The theoretical amount of calcium oxide needed to absorb all the CO2 produced from 5 g of pine bark in conventional biomass gasication was determined theoretically using thermodynamic calculations. These calculations gave a sorbent to biomass molar ratio of unity. The temperature was varied in the same range as the base case i.e. from 500 to 700 C. Table 3 gives the gas composition of the main constituents (H2 , CO, CO2 and CH4 ) and the total gas yield at different gasication temperatures and Fig. 3 shows the yields at those temperatures. On comparison with the base (no sorbent) case it was found that the total gas yield increased substantially in the presence of the sorbent. At 500 C the total gas yield had more than doubled (from 549.9 to 1360 ml/g) and at 600 C it had increased by almost 62% (from 874.8 to 1418.1 ml/g). The hydrogen yields at 500 C (719.4 ml/g, refer Fig. 3) and 600 C (852.3 ml/g) in

(6)

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10 1 Pressure (atm) 0.1 0.01 CaCO3(s) = CaO(s)+ CO2 (g) 0.001 0.0001 500 550 600 650 700 750 800 850 900 950 1000 Temperature (C)
Fig. 4. Equilibrium CO2 partial pressure as function of temperature.

Carbonation favored in this region CaO (s)+CO2 (g) = CaCO3(s)

Table 4 Gas composition (vol%) during initial gasication phase (rst 15 min)
T 600 C (no CaO) 600 C (with CaO) H2 (%) 60.2 83.0 CH4 (%) 3.1 1.5 CO (%) 9.0 6.3 CO2 (%) 27.7 9.2

Calcination favored in this region

90 80 70 60 Vol (%) 50 40 30 20 10 0 15

Gas composition Vs time at 600C (in presence of CaO) H2 CH4 CO CO2

Fig. 6. Tar laden condensate samples of plain gasication (left) and sorbent enhanced gasication.

30 Time (min)

45

60

Fig. 5. Gas composition vs. time.

presence of sorbent were comparable to the yield at 700 C (712.2 ml/g) for the base case. Comparing the results of the gas yields for the two cases (Figs. 2 and 3) it was observed that the yield of H2 and CO2 in the product gas has increased in presence of calcium oxide. The three ways CO2 is generated in the product gas are: direct decomposition of the original biomass, cracking of tars/hydrocarbons in the presence of steam and the watergas shift reaction (reactions (6)(8)). The CO2 absorption by calcium oxide is strongly dependent on the partial pressure of CO2 in the product stream at the specied gasication temperature. When the gasication temperature is less than the equilibrium temperature corresponding to the CO2 partial pressure, CO2 is absorbed and the sorbent gets converted to CaCO3 ; above this temperature CaCO3 desorbs to produce the original CaO as shown in Fig. 4 [11]. Fig. 5 shows how the gas composition varies with time (at a gasication temperature of 600 C in the presence of CaO). Table 4 gives the gas composition during the initial phase (rst 15 min) of gasication. It is observed that during the initial phase the CO2 in the product gas was very low and after about 45 min, it reached a quasi-steady state as shown in Fig. 5. CO2 absorption took place

until the gasication temperature corresponding to the partial pressure of CO2 was less than the equilibrium temperature, after which no CO2 absorption took place. Since the only source of carbon in the experiment is the original biomass, all the CO2 produced has to come either from the direct decomposition of biomass or through steam reforming of tars and hydrocarbons in presence of CaO or through the watergas shift reaction. In the past, some research groups have studied the tar reforming ability of calcium oxide salts (dolomite or pure calcite), while conducting experiments on raw gas cleaning of the products of biomass gasication [12,13]. The objective of those studies was to clean the tars and particulates in the raw gas, whereas, in the present study the objective was to enhance the hydrogen yield of biomass gasication. Since the amounts of biomass and steam supplied in the base case and the sorbent enhanced case are the same, it is hypothesized that the additional CO2 is coming from the reformation of tars while at the same time producing additional hydrogen as per the following reaction: Tars+steam H2 +CO2 +CO+lower hydrocarbons+ , HR > 0. (9) The tars and the hydrocarbons are reformed in presence of CaO thereby producing additional hydrogen and this is evident from the increased hydrogen yields even at gasication temperatures as low as 500.600 C (Figs. 2 and 3). Samples of the tar-laden condensate were collected for the two experiments (with and without sorbent) conducted at 600 C and are shown in Fig. 6. It was observed that the tar-laden water from the plain biomass gasication (dark) had
CaO

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more particulates and suspended matter as compared to the sorbent enhanced gasication case. The CO and CH4 concentrations in the product gas are lower for the sorbent enhanced case as compared to the base case (Tables 2 and 3 except for the CH4 concentration at 700 C case which is possibly due to experimental error). The hydrogen yield (ml/g) has increased substantially in presence of CaO sorbent (Figs. 2 and 3). This is attributed to the watergas shift reaction being driven in favor of hydrogen in presence of CaO. The gas composition during the initial phase shows very high hydrogen concentration for the sorbent enhanced case as compared to the base case (83% vs. 60.2%). It is hypothesized that the additional hydrogen, over and above that produced from direct biomass gasication comes from the hydrocarbon and tar reforming. This suggests that the calcium oxide played a dual role of a sorbent and a catalyst. The carbon conversion efciency (Table 3) for the sorbent enhanced case is found to be higher than the base case especially at low temperature. The product gas, though rich in hydrogen also contains other gases (CO, CH4 , CO2 and some higher hydrocarbons). The product gas must be cleaned and hydrogen must be separated for further use. The hydrocarbon impurities can be reformed by sending the product gas over a catalyst bed (such as Ni/Al2 O3 ). This will produce additional hydrogen. The CO in the product gas can be removed by passing it through watergas shift reactor where the catalyst will oxidize all CO to CO2 and reduce the steam thereby producing additional hydrogen. The hydrogen can be nally separated from CO2 using a pressure swing adsorption unit (PSA) to get a pure hydrogen stream. Recently, it has been found that noble metal catalysts have excellent tar reforming and hydrogen enhancing abilities when used in biomass gasication [5,14]. It may be interesting to study the combined effect of using Noble metal catalysts with simple inexpensive sorbents like calcium oxide. 5. Summary and conclusion Southern pine bark was steam gasied in presence of calcium oxide sorbent at various temperatures in the range 500700 C. The total gas yield in the presence of sorbent more than doubled at a gasication temperature of 500 C and at 600 C was almost 62% higher than the base case. At 600 C, the hydrogen yield and carbon conversion efciency increased by 48.6% (573852.3 ml/g) and 83.5% (30.356%), respectively, for the sorbent enhanced case. It was also observed that the hydrogen yield for the sorbent case at 500 and 600 C was more than the conventional hydrogen yield at 700 C. This suggests that it is possible to operate the gasier at a lower temperature while using the sorbent and still get the same (or higher) hydrogen yield. The absorption of CO2 by calcium oxide depends on the equilibrium temperature corresponding to the partial pressure of CO2 . The calcium oxide reagent reformed the tars and hydrocarbons in the product gas, thereby, playing the dual role of sorbent and catalyst. The CO and CH4 concentrations in the product gas were lower while using the sorbent. The increasing gas and

hydrogen yield trend was observed until a gasication temperature of 700 C after which the yields were similar to the base case. This study has only presented the results of hydrogen enhancement during biomass steam gasication by using a sorbent. However, for this method to become viable, the sorbent must be recovered and regenerated, which is recommended for further study. Acknowledgments The authors wish to acknowledge that this work was carried out under US DOE Grant: DE-FG36-04GO14224. The authors would also like to thank Huffman Laboratories Inc, Golden, CO for carrying out the elemental analysis of biomass pine bark sample. References
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