Energy Conversion and Management 44 (2003) 18751884

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Biomass pyrolysis/gasication for product gas production: the overall investigation of parametric eects
G. Chen
a

a,*

, J. Andries a, Z. Luo b, H. Splietho

Faculty of Design, Engineering and Production, Section Thermal Power Engineering, Delft University of Technology, Mekelweg 2, 2628 CD Delft, The Netherlands b Institute for Thermal Power Engineering, Zhejiang University, Yugu Road 20, Hangzhou 310027, China Received 28 November 2001; received in revised form 22 April 2002; accepted 3 August 2002

Abstract The conventional biomass pyrolysis/gasication process for production of medium heating value gas for industrial or civil applications faces two disadvantages, i.e. low gas productivity and the accompanying corrosion of downstream equipment caused by the high content of tar vapour contained in the gas phase. The objective of this paper is to overcome these disadvantages, and therefore, the eects of the operating parameters on biomass pyrolysis are investigated in a laboratory setup based on the principle of keeping the heating value of the gas almost unchanged. The studied parameters include reaction temperature, residence time of volatile phase in the reactor, physico-chemical pretreatment of biomass particles, heating rate of the external heating furnace and improvement of the heat and mass transfer ability of the pyrolysis reactor. The running temperature of a separate cracking reactor and the geometrical conguration of the pyrolysis reactor are also studied. However, due to time limits, dierent types of catalysts are not used in this work to determine their positive inuences on biomass pyrolysis behaviour. The results indicate that product gas production from biomass pyrolysis is sensitive to the operating parameters mentioned above, and the product gas heating value is high, up to 1315 MJ/N m3 . 2002 Elsevier Science Ltd. All rights reserved.
Keywords: Biomass; Pyrolysis/gasication; Parameters; Eect; Product gas

Corresponding author. Tel.: +31-15-2786541; fax: +31-15-2787204. E-mail address: g.chen@wbmt.tudelft.nl (G. Chen).

0196-8904/02/$ - see front matter 2002 Elsevier Science Ltd. All rights reserved. PII: S 0 1 9 6 - 8 9 0 4 ( 0 2 ) 0 0 1 8 8 - 7

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1. Introduction More attention has been paid in recent years to renewable energy, especially biomass energy, due to the fact that increasing CO2 , NOx and SOx emissions in the atmosphere are resulting from the increasing application of fossil fuels and man fears their accompanying shortage occurring in the near future. Biomass is a renewable resource and, compared with fossil fuel, has a much shorter period of life cycle (life cycle is here dened as the duration of the period from the growth of biomass to its nal utilisation by mankind), and therefore, the application of biomass for energy can lead to zero net CO2 emission in a very short life cycle period since carbon in the form of CO2 and energy are xed by photosynthesis during biomass growth. Compared with other renewable energy resources, biomass is abundant in annual production (up to 2740 Quads, by NREL web-site), with a geographically widespread distribution in the world [1]. A good solution for technical application of biomass energy is conversion of biomass by a pyrolysis/gasication process [29]. Unfortunately, pyrolysis, especially ash pyrolysis technology, has been considered as a good solution to convert biomass only to liquid fuel, not to gaseous fuel. The reasons that strongly support this approach are that the gas yield from conventional pyrolysis technology is very low, normally below 40 wt.% [1013] and the accompanying corrosion is serious to downstream equipment, like a gas turbine/engine, caused by the high content of tar vapour contained in the gas phase [3]. However, pyrolysis gas, compared with conventional gasication gas, is more advantageous, as it is higher in heating value and, consequently, can be applied well to the downstream gas turbine or other combustion engines for power generation or used as a substitute for civil gas for cooking. Furthermore, when integrated with gas turbine combustion, this kind of gas can overcome the challenge incurred by combustion of conventional gasication gas [3]. In the latter case, more fuel gas is needed in order to operate the turbine with the same turbine inlet temperature, and accordingly, signicant changes in the turbines conguration are required. This work tries to make people condent in gas production through the pyrolysis route. The nal goal of the current work is intended to increase the product gas production from biomass pyrolysis in a xed bed reactor and, in parallel, to reduce tar corrosion to downstream equipment by converting tar to gas in the pyrolysis mechanism. The main research activities here are concentrated on the parametric eects, including: reaction temperature, residence time of vapour phases, physico-chemical pretreatment, heating rate of the external heating furnace, heat and mass transfer ability of the setup used, the running temperature of a separate cracking reactor and the geometrical conguration of the pyrolysis reactor.

2. Experimental apparatus and method 2.1. Experimental apparatus Pyrolysis of biomass material was performed in a batch pyrolysis assembly as shown in Fig. 1, which can contain up to 500 g of sawdust ne. Generally speaking, the pyrolysis assembly consists of three parts: reactor part (pyrolysis reactor, cracking reactor and heating furnace), condenser and purication part (condenser I and II, dryer), and gas storage part (gas tank or water tank). The pyrolysis reactor was made of stainless steel (total height, 750 mm; 80 mm i.d.) and normally

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Fig. 1. Laboratory-made batch biomass pyrolysis apparatus.

is immersed in an externally heated furnace lined with insulation materials of silicaalumna wool. The outlet of the pyrolysis reactor is connected to a cracking reactor via a connecting tube, and thus, the volatile phase leaving the pyrolysis reactor is subjected to an additional cracking reaction and afterwards ows into a condenser. The condenser consists of two stages, one using hot water (condenser I) and the other using mixed ice/water (condenser II). Following condenser II is a spherical dryer lled with silica-gel pellets (the dryer is not shown in Fig. 1). Most of the water entrained by the pyrolysis gas and a little, still uncondensed, tarry components are further removed here. The gas exiting from the spherical dryer is rst introduced into a water tank, followed by a gas vent. The connecting tube before the condenser is always well insulated to prevent tarry components condensing. The capacity of the external heating furnace is 4 kW at rst and then is changed to 8 kW in order to shorten the operational time. Of this power, 2 kW is set to run the cracking reactor. Nitrogen is passed through a owmeter, serving as a purge gas and protective gas to avoid coking occurring on the surface of the reactor before and after operation. The agitator, a metallic rod, is operated manually in only a few experiments. The reactor temperature is measured by thermocouples welded onto its inner wall and can be automatically switched on or o by a temperature controlled program. The further description of this apparatus is shown in the thesis of Chen [10]. 2.2. Experimental method During startup, an inert gas is used to purge air out of the pyrolysis reactor, which has already been lled with biomass particles. As the temperature of the pyrolysis reactor is raised above 100 C, gaseous products are generated from the inherent moisture, and afterwards, as the temperature is increased further, up to 200 C, more gaseous products are produced from the biomass. At this time, the ow of inert gas is turned o because the released gases are of sucient positive pressure and, thus, can eectively prevent air from entering the reactor. The duration of operation at a certain reaction condition is determined by ensuring that no further condensation is occurring in the cold traps. As a result of the fact that determination of

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further condensation of the volatile phase is relatively much more dicult, another option is taken in terms of the gas only. If the value of gas yield, indicated in a cumulative volumetric owmeter, in the last time interval stays within 5% of that in the time interval corresponding to a temperature of 400450 C, then the pyrolysis reaction can be thought to end. The residence time of the volatile phase is changeable during our experiments, dependent on the velocity of the carrier gas, like nitrogen. The gaseous components generated inside the pyrolysis reactor travel rst to the cracking reactor through a teon tube, then to condenser I and condenser II, further to the dryer and, at last, to the water tank where it is collected. In condenser I, most of the tarry components with boiling temperature above 100 C can be collected, and the others are quenched further in condenser II and separated from the main gaseous ow. The inlet of the gas ow is at the bottom of the condenser so that the oil vapours have to pass through the whole pool of cold pyrolysis liquid, thereby enhancing the quality of the pyrolysis gas. At the end of every experiment, the pyrolysis residue is weighed to determine the yield, and the gas yield is calculated directly for most runs, based on its measured volume, and the gas components are analysed by gas chromatography. However, for some pyrolysis experiments, where the mass balance of the experimental assembly is considered, the pyrolysis liquid is collected under special requirements and afterwards weighed. In this case, the condensers and all connecting tubes are washed, and the packing materials are extracted with dierent solvents, depending on the nature of the tars arising from the biomass material used: methanol for rice husk; 1:1 mixture (by volume) of methanol and acetone for sawdust and successive extraction with dichloromethane and acetone (not methanol as indicated by Stiles and Kandiyoti [14]) in the case of rice straw and cotton stalk. The mass balance for these experiments is larger than 95%.

3. Experimental results and discussions During the experiments, the radial temperature gradient and axial temperature dierence may be neglected, and the reactor temperature here is indicated in terms of the mean value of the top and bottom surface temperatures. The experimental data is taken as eective only when the residual weight inside the reactor at the end of operation is repeatable. This requirement sometimes wastes our time and eorts. However, it is a prerequisite for a good experiment and also for comparison of results with dierent conditions. For the concern of temperature only, the temperature dierence between the top and bottom surfaces should be within 15 C. In order to get further insight into the design of a potential pyrolysis reactor, here the geometrical conguration of the reactor is also investigated. All the comparable data are based on standard run condition: 1 atm pressure, atmospheric temperature of 25 C, occupied volume by biomass particles of 95% of the whole reactor, reaction temperature 800 C, temperature of the connecting tube and tubular cracking reactor 500 C and the mean size of feedstock for rice straw 2 10 mm and for sawdust 0.25 mm. Table 1 shows the elemental and proximate analysis data of the biomass feedstock used experimentally. The bulk densities of the rice straw and sawdust are 79.1 kg/m3 , 166.5 kg/m3 , respectively. Please note: the properties of the biomass feedstock are completely the same as those we can obtain from farmers or wood-processing factories. We just cut the rice straw

G. Chen et al. / Energy Conversion and Management 44 (2003) 18751884 Table 1 Analysis data of used biomass feedstock Type Elemental analysis (wt.%) C Rice straw Sawdust
a

1879

Proximate analysis (wt.%) S 0.10 0.06 O

a

H 5.01 4.86

N 1.07 1.38

M 9.96 12.27

A 15.23 0.83

V 69.11 70.55

FC 5.70 16.35

Caloric value (kJ/kg) 15 175 18 064

33.96 45.66

34.67 34.94

Dierence.

Table 2 The eect of heating rate on the gas yielda Biomass types Rice straw Sawdust
a

Original heating rate (low rate) 49 56.2

Enhanced heating rate (high heating rate) 65.7 72.4

Relative change of gas yield (%) 34.1 () 28.8 ()

All the end products of gas, liquid and solid in this paper are expressed in terms of weight percentage; ()) and () represent the total gas yield is decreased or increased, respectively.

using a very simple way. Therefore, to some extent, the results obtained here could be easily applied to naturally harvested biomass wastes. 3.1. Heating rate of the external heating furnace An additional heater of large thermal capacity was used in this test to get a high heating rate. The cracking reactor is set at a temperature of 700 C, not 500 C as in the standard run. The comparison of two heating rates is very conspicuous, as shown in Table 2. The high heating rate results in much higher product gas yield, for rice straw up to 65.7 wt.% and for sawdust up to 72.4 wt.%. It is well known that a high heating rate is benecial to gas production, however normally, the heating rate is not so inuential. The reason here may be attributed to the original reactor of too low heating rate. In that condition, when the reactor temperature reaches the level suitable for starting biomass pyrolysis, most of the volatile phase is quickly released from the biomass, however there is no chance for its secondary decomposition due to the still low temperature level. 3.2. Reactor temperature Fig. 2 presents the yields of the dierent pyrolysis phases of rice straw and sawdust corresponding to the experiments conducted with reaction temperature between 500 and 950 C. It can be observed that an increase in temperature leads to increases in gas production and decreases in the solid fraction. The liquid fraction yield, on the other hand, goes through a maximum at about 500 C, which suggests that the gas formation increases mainly happens from this point, due to cracking of the liquid fraction developed after this temperature. However, much dierent from the literature [5] is the solid fraction, which decreases in total with the increase of reaction

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Fig. 2. The products of rice straw and sawdust pyrolysis at dierent temperature.

temperature, but in the curve, two temperature transitional points can be found, representing the start and end of the gasication reactions (reactions 1 and 2) involving steam vapour and char. C CO2 ! 2CO reaction 1; endothermic reaction 2; endothermic

C H2 O ! CO H2 3.3. Residence time

The inuence of residence time of the volatile phase on the yields of rice straw and sawdust pyrolysis is shown in Table 3. It can be seen that an increase in residence time of the volatile phase results in increasing values of gas yield. This could be explained by the cracking reaction occurring in the primary pyrolysis product of liquid. The longer is the residence time of the volatile phase (gaseous and liquid products), the better is the cracking reaction. Also in Table 3, the signicant increase of gas yield is between 2.0 and 3.0 s, and afterwards, the increase is small. This result means most of the tarry components decompose with a residence time of 23 s in our experimental conditions. Compared with the literature [15], the residence time required by our experiments is
Table 3 The eect of residence time on gas yield Biomass types Rice straw Sawdust Residence time (s) 1.3 35.5% 42.2% 2.0 36.8% 44.3% 3.0 40.0% 46.5% 4.5 41% 47% 10 41.2% 47.2%

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obvious longer. This could be due to a low average temperature and low reactivity of our fuel particles. 3.4. The eect of physico-chemical pretreatment The physico-chemical pretreatment of the biomass feedstock includes mechanical grinding and chipping (physical pretreatment), moisture removal or addition and ash removal (chemical pretreatment, as detailed in the literature [10]). Table 4 presents the gas yield with physical pretreatment and the relative increase of gas yield as the particle size of the biomass feed is smaller. The change of gas yield with chemical pretreatment is shown in Table 5. From Table 4, it can be seen that under the xed bed of pyrolysis, the small particle with very close approximation of spherical shape is favorable to gas yield. In Table 5, it can be observed that moisture addition to the biomass particles causes a small increase in gas yield. On the contrary, moisture removal results in a slight decrease, and also, ash removal yields the same result. In the former case, the addition of water could further the gasication reaction of char with the catalytic assistance of the alkali metals inherent in biomass ash. Contrarily, ash removal directly leads to the loss of K and Zn, and thus, makes the gasication reaction weak. 3.5. The eect of heat and mass transfer ability The improvement of heat and mass transfer ability of the reactor was achieved in our experiments by a stirrer combined with a multi-layer stainless steel mesh heated by electrical power. Table 6 gives the corresponding gas yield before and after using the stirrer and mesh. The
Table 4 The eect of physical pretreatment on gas yield Biomass types Rice straw Saw dust Original size 2 10 mm 10 4 2 mm Original gas yield Modied size 35.5% 37.0% 0.132 mm 0.25 mm Modied gas yield 40% 42.2% Relative increase 12.7% 14.0%

Table 5 The eect of chemical pretreatment on gas yield Biomass types Rice straw Sawdust
a

No pretreatment 35.5% 42.2%

Moisture-removing 35.1% ()) 42.0% ())

a

Moisture-adding 35.7% () 42.4% ()

Ash-removing 34.1% ()) 41.5% ())

()) and () represent the total gas yield is decreased or increased, respectively.

Table 6 The eect of heat and mass transfer ability on gas yield Biomass types Rice straw Sawdust Before improvement 35.5% 42.2% After improvement 40.1% 52.3% Relative increase 15% 24.1%

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observed obvious increase could be related to the intensive secondary reactions associated with the tarry components and also with the char gasication reaction. The heat transfer improvement exerts a positive eect on the tarry components decomposition, while the mass transfer improvement favours the char gasication reaction due to the increased contact between the char and steam surfaces (see reactions 1 and 2). 3.6. The eect of cracking reactor The dependence of gas yield on the running temperature of the cracking reactor is given in Table 7. From Table 7, one can observe that the gas yield is strongly inuenced by the temperature of the cracking reactor. For rice straw, if the temperature of the cracking reactor is 600 C, the gas yield is up to 39% in volume, increasing about 9.9%, while increasing to 49% at the temperature of 700 C. After that temperature, a slight increase can be observed further. This can be due to the cracking reaction of the tarry component, usually occurring nearby the temperature of 700 C. This result is very useful for selection of the cracking reactor in an economic point of view. However, it is still necessary to clarify that under other experimental setups and conditions, the cracking reactor may have no obvious inuence on the product gas yield. In our experiments, the vapour phase from the biomass decomposition has insucient temperature level and residence time in the pyrolysis reactor and, thus, almost cannot be subjected to any cracking reaction, while in other setups the tarry components of the vapour phase could be subjected to cracking in the pyrolysis reactor. 3.7. The eect of geometrical conguration of the reactor Based on equivalent volume, two pyrolysis reactors were used for our comparison, one is cylindrical in shape and the other is rectangular in shape. The experimental results are shown in Table 8. It can be found that the rectangular reactor is better than the cylindrical one. The possible reason is that the former reactor has a bigger surface area per unit of volume and thereby strengthens the heat transfer between the biomass particles and the reactor.
Table 7 The eect of cracking reactor on gas yield Biomass types Rice straw Sawdust Cracking reactor 500 C 35.5% 42.2% 600 C 39% 45% 700 C 49% 56.2% 900 C 54% 60.3%

Table 8 The eect of geometrical conguration of the reactor on gas yield Biomass types Rice straw Sawdust Cylindrical 35.5% 42.2% Rectangular 36.1% 43.4% Relative change 1.7% () 2.8% ()

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3.8. The heating value of product gas The heating value of the gas yielded in all the experiments is between 1315 MJ/N m3 , much higher than the data reported by conventional air, even oxygen, gasication, approximately two times in value. This means that pyrolysis gas can be applied well to downstream gas turbine/gas engine combustion for power generation or used as a substitute for civil gas for cooking. When integrated with gas turbine combustion, this high heating value gas can overcome the challenge incurred by combustion of gas from normal gasication processes. In the latter case, more fuel gas is needed in order to operate the turbine with the same turbine inlet temperature, and thus, changes in the turbines conguration are required [3].

4. Concluding remarks The total gas yield of biomass pyrolysis is seriously subjected to the constraints of many operating variables. The increase in reaction temperature can lead to a noticeable increase of gas yield. Long residence time of the volatile phase in the reactor is favourable to gas yield. Two ways of pretreatment appear to have dierent eects on the gas yield, but the physical pretreatment is predominant for the production of gas. The improvement of heat and mass transfer ability of the reactor results in an obvious increase of gas yield, however this increase is still slight as far as the heating rate of the external furnace is concerned. The gas yield is very sensitive to the temperature of the cracking reactor and also appears a little sensitive to the conguration of the pyrolysis reactor. From an economic point of view, the temperature of 700 C for the cracking reactor is thought to be preferable. A rectangular shape of the pyrolysis reactor is advantageous compared to a cylindrical reactor. The catalytic application to the biomass pyrolysis process is expected to have a positive eect, although very unfortunately, due to a time limit, this work still has not been done. Further considerations should be given to investigation of the combined eect of the above mentioned parameters on the product gas yield.

Acknowledgements This work would not have been possible if not for the support from Zhejiang University, China, and the Delft University of Technology. The authors would like to take this opportunity to thank all their colleagues for their great help.

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