Joyce, J.A. et al. Proc. Aust. Soc. Sugar Cane Technol., Vol.

28: 2006 __________________________________________________________________________

PRESSURISED GASIFICATION OF CANE WASTES By J.A. JOYCE1, T.F. DIXON2 and J. DA COSTA3 University of Qld (formerly of Sugar Research Institute) Corresponding author jjoyce@easynet.net.au 2 Tarong Energy Corporation Limited (formerly of Sugar Research Institute) 3 University of Qld, Division of Chem. Eng.
1

KEYWORDS: Gasification, Cogeneration, Bagasse, Cane Trash, Char, Ash.

Abstract THIS PAPER reports the outcomes from a PhD study into the pressurised flow gasification of sugarcane processing wastes (bagasse and cane harvesting trash). Pressurised gasification has been proposed as a means to improve the cogeneration cycle efficiency of sugarcane factories. The primary objective of this study was to determine the gasification reactivity of bagasse and cane trash, to provide data for the design of commercial pressurised gasifiers. For design purposes, gasification reactivity is defined by (a) the amount of initial conversion by pyrolysis and (b) the reaction rate of the resulting char residual. In this study these two parameters were measured by a combination of conventional techniques and in a purpose designed reactor. The char and ash residues were also characterised by optical microscope, electron microscope, gas adsorption and x-ray analytical techniques, to gain a better understanding of the processes occurring during gasification. The key findings were: 1. Pressurised gasification processes are at a significant disadvantage to un-pressurised designs, due to significant inhibition of the initial pyrolysis (fuel conversion) step at elevated pressures. 2. Within the range of temperatures and residence times expected in commercial biomass gasifiers, the rate of char gasification was so low as to not contribute significantly to overall fuel conversion. 3. Char gasification showed a significant time dependent loss of reactivity in entrained flow experiments, which was attributed to coke formation and trapping of carbonaceous material by the silicate species derived from the original biomass. The findings highlight significant issues with regards to proper fuel conversion in biomass gasifiers, particularly pressurised systems. The implications of the findings to the selection and design of advanced cogeneration cycles are discussed. Introduction Hobson and Dixon (1998) described the potential for biomass integrated gasification combined cycle cogeneration to enhance the cogeneration efficiency of the Australian sugar industry. This was further expanded to include implementation issues by Joyce et al. (1999). Progress in the development of a suitable pressurised biomass gasification technology for the Australian industry was described by Hobson et al. (2003). The work reported here is one component of the overall project described by Hobson and his coworkers, i.e. a PhD study into the gasification reactivity of sugarcane processing wastes
419

Joyce, J.A. et al. Proc. Aust. Soc. Sugar Cane Technol., Vol. 28: 2006 __________________________________________________________________________

(bagasse and cane harvesting trash) under pressurised entrained flow conditions. The overall objective of the study was to provide data for the design of commercial pressurised gasifiers. Hobson and Dixon (1998) explained the reasoning behind pressurised gasification, i.e. for direct firing of gas turbines with compression ratios up to 18:1. Un-pressurised gasification processes require compression of the product gas, which results in gas handling issues and efficiency penalties. Figure 1 outlines the concept of biomass gasification at the core of the investigation. After initial drying, there are two steps to biomass gasification; pyrolysis (which is very rapid) and gasification of the residual char (which is generally 1001000 times slower than pyrolysis). For gasifier design purposes, fuel reactivity is best defined by (a) the amount of initial conversion by pyrolysis (circled in Figure 1) and (b) the reaction rate of the resulting char residual (underlined).
Oxygen source Drying - Devolatilisation / Pyrolysis Partial Volatile Combustion

Gases (H2O, CO, CO2, CxHyOz, H2)

25-90% 1-20%

Oils/Tars

Feedstock

5-50%

Soot

Char

Ash

Fig. 1The steps in biomass gasification.

The conditions of interest in the study were those typically proposed for pressurised biomass gasification; namely pressures up to 20 barg and temperatures in the range of 600 to 900oC. The study also focussed on reactivity under entrained flow conditions. In simple terms, this means conditions whereby the fuel particles are being transported by the reacting gases, as opposed to being relatively fixed in space with a reactant gas flowing past. Entrained flow is representative of the single pass transport reactors and circulating fluidised bed processes typically proposed for large scale gasification. Fuel characteristics Table 1 outlines of the typical fuel characteristics of cane wastes and three other fuels for comparison. The characteristics of interest for cane wastes are the relatively high ash content and the high proportion of silica in ash. Fuel conversion Fuel conversions in conventional bagasse boilers are in the range of 9098% for incineration processes and efficient combustion respectively. Coal fired utility boilers target fuel conversions in excess of 99% (Stultz and Kitto, 1992). In this study fuel conversions in excess of 98% were considered desirable. Fuel conversion is commonly described in terms of the carbon-in-ash value; where low carbon-in-ash values correspond to higher fuel conversions. A fuel conversion of 98% corresponds to carbon-in-ash values of 11 for 15% ash fuel (e.g. cane trash) and 28% for a 5% ash fuel (e.g. bagasse).
420

Joyce, J.A. et al. Proc. Aust. Soc. Sugar Cane Technol., Vol. 28: 2006 __________________________________________________________________________

Literature Published data on the pressurised gasification of biomass, let alone bagasse or cane trash was all but non-existent when the project commenced in 1998. During the intervening period, several useful works were published. Readers are referred in particular to Antal and Gronli (2003), a review paper summarising knowledge of the effect of pressure, moisture content and gas flow on char yields for a wide variety of biomass fuels including bagasse. They focussed on application of the knowledge to charcoal production.
Table 1Cane waste fuel characteristics (adapted from Joyce, 2005).
Characteristic Moisture Silica%ash Total ash C H O S+N+Cl etc. Higher heating value Volatiles by proximate analysis Basis Wt% as delivered Wt% Wt% dry MJ/kg dry basis Wt% dry Bagasse 4552 50 80 26 47 6 42 0.5 19.319.6 83 Cane trash 2560 ~60* 415 44 5 39 1.0 16.0 18.8 82
** *

Hard woods 4060 2 15 0.31.0 50 6 43 0.25 ~19.5 8083

Soft woods 3545 30 40 0.10.4 50 6 43 0.5 ~20.0 81

Peat 5060 ~25 48 54 6 3235 1.52.5 ~24.5 7378

* More variable than bagasse as this depends on ambient weather conditions and technique used to recover the trash. ** Higher numbers indicate higher levels of soil contamination.

Mochidzuki et al. (2002). Another study focussed on charcoal from a variety of biomass feedstocks, but with application to the prediction of char yield under pressurised conditions. Henrich and Weirich (2002) described the selection and experimental investigation of a two-step pyrolysis/gasification process for grass-like biomass materials with high ash contents. The biomass is initially liquefied by fast pyrolysis at 500C under atmospheric pressure to maximise conversion. Then a dense slurry is prepared from the pyrolysis oil and residual char for firing in a slagging entrained flow gasifier operating at high temperature and pressure. Gabra et al. (2001a) and Gabra et al. (2001b) discussed entrained flow gasification of sugarcane bagasse and cane trash, in a cyclone gasifier under atmospheric conditions. Overall fuel conversions were low (less than 8595% on a dry ash free basis). It is one of the few studies that has examined the liberation of inorganic species from cane wastes under entrained flow gasification conditions. Methods The two fuel reactivity parameters were measured by a combination of conventional techniques and in a purpose designed reactor. In addition, the char and ash residues were also characterised by optical microscope, electron microscope, gas adsorption and x-ray spectroscopy techniques, to gain a better understanding of the processes occurring during gasification.
421

Joyce, J.A. et al. Proc. Aust. Soc. Sugar Cane Technol., Vol. 28: 2006 __________________________________________________________________________

In situ thermogravimetric analysis Char preparation conditions, i.e. time temperature history and reaction environment, are widely reported to impact on the gasification reactivity of residual chars from pyrolysis (Reed, 2002). Hence, an experimental technique that avoided the cooling and handling of chars prior to gasification was attempted. The Thermogravimetric Analyser (TGA) is a very common experimental apparatus for characterising thermal reaction rates. The measurements are achieved by directly monitoring the weight loss from a sample, which is suspended under a microbalance in a temperature controlled chamber that can be flushed with preheated reactant gases. Samples of the raw bagasse and cane trash were loaded into specially designed TGA sample baskets. With the reaction zone and reactant gas flow preheated to the experiment temperature, the sample basket was rapidly lowered into the reaction chamber where it pyrolysed to char which was then gasified. The sample temperature history in a TGA is not measurable, because a thermocouple cannot be placed in physical contact with the sample. Hence the sample heating rate was estimated by calculation. This was 35oC/s; which meant that, for the first 150 to 200 seconds of a typical experiment, the sample was still heating to the target reaction temperature. A brief pressurised TGA study was completed by staff at HRL Ltd., Mulgrave, Melbourne, on sub-samples of the standard materials used throughout the project. Both isothermal (constant temperature) and temperature ramped experiments were performed. WMR/TGA The wire mesh reactor (WMR) technique involves sandwiching a small sample (typically less than 25 mg) between two pieces of fine wire mesh, which is then electrically heated in a controlled manner. Aiman (1989) described the use of the technique to characterise the pyrolysis behaviour of bagasse under the rapid heating conditions expected in a suspension fired boiler, i.e. ~1000oC/s. Similar heating rates are expected in a cane waste gasifier (in comparison to ~4oC/s for the in situ TGA technique). WMR can be used to generate residual chars for subsequent reaction in a TGA. Roberts and Harris (2003) compared this technique to other methods for predicting real world gasification reactivity. A brief pressurised WMT/TGA study was completed at CSIROs Energy Technology division Pinjarra Hills laboratory, using reference samples collected for the project. PCG reactor It was demonstrated in the study that bagasse and cane trash are very difficult to sample representatively, particularly for small samples. Hence, the accuracy of the WMR/TGA and TGA techniques is limited by the sample sizes that these techniques can accommodate, that is less than 100 milligrams. In addition the two TGA techniques do not react the residual chars under entrained flow conditions. As a result a reactor was custom designed to achieve the pressurised entrained flow gasification of gram sized samples at a constant known temperature. It took six months to complete the design, which included a unique high temperature coupling arrangement (described in Nix and Joyce, 2003). The screw couplings allowed the reactor to be pulled apart to allow the char residual to be recovered for weighing and analysis. The pressurised circulating gasifier (PCG) is illustrated in Figure 2. The apparatus was installed at the Sugar Research Institute in Mackay in 2000. The basic principle involves: (a) operation of the pressurised reactor inside an electric furnace to ensure a known reaction temperature;
422

Joyce, J.A. et al. Proc. Aust. Soc. Sugar Cane Technol., Vol. 28: 2006 __________________________________________________________________________

(b) constant preheated reactant gas flow (high purity CO2/N2 mixtures) into the reactor and discharge via a 7 micron sintered stainless steel filter; (c) injection of the raw sample followed by recirculation in the reactor until the experiment is completed; (d) monitoring of the CO concentration in the gas discharge as a direct measure of carbon dioxide gasification rate, i.e. via the relationship C + CO2 ! 2 CO.

Gas outlet to analyser Sample injection Recycle loop Char recycle Preheated gas Adjustable inlet nozzle which drives gas recycle loop. Gas heat exchanger and pre-heater

Fig. 2The pressurised circulating gasifier apparatus. External electric furnace housing not shown.

Char characterisation techniques To better understand the results of the reactivity experiments, the residual chars from the experiments were examined by optical microscope and a number of sophisticated analytical techniques. These were: " Scanning electron microscopy and Energy Dispersive Spectroscopy (SEM/EDS) " Transmission electron microscopy Energy Dispersive Spectroscopy (TEM/EDS) " Nitrogen gas adsorption pore analysis " X-ray photo electron spectroscopy (XPS)
423

Joyce, J.A. et al. Proc. Aust. Soc. Sugar Cane Technol., Vol. 28: 2006 __________________________________________________________________________

Results and discussion Char yield Char yield is the complement of volatile yield (fuel conversion) for the initial pyrolysis step in gasification. The experimental results for char yield varied from 4 wt% (dry ash free basis) to 40 wt%, in response to changes in temperature, pressure, initial ash content, relative gas flow rates past the samples and heating rate. Obviously this range is very significant with regards to gasifier design as it corresponds to a range of 60 to 96% initial fuel conversion (prior to gasification of the char residue). The char yield results from the experiments were used to formulate a char yield model. The model was based on an understanding of the influences on char yield derived from a literature survey and refined using multivariate parameter fitting software. The model equation developed was: Char yield (% daf) = 100 x (0.1043 x 573.15/T + 0.0804 log (P+I) + 0.6597 Ash 0.2037 log (Char Environment Factor) + 0.2301)

where T is the absolute temperature in Kelvin, P is the pressure in barg, Ash is the fraction of ash in the sample on a dry basis and the Char Environment Factor (CEF) is a parameter characterising the heating rate, mass transfer conditions and residence time of the experiment. Values of CEF for fully entrained flow conditions are in the range 3060. Values for charcoal processes are close to one. The means to determine CEF is more fully explained in Joyce (2005). When the model predictions where compared against three additional experimental results and 23 data sets from literature, a correlation coefficient (R2) of 0.93 and standard error of prediction of 3.2 units of char yield resulted. The key findings from the modelling exercise were: " Char environment factor, within the experimental range of 160 units, is the primary influence on char yield (contribution to the range in predicted char yield was 36 units). This influence diminishes at values of CEF above 20, due to the log form of the relationship. " Pressures in the range 120 barg have a significant positive effect on char yield (contribution to the range in predicted char yield was 8 units). The effect of pressure rapidly diminishes once the pressure exceeds 5 barg, due to the log form of the relationship. " Ash content, within the range 515 wt%, has a significant positive influence on char yield (contribution to the range in predicted char yield was 7 units). " For the temperature range examined (i.e. 600900oC), temperature has a relatively small negative influence on char yield (contribution to the range in predicted char yield was 2 units). Char reaction rate Table 2 summarises the experimental results for initial char reactivity against chars from a typical low reactivity high rank coal fuel and a typical biomass fuel using the PCG. The comparison places the reactivity of the chars between that of woody biomass chars and a high rank coal chars. The experimental data showed a significant spread between the three methods used and, in the case of the PCG experiments, a rapid (roughly ten-fold) loss of rate with reaction time.
424

Joyce, J.A. et al. Proc. Aust. Soc. Sugar Cane Technol., Vol. 28: 2006 __________________________________________________________________________

Subsequent analysis attributed the poor reactivity of the chars to low surface area for reaction, the presence of an un-reactive coke (soot) coating on the chars and, at high levels of conversion, trapping of carbon in the silicate ash structures. This is discussed further in a subsequent section.
Table 2Char CO2 gasification rate results (wt% per minute) in comparison to literature.
Details 800oC This work High rank coal Bagasse Cane trash Softwood 0.42 17 30 Literature 0.06 n/a 13 210 90 850oC This work Literature 0.12 n/a

Chars can also be gasified by steam ( C + H2O ! CO + H2 ), at rates typically 35 times greater than those commonly measured for CO2. However, this was not examined in the study. It is apparent from the results that even when taking into account co-conversion by steam gasification, char conversions of 5090% (necessary to achieve overall fuel conversion in excess of 98%) may require tens of minutes at temperatures under 900oC. Temperatures beyond 900oC are typically avoided because the ash particles can become sticky and create serious handling problems inside the gasifier. An alternative is temperatures in excess of 1200oC, where the ash can handled a molten slag, but this presents materials challenges. Char analysisAsh transformations and carbon trapping The dominant feature observed in the chars was the silica backbone that was left intact after conversion of the bulk of the organic matter, despite having been exposed to high temperatures for long periods and circulated at velocities in excess of 4 m/s. Agglomerated carbonaceous masses were observed attached to the plant cell residuals; suggesting that coke agglomerates (or their precursors) had either been captured by the plant cell structures, or that these had provided an initiation site for their formation. Similar coke deposits have been described by other researchers. Separate ash particles were not generally evident in the char samples. In some instances these may have been the condensation sites of the isolated agglomerates that were present; in other instances these may have become attached to the silica structures. XPS and EDS analysis confirmed that all surfaces in the samples were not only coated with a layer of carbon, but that some carbon had also been absorbed into the ash matrix, thereby isolating it from reaction with CO2. The key findings of the char analysis are summarised in Table 3. Conclusions The key findings and conclusions of the work were : " The best way to maximise conversion (minimise char yield) in the first step of gasification is to disperse and transport the fuel particles under highly turbulent flow conditions (i.e. entrained flow conditions) at low pressures and high temperatures. Measures to increase heating rate (by pre-drying and/or size reducing the feedstock) and to minimise ash content (by
425

Joyce, J.A. et al. Proc. Aust. Soc. Sugar Cane Technol., Vol. 28: 2006 __________________________________________________________________________

"

"

eliminating soil contamination) will also assist. Under such conditions initial fuel conversions in excess of 96% should be readily achievable; thus leaving less char residual to deal with subsequently. Within the range of temperatures (<900oC) and the residence times expected in commercial biomass gasifiers (less than minutes), the rate of cane waste char gasification is so low as to not contribute significantly to overall fuel conversion. Char gasification rate showed a time dependent decrease in the entrained flow experiments. This was attributed to coke formation on the char surface, followed by carbon trapping in the ash matrix at high levels of conversion. Both findings are significant contributions from this work, because they highlight key mechanisms that may hinder fuel conversion in biomass gasifiers.

Table 3Summary of observations from the char analysis.

Sample details Image Observations Uniform glassy carbon coating over a silicate backbone. The coating shows signs of shrinkage, which suggests a glass or molten state was present prior to cooling. TEM analysis determined this to be non-crystalline carbon (not graphitic). Char surface appears nonporous and gas adsorption analysis confirmed this to be true even at the microporous level. 28wt% carbon in ash by XPS analysis of a crushed sample. Sample had a low porosity / 2 surface area (<100 m /g). SEM/EDS and TEM/EDS analysis indicated a complete surface covering with carbonaceous matter and intimate mixing of silicates and carbon below the surface.

Optical microscope scope image of a char from inert pyrolysis of bagasse in a stagnant atmosphere at 20 Barg, 600oC.

1 mm
Vascular residual with agglomerated masses attached

Char from pressurised gasification of cane trash in 50% CO2/N2 o at 800 C. 98% fuel conversion.

426

Joyce, J.A. et al. Proc. Aust. Soc. Sugar Cane Technol., Vol. 28: 2006 __________________________________________________________________________
Sample details Image Observations

Sample details as above. Plant rind (outer stalk) residual.

A common structure present even at high levels of conversion. The dark spots are cane stalk silica cells. However, EDS analysis indicated they had carbon and other inorganics absorbed into them during gasification.

Ashed sample from cane trash gasified in 50 vol% CO2 at 750oC Nominal 100% conversion.

1 mm

Carbonaceous deposits were clearly visible in some ash particles. This is unexpected given that this ash sample was prepared by oxidation in a muffle furnace in air for 6 hours o at 600 C. Total of 2 wt% carbon in ash. SEM/EDS, TEM/EDS and XPS analysis confirmed that iron, aluminium and other metals from the within the plant cells and soil particles migrated into the clear amorphous silica to form coloured crystalline silicates during gasification. These silicates were found to be mesoporous and had absorbed carbon compounds into these pores. Subsequent sintering trapped the carbon deposits.

Close up of selected material from an ash sample.

1 mm

This work has provided an overall picture of how fuel conversion progresses during the pressurised entrained flow gasification of sugarcane wastes. It has also highlighted the significance of silicate chemistry in the thermo-chemical conversion of these materials. Such findings may also have relevance to any process that aims to chemically convert bagasse or cane trash (such those conducted in bio-refining). Implications for advanced cogeneration cycle designs using cane processing waste fuels One of the key outcomes of the study is that pressurised gasification significantly depresses the initial step of fuel conversion (pyrolysis), which cannot be readily compensated for by the char gasification step. This suggests that pressure conditions should be avoided for at least the first stage of the fuel conversion process. Alternatively, a growing number of proposed processes aim to convert residual char by combustion rather than gasification, to circumvent the limitation imposed by poor char gasification rates.
427

Joyce, J.A. et al. Proc. Aust. Soc. Sugar Cane Technol., Vol. 28: 2006 __________________________________________________________________________

Examples include pressurised fluidised bed combustion (PFBC) which has been extensively developed for coal firing, air segregated gasification systems (where the gasification air is introduced to contact with char rather than the biomass feed) and direct biomass fired turbine systems. Waste char combustion is also quite feasible in sugar factories, where existing boilers can be readily adapted to co-firing char. Finally, an alternative to pressurised cycles as a means to reduce gas volumes, equipment sizes and gas cleaning demands, is oxygen blowing (or oxygen-enriched air blowing), instead of air blowing. This adds additional complication and hence expense to the design, but is a popular approach in the fields of coal gasification and synthesis gas production. Acknowledgements Funding was provided for this work by Stanwell Corporation Ltd., Queensland Department of Mines and Energy, Sugar Research Institute and the Australian Research council and is gratefully acknowledged. The authors would also like particularly to acknowledge to the contributions made by the following people: Dr Jamie Riches for performing the SEM/EDS investigations reported in this work. Mr Keith Nix of Nixenco Ltd. for his contributions to the design of the pressurised reactor developed specifically for the work. Dr Barry Wood for substantial assistance provided in performing the XPS study. Dr David Harris and Dr Daniel Roberts of the CSIRO Energy Division, for arranging the WMR/TGA experiments reported in this work. Dr John Barry for performing the TEM/EDS investigations reported in this work. Our colleagues in the department of Chemical engineering, including Mr Steven Coombs, Mr David Page, Mr Luke Matthew, Mr Chaoqing Lu, Ms Sharon Matheson and many others, who provided practical assistance and academic input. REFERENCES Aiman, S. (1989). The Kinetics of Bagasse Pyrolysis. Department of Chemical Engineering. Sydney, University of New South Wales, Sydney. Antal, M.J.J. and Gronli, M.G. (2003). The art, science, and technology of charcoal production. Ind. Eng. Chem. Res., 42: 16191640. Gabra, M., Pettersson, E., Backman, R. and Kjellstrom, B. (2001a). Evaluation of cyclone gasifier performance for gasification of sugar cane residuePart 1: gasification of bagasse. Biomass and Bioenergy, 21: 351369. Gabra, M., Pettersson, E., Backman, R. and Kjellstrom, B. (2001b). Evaluation of cyclone gasifier performance for gasification of sugar cane residuePart 2: gasification of cane trash. Biomass and Bioenergy, 21: 371380. Henrich, E. and Weirich, F. (2002). Pressurised Entrained flow gasifiers for biomass. International Conference on Incineration & Thermal Treatment Technologies, New Orleans, Louisiana, University of Maryland. Hobson, P. and Dixon, T.F. (1998). Gasification technology prospects for large-scale, high-efficiency cogeneration in the Australian sugar industry. Proc. Aust. Soc. Sugar Cane Technol., 20: 19. Hobson, P.A., Dixon, T.F., Wheeler, C. and Lindsay, N. (2003). Progress in the development of bagasse gasification technology for increased cogeneration in the Australian Sugar Industry. Proc. Aust. Soc. Sugar Cane Technol., 25: (CD-ROM).
428

Joyce, J.A. et al. Proc. Aust. Soc. Sugar Cane Technol., Vol. 28: 2006 __________________________________________________________________________

Joyce, J.A. (2005). Pressurised Entrained Flow Gasification of Sugar Cane Wastes for Cogeneration (PhD thesis). Division of Chemical Engineering in the School of Engineering, University of Qld. Joyce, J.A., Hobson, P.A., Dixon, T.F. and Mason, V. (1999). Gasification technology for large scale cogeneration in the Australian sugar industry. Proc. Intl. Soc. Sugar Cane Technol., 23. Mochidzuki, K., Paredes, L.S. and Antal, J.M.J. (2002). Flash Carbonisation of Biomass. AIChE 2002 Annual Meeting. Reactor Engineering for Biomass Feedstocks, Indianapolis. Nix, K.J. and Joyce, J.A. (2003). Couplings for high pressure and temperature to AS1210. Operating Pressure Equipment. Seventh International Conference, Sydney, Australia, The Institute of Materials Engineering Australasia Ltd and The Welding Technology Institute of Australia: 11. Reed, T.B. (2002). Encyclopaedia of Biomass Thermal Conversion. The principles and technology of pyrolysis, gasification & combustion. Boulder, Colorado, USA, Biomass Energy Foundation. Roberts, D. and Harris, D. (2003). The role of bench-scale reactivity data in the assessment of coals for use in gasification. Twelfth International Conference on Coal Science, Cairns, Australia: 10. Stultz, S.C. and Kitto, J.B. Ed. (1992). Steam Its Generation and Use. Barberton, Ohio, USA, The Babcock and Wilcox Company.

429