Documenti di Didattica
Documenti di Professioni
Documenti di Cultura
1. INTRODUCTION
In recent years, pressures on global environment and energy security have led to an increasing
demand on renewable energy sources and diversification of energy supplies. Among these
resources, biomass could exert an important role, since it is considered a renewable and an
environmentally safe way of providing energy for electricity, heating and cooling (Fernández-
Llorente and Carrasco-García, 2005). The use of biomass aims at increasing overall conversion
Proceedings Venice 2010, Third International Symposium on Energy from Biomass and Waste
Venice, Italy; 8-11 November 2010
2010 by CISA, Environmental Sanitary Engineering Centre, Italy
Venice 2010, Third International Symposium on Energy from Biomass and Waste
efficiency, achieving cost reductions, further reducing the environmental impact and ptimizing
the technologies in different regional conditions.
The main advantage of recovering energy from biomass is the CO2 neutrality of this energy-
production process (Sami et al., 2005; Doshi, 2009). However, this process produces a solid by-
product, namely ash, that has to be environmentally managed. The quantity and quality of ash
produced in biomass combustion are strongly influenced by the characteristics of the type of
biomass (Bridgeman et al., 2007; Masiá et al., 2007) used as well as the type of combustion
technology applied (Olanders and Steenarir, 1995; Rajamma et al., 2010).
Because of their content on nutrients like calcium, potassium and phosphorus and its efficacy
in modification of soil health and crop performance, fly ash has great potentiality in agriculture
(Basu et al., 2009); however other uses have been studied, for example in concrete (Wang and
Baxter, 2007; Wang et al., 2008a; Wang et al., 2008b ). In all of these processes, it is essential to
have a thorough knowledge of the composition before the ash is utilized.
Studies of the chemical composition of wood ash in the past have primarily been restricted to
the elemental composition as the focus was largely on the agricultural use of wood ash, but little
has been said about the formation reactions of the ash during combustion. However, the
problems of ash deposition on heat transfer surfaces in boilers still remain. Even though mineral
matter transformations during coal combustion have been extensively investigated limited
information is available on mineral matter behavior in wood (Olanders and Steenari, 1995).
To understand what occurs during combustion it is essential to investigate what compounds
exist in the ash and what reactions occur in their formation. The present work aims to apply
thermal gravimetric test to bottom and fly ash from four domestic boilers, applying different
technologies to burn pellets and to remove the ash, used to heat water for public buildings
located in population centers. Thermogravimetric analysis (TGA/DTG) and chemical content
have been developed to characterize bottom and fly ash to obtain conclusions about the
combustion process of pellets and possible uses for the ash.
2.1 Materials
2.1.1. Pellets
Pellets used in boilers were all produced at a privately-owned industrial plant in Granada (Spain)
using basically prunning residues from olive trees although other wood waste could be mixed in
the process, for example almond trees, poplars and sawdust.
Chemical analyses of inorganic elements are given in Table 2. The data in the table show that the
ash samples were rich in CaO (values ranging between 43.97 and 64.16%) and that the sum of
SiO2, Al2O3 and Fe2O3 ranged between 11 and 21.21%. Some phosphorous compounds have
been also detected, probably originated mainly from the biomass used (Steenari and Lindqvist,
1999). Calcium is also an important component in wood, and, as might be expected, the CaO
levels in the ash from combustion of the agriculture biomass were higher than those detected
from the combustion of coal or co-combustion of wood and coal with values ranging between
5.73 and 19.59% respectevely (Koukouzas et al., 2009).
On the one hand the presence of certain inorganic elements expressed in the usual way for
fuels, SiO2, Al2O3 and CaO are reported on ash basis to asses ash propensity to slagging and
fouling problems (Suárez-García et al., 2002); on the other hand the presence of SiO2, Al2O3 and
Fe2O3 indicated the possibility of ash exhibiting pozzolanic properties and in consequence their
potential use in concrete should be studied.
Venice 2010, Third International Symposium on Energy from Biomass and Waste
Thermal gravimetric analysis reveals the loss on ignition (LOI) of ash (see Figure 1). It is usually
taken as a measure of the amount of the unburned carbon remaining in the fly ash, is one of the
most significant chemical properties of the samples analysed. In general, total LOI was higher in
the case of fly ash (Table 3) with values similar to other studies (Pastor-Villegas et al., 1999;
Rajamma et al., 2009) except in the case of heating H2 with lower values. In general, low-carbon
ash is required because carbon may interfere with air entrainment by adsorbing entrainment
additives although the carbon content does not always have this effect (Koukozas et al., 2009). In
addition to unburned carbon, the LOI may also partly represent material released from different
minerals in the ash when the material is subjected to the high temperatures associated with LOI
determination (Brown and Dykstra, 1995).
For clues regarding combustion process in domestic heating, the mass loss was measured by a
thermal gravimetric analyzer. Results of the thermogravimetric analysis of the bottom (B-H1, B-
H2, B-H3 and B-H4) and fly (F-H1, F-H2, F-H3 and F-H4) ash samples in air are shown in
Figures 2 and 3. Thermal gravimetric analysis of the ash also reveals two major variations in
weight in both types of ash and for all type of domestic heating, although the percentage of
weight loss was different depending on the ash type and on the source. The initial mass loss was
detected around 400 ºC and the second one occurred in the range of 600-700 ºC. Some studies
have related these results to the presence of organic matter and calcite (Pastor-Villegas et al.,
1999; Vamvuka et al., 2008).
The mass loss observed at temperatures over 400°C was lower than the second one and it has
been found to be due to the decomposition of the organic matter content. This could be due to
volatilisation of unburnt carbon and other organic matter present due to incomplete combustion
of biomass used as domestic heating fuel (Tsukada et al., 2003; Umamaheswaran and Batra,
2008).
The data in Table 3 show percentage of weight loss detected for different types of ash. Weight
loss for bottom ash was lower than that for fly ash except for H2 with similar values; these
results revealed that the presence of organic matter was higher in the fly ash. Lower weight loss
was related to lower percentage of carbon (Table 4); fly ash from heating H3 had the higher
percentage of weight loss (3.5%) corresponding to the higher percentage of C (5.35%); on the
other hand, the lower percentage of weight loss (0.7%) corresponded to bottom ash from heating
H3 with a percentage of carbon.
Other authors have detected weight loss in the range of 300-600 ºC (Rajamma et al., 2009)
although higher percentage values were obtained; for example in the case of cashew nut shell the
weight loss detected in this temperature range was 85%, 28% for bagasse ash, 32% for areca nut
ash (Umamheswaran and Batra, 2008) and 7.1% for straw ash. The presence of organic matter in
ash is related to higher loss on ignition; in fact, although the biomass is burnt under sufficiently
high temperature in the heating process, there is always some inefficiency on carbon conversion
due to kinetic and mass transfer limitations; consequently, the ash contain a certain amount of
organic matter.
Some authors have detected a second mass loss at around 800ºC for fly ash from municipal
waste combustion (Pastor-Villegas et al., 1999; Tsukada et al., 2003; Rajamma, et al., 2009). In
this case the second peak was detected in a slightly lower temperature range, between 600 and
700 ºC (Figures 2 and 3). In this case the weight loss could be mainly attributed to the thermal
decomposition of carbonates, for example CaCO3 (calcite) (Rajamma et al., 2009). Weight loss
in this second peak was higher than the first one, with values higher than 10%, except for
samples from heating H2 (Table 4); these results indicated that ash from heating H1, H3 and H4
contained more calcite compared to H2.
Venice 2010, Third International Symposium on Energy from Biomass and Waste
Fly ash from heating H2 and H3 showed also an initial small mass loss at low temperatures, over
110°C. The initial mass loss observed at this range of temperatures could be due to the
evaporation of water adsorbed by the ash when stored for a period of time after preparation
(Misra et al., 1993).
4. CONCLUSIONS
Chemical analyses of inorganic elements of bottom and fly ash from domestic heating showed a
high percentage of CaO because of the origin of the pellets used, biomass from olive trees and
other agricultural waste. Some propensity to slagging inorganic compounds should be also
detected and the presence of pozzolanic compounds (SiO2, Al2O3 and Fe2O3) indicated the
potential of using ashes in concrete.
Thermal gravimetric analysis revealed loss on ignition in two phases. The first one was
related to organic matter content and the second one to calcite content. Results showed higher
weight loss for fly ash than for bottom ash just like a higher loss on ignition in the second phase.
This result could be explained because of the high percentage of calcite in the ash from the fuels
used.
Complementary studies are necessary to improve combustion efficiency of domestic heating
to reduce the presence of unburned carbon and minerals in the ash that could produce problems
during the heating process. These studies should also evaluate more properties of ash to be used
in the production of concrete.
Venice 2010, Third International Symposium on Energy from Biomass and Waste
ACKNOWLEDGEMENT
This research has been funded by the Innovation and Science Division of the Andalusian
Regional Government (Research Projects P08-RNM-03584 and TIC-02913), the Spanish
Ministry of Science and Innovation (Research Project CTM2009-07199).
REFERENCES
Basu M., Pande M., Bhadoria P.B.S. and Mahapatra S.C. (2009). Potential fly-ash utilization in
agriculture: A global review. Progress in Natural Science 19, 1173-1186.
Bridgeman T.G., Darvell L.I., Jones J.M., Williams P.T., Fahmi R., Bridgwater A.V.,
Barraclough T., Shield I.,Yates N., Thain S.C. and Donnison I.S. (2007). Influence of particle
size on the analytical and chemical properties of two energy groups. Fuel 86, 60–72.
Brown C.R. and Dykstra J. (1995). Systematic errors in the use of loss-on-ignition to measure
unburned carbon in fly ash. Fuel 74, 570-574.
Doshi V., Vuthaluru H.B., Korbee R. and Kiel J.H.A. (2009). Development of a modeling
approach to predict ash formation during co-firing of coal and biomass. Fuel Processing
Technology 90, 1148–1156.
Fernández-Llorente M.J. and Carrasco-García J.E. (2005). Comparing methods for predicting the
sintering of biomass ash in combustion. Fuel 84, 1893–1900.
Koukouzas N., Ward C.R., Papanikolaou D., Li Z. And Ketikidis C. (2009) Quantitative
evaluation of minerals in fly ashes of biomass, coal and biomass-coal mixture derived from
circulating fluidised bed combustion techonology. Journal of Hazardous Materials 169, 100-
107.
Masiá A.A.T., Buhre B.J.P., Gupta R.P.and Wall T.F. (2007). Use of TMA to predict deposition
behavior of biomass fuels. Fuel 86, 2446-2456.
Olanders B.and Steenari B-M. (1995). Characterization of ashes from wood and straw. Biomass
and Bioenergy 8, 105-115.
Pastor-Villegas J., Gómez-Serrano V., Durán-Valle C.J. and Higes-Rolando F.J. (1999).
Chemical study of extracted rockrose and of chars and activated carbons prepared at different
temperaturas. Journal of Analytical and Applied Pyrolysis 50, 1-16.
Rajamma R., Ball R.J., Tarelho L.A.C., Allen G.C., Labrincha J.A.and Ferreira V.M. (2009).
Characterisation and use of biomass fly ash in cement-based materials. Journal of Hazardous
Materials 172, 1049-1060
Sami M., Annamalai K. and Wooldrigde M. (2001). Co-firing of coal and biomass fuel blends.
Progress in Energy and Combustion Science 27, 171–214.
Steenari B.M. and Lindqvist O. (1999). Fly ash characteristics in co-combustion of wood with
coal, oil or peat. Fuel 78, 479-488.
Suárez-García F., Martínez-Alonso A., Fernández-Llorente M. and Tascón J.M.D. (2002).
Inorganic matter characterization in vegetable biomass feedstocks. Fuel 81, 1161-1169.
Tsukada M. , Yamada H. and Kamiya H. (2003). Analysis of biomass combustion ash behavior
at elevated temperaturas. Advanced Powder Technology 14, 707-717.
Umamaheswaran K., and Batra V.S. (2008). Physico-chemical characterisation of Indian
biomass ashes. Fuel 87, 628–638.
Vamvuka D., Zografos D. and Alevizos G. (2008). Control methods for mitigating biomass ash
Venice 2010, Third International Symposium on Energy from Biomass and Waste