Effect of biomass on temperatures of sintering and initial deformation of
Sintering temperatures and the initial deformation temperatures of ashes from Turkish Elbistan lignite,and biomass species such as hazelnut shell and rice husk were investigated up to 1450 ?C by Heating Microscope Technique. Sintering temperatures were found 1300?C, 1269?C, and 1320 ?C for hazelnut shell, rice husk, and lignite, respectively, while the intial deformation while the initial deformation temperatures were>1450?C,1370?C, and>1450?C.Lignite/biomass blends were prepared by adding of biomass into coal in the ratios of 5 or10 wt.%, and then effects of biomass presence on sintering temperature and the initial deformation tem-perature were tested. It was determined that the addition of potassium-rich hazelnut shell reduced the sintering temperatures to 919?C and 730 ?C for the blends of 5 and 10 wt.%, respectively. Also, initial defor-mation temperature dropped to 788 ?C in case of the blend of 10 wt.%. Such a big antagonistic in?uence of hazelnut shell on the thermal behaviour of ash is
attributed to the interaction of potassium from biomass with silicon compounds found in mineral matter of lignite. In addition, concentration of CaO may be another reason for this. On the other hand, the presence of rice husk showed limited effect on the sinter-ing temperature as well the initial deformation temperature.
Co-?ring of coal with biomass is of great interest owing to sev-eral factors such
as controlling of carbon dioxide emissions, mak-ing use of the energy potential of biomass, ef?cient removal of residues, and environmental restrictions on land?ll areas, etc.
However, co-utilization of biomass in the existing combustion systems often leads to serious problems such as deactivation of SCR (selective catalytic reduction) catalysts, slagging, fouling, and clinker formation. These deposit formations are generally attributed to the high alkali content of the biomass material. Some biomass, especially the annual biomass has a high alkali content, which may form low melting point ash during combustion. The low melting ash constituents can induce formation of agglomerates, in addition to deposition and corrosion. In case of fluidized bed system, accumulation of the agglomerates may lead to loss of fluidization (defluidization) and unscheduled shutdown of the plant. Formation of melts, which are responsible for the formation of agglomerates, depends on the type of fuel. The formation of low temperature eutectics is considered as the initiator of agglomerates.
Four different fusion characteristics such as initial deformation temperature,
softening temperature, hemispherical temperature,and fluid temperature are taken into account by ASTM fusion test method to evaluate the fusion characteristics of an ash sample. However, it has been observed in Exxon0s pilot plant gasification process that agglomerates are formed during operation several hundred degrees below the initial deformation temperatures of coal ash tested by ASTM procedure.
Agglomeration of ash may be influenced by various parameters such as the inorganic composition, the particle size and size distribution,the bed temperature and atmosphere under which the operation is conducted. Therefore, the determination of the initial deformation temperature may be a predictor to foresee the extent of the ash related problems.
Accordingly, some fouling or slagging indices are used to predict extent to which a particular fuel will slag or foul upon utiliza- tion. These indices are derived from arious techniques which in- clude the ash fusibility temperature (AFT) test, oxide analysis and ash viscosity measurements. The ash fusibility test has been the most accepted method of assessing whether an ash will foul or slag on the heat transfer surfaces of boilers.
There are techniques through which the melting point of bio- mass ash can be raised to reduce the deposition problems. These are use of additives, use of alternative bed materials in the case of ?uidized bed combustion, and co-?ring with other fuels,
e.g. coals. Additives which can raise the softening temperature of ash are kaolin, ceramic, alumina, calcium oxide, magnesium oxide and dolomite.
Turkey has a great deal of potential for agricultural waste bio-mass species. For an instance, about 70% of world hazelnut production is carried out in this country. So its woody shells present an important source of energy. However, alkali content of its ash is quite high.
On the other hand, approximately 90% of ash from rice husk is consisted of acidic SiO2 so rice husk can be given just a different type of biomass species regarding the alkali/acidic constituents in ash.
Besides, lignitic coals are the most important national primary fossil fuels of Turkey that nearly 8% of annual world lignite con- sumption is performed in Turkey. Among these lignites, Elbistan lignite, which has a low coali?cation degree with an
age of Plio- cene, has the highest deposits and it is used in power stations. Its mineral matter content is 37.5%, and the major constituent in bot- tom ash is CaO . Original lignite has some inorganic phases such as calcite (27.4%), quartz (4.8%),
illite (2.6%), and pyrite (1.6%) .
The aim of this study is to compare the ash-related characteris- tics of hazelnut shell, rice husk, and Elbistan lignite, and to inves- tigate effects of the presence of these biomass materials on the sintering temperature and the initial deformation temperature of lignite ash during co-combustion.
2. Material and methods
Elbistan lignite, hazelnut shell, and rice husk were first air-dried in laboratory for two weeks, representative samples were taken,and then particle sizes were reduced to 60 mesh (-0.25 mm).Proximate analyses and the calorific value measurements were carried out according to the related ASTM standards. Ultimate analyses were conducted by a Eurovector EuroEA3000 model elemental analyzer.Major biomass ingredients such as holocellulosics (holocellulosics+ celluloses), lignin, extractives, and a-cellulose in hazelnut shell and rice husk were determined by the following analytical procedures. Extractive components were determined according to ASTM D1105. The bulks remaining after alcohol–benzene extractions were used to obtain
the holocellulosics by means of NaClO2 extraction procedure. The lignin contents of the samples were found according to the method of van Soest . a-Cellulose contents were determined according to TAPPI T203 om-88 standard. Lignite/biomass blends were prepared by properly mixing of ground (-0.25 mm) Elbistan lignite by hazelnut shell or rice husk with the same particle size. The contributions of biomass in these blends were 5 and 10 wt.%. Ashing of lignite was performed at 750 ?, while
biomass species were ashed at 600? according to ASTM D3174 and ASTM E1755
standards, respectively. Ash of lignite/biomass blends was obtained at 750 ?.
Analyses of ashes were carried out by XRF and XRD techniques. For this purpose, Rigaku Primus II XRF, and Panaltic X0Pert PRO (XRD) were used. SEM images of ashes were obtained using a JoelTM Model JSM-T330 operated at 25 kV and linked with an energy dispersive (EDS) attachment. Heating Microscope Technique was applied in order to investigate the thermal behavior of the ashes. For this purpose, Leitz Heating Microscope model 2004 was used. The pretreatment of the ashes for this procedure includes grinding to 63 lm, moisture fixation at about 4–5 wt.%, and
tabletting to form cubic patterns with dimensions of 2 .22 mm. Cubic patterns were then placed on an alumina plate and heated up to 1450 ?. Variations in the size of
the sample at a heating rate of 40 ?/min were monitored, and evaluated according to
DIN 51730. Burning characteristics of the original fuel samples were investigated by
non-isothermal thermogravimetric analysis method using a Shimadzu TG 41 thermal analyzer with a cylindrical- alumina crucible. Initial weight of the samples was 40 mg, temperature was raised from ambient to 900? by a heating rate of 40 ?/min under
dry air flow of 40 mL/min, and then enough hold time was allowed at this temperature to get the fixed final weights. All the experiments were repeated three times to check the reproducibility of the results, and the mean values were used provided that the deviations were within 5%.
3. Results and discussion
Table 1 shows the results of the proximate and ultimate analyses, and the calorific value for both lignite and biomass samples. Although the lowest fixed carbon belongs to hazelnut shell, it has the highest calorific value. This predicts that volatile matter of this biomass is rich in combustible constituents and it makes important contribution to the calorific value. As to ash contents, hazelnut shell has a different situation that its ash content is considerably lower than the other samples. High mineral matter content in Elbistan lignite led to formation of high content of ash. Although its C content is higher than those of biomass species on dry-ash-free basis, its actual C content on original basis and consequently the calorific value is considerably lower. Major organic ingredients of the biomass species are given in Table 2. Hazelnut shell which has a woody structure is rich in lignin. Whereas, holocellulosics showing high reactivity during combustion or other thermal conversion processes such as pyrolysis and gasification are the most important ingredients of rice husk. Fig. 1 illustrates the thermogravimetric analysis curves through which it is possible to see that they have different burning characteristics. Biomass samples are highly reactive at low temperatures, and accordingly important mass losses from these samples took place even before 300 ?. Most of the biomass
matrix is comprised of oxygen containing polymers of cellulose, holocellulosics, and lignin which are linked together with weak ether bonds with bond energies between 380 and 420 kJ/mol. These bonds are sensitive to heat even at low temperatures, and extensive decomposition took place during the initial stages of the thermal decomposition。
Analysis results of the samples
Major organic ingredients of the biomass samples (%, dry).