Devolatilization and Combustion Kinetics of Low-Rank Coal Blends from Dynamic Measurements D. Vamvuka,* E. Kastanaki, and M. Lasithiotakis Department of Mineral Resources Engineering, Technical University of Crete, Chania 73100, Greece The aim of this work was to investigate the devolatilization and combustion behavior of some low-rank coals and their blends to gather data useful for the development of the coprocessing of these fuels. Nonisothermal thermogravimetry experiments were carried out in inert and air atmospheres, over the temperature range of 25-850 °C, at a heating rate of 20 °C/min, and with a material particle size of -100 μm. Four blending ratios were used. The samples presented similar thermochemical reactivities. The differential thermogravimetric data for devolatilization were fitted successfully to an independent, first-order parallel reactions model, while those for combustion were fitted to a power law model. Blending did not cause any significant interactions during devolatilization in the solid phase, so that the thermal conversion of blends could be sufficiently predicted based on the thermogravimetric data of the individual fuels. However, this was not true in the case of char combustion. Introduction The rational use of coals is of most importance because this energy source is widely distributed around the world. Brown coals constitute the major energy resource in Greece. Of the 6.7 billion tons of proven reserves, 3.85 billion tons are mineable, while indicated reserves amount to 1.6 billion tons and inferred reserves are estimated at 2.3 billion tons. The annual lignite production is over 63.5 million tons, which makes Greece the second-largest lignite producer in the Eu- ropean Community market. 1 This amount covers 70% of the demand for electricity production; however, it is characterized by high ash contents (30-50%), which results in a lower availability and a higher running cost of the plants as well as in environmental pollution. A key to the confident use of lower quality coals is probably blending. Coals can be blended to provide a fuel that possesses better combustion properties and behavior than those of the component coals by them- selves. They are also blended to help solve existing problems at power stations, improve boiler performance, meet emission limits, and reduce costs. On the other hand, a blended product, closely resembling the design coal specification, may not burn in the same way. Interactions can occur between the component coals, which may or may not be beneficial. 2,3 Thus, the compatibility of the alternate coal with respect to the combustion performance has to be properly evaluated. A deep knowledge of the thermal behavior and the reactivity of the blends during devolatilization and combustion is necessary for developing predictive mod- els for these processes. However, because these involve a complex set of reactions, accurate kinetics is not easy to obtain. Thermal analysis techniques, such as ther- mogravimetric analysis (TGA), have been widely used in recent years 4-15 because they provide a rapid quan- titative method for the examination of these processes under nonisothermal conditions and enable the estima- tion of the effective kinetic parameters for the various decomposition reactions. Several methods are available for the evaluation of TGA data for kinetic purposes, with the great majority being referred to individual coals. Very few studies deal with the kinetics of coal blends. 11,16 The most common approach approximates the overall process as a first- order decomposition occurring uniformly throughout the particle. 4-6,8-10,14,15,17 However, for many authors, a simple first-order model is inadequate, and the coal pyrolysis or combustion is described as a series of consecutive or parallel first-order/nth-order processes occurring in different time and temperature inter- vals. 12,18-23 The differences in the kinetic parameters reported by these studies are related to the experimen- tal methods, operating conditions, data analysis, and chemical composition of the raw materials used. In this work, TGA data from different low-rank coals and their blends have been investigated in nitrogen and air and kinetic models have been developed. The aim was to obtain some information on the pyrolysis and combustion of these fuels, as a first step necessary for the evaluation of their cofiring, in an effort for the rational use of poor coals. Experimental Section Materials. A lignite from the Ptolemais basin, a dry lignite from the briquetting plant of Ptolemais-Amy- nteon, and one peat from the Phillipous basin, in northern Greece, as well as blends of the lignite with each of the other coals in proportions 80:20, 60:40, 40: 60, and 20:80, were used in this work. After air-drying, the samples were milled and sieved to the desired particle size. The characterization of these samples is shown in Table 1. The proximate analysis was carried out according to the ASTM standards (D3172-89), the ultimate analysis was performed using a LECO CHN- 600 type analyzer, and the calorific value was deter- mined using a LECO AC-300 type calorimeter. TGA. The experimental system used was a TGA/ differential thermogravimetry (DTG) Perkin-Elmer ther- mobalance (precision of temperature measurement (2 °C; microbalance sensitivity <5 μg), with which the sample weight loss and rate of weight loss as functions * To whom correspondence should be addressed. Tel.: +30 821 37403. Fax: +30 821 64802. E-mail: vamvuka@mred.tuc.gr. 4732 Ind. Eng. Chem. Res. 2003, 42, 4732-4740 10.1021/ie020758m CCC: $25.00 © 2003 American Chemical Society Published on Web 08/27/2003