Quantitative Evaluation of Minerals in Lignites and Intraseam Sediments from the Achlada Basin, Northern Greece Nikolaos Koukouzas, Colin R
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Subscriber access provided by American Chemical Society Article Quantitative Evaluation of Minerals in Lignites and Intraseam Sediments from the Achlada Basin, Northern Greece Nikolaos Koukouzas, Colin R. Ward, Dimitra Papanikolaou, and Zhongsheng Li Energy Fuels, Article ASAP • DOI: 10.1021/ef8010993 • Publication Date (Web): 09 March 2009 Downloaded from http://pubs.acs.org on March 20, 2009 More About This Article Additional resources and features associated with this article are available within the HTML version: • Supporting Information • Access to high resolution figures • Links to articles and content related to this article • Copyright permission to reproduce figures and/or text from this article Energy & Fuels is published by the American Chemical Society. 1155 Sixteenth Street N.W., Washington, DC 20036 Energy & Fuels XXXX, xxx, A Quantitative Evaluation of Minerals in Lignites and Intraseam Sediments from the Achlada Basin, Northern Greece Nikolaos Koukouzas,*,† Colin R. Ward,‡ Dimitra Papanikolaou,† and Zhongsheng Li‡ Centre for Research and Technology Hellas, Institute for Solid Fuels Technology and Applications, Mesogeion AVe. 357-359, GR-15231 Halandri, Athens, Greece, and School of Biological, Earth and EnVironmental Sciences, UniVersity of New South Wales, Sydney, NSW 2052, Australia ReceiVed December 16, 2008. ReVised Manuscript ReceiVed January 27, 2009 Seven core samples (five lignite samples and two intraseam nonlignite rock samples) from the Achlada open-cut mine in northern Greece were characterized by X-ray diffraction (XRD) and X-ray fluorescence (XRF) techniques. Quantitative evaluation of the mineral phases in each sample was made from the powder X-ray diffractograms using Siroquant commercial interpretation software, which is based on Rietveld principles. The main minerals in the low-temperature ash (LTA) ash of the lignites are kaolinite and illite, with bassanite and quartz in minor proportions. The nonlignite rock samples mainly consist of illite, mica (2M1), and kaolinite (poorly ordered), along with quartz, chlorite (ferroan), feldspar (albite), rutile, and dolomite. Oriented-aggregate XRD study further shows the presence of smectite, and interstratified illite/smectite (I/S), in the clay fractions of the lignite and rock samples, with the mineral matter of the lignites being richer in kaolinite, smectite, and I/S than in mineral matter of the nonlignite materials. The differences in mineralogy between the lignite and the rock materials probably reflect selective concentration of minerals in the original peat during deposition, combined with authigenic precipitation of minerals such as kaolinte in the peat deposit. Inferred chemical analyses derived from the XRD data show reasonably good correlations with chemical data obtained by direct ash analysis, especially if the smectite and I/S are taken into account. This provides a link between mineralogical and chemical studies that may be valuable in evaluating the behavior of the lignite under different utilization conditions. 1. Introduction Achlada, and also the associated intraseam nonlignite sediments, Lignite is the major source for the generation of electricity to correlate the data with the chemical composition of the lignite in Greece, where it is used to produce some of the least- ash. The chemical composition of the combustion products from expensive and most cost-effective electric power within the this coal characteristically shows high concentrations of calcium European Community. There are 60 lignite basins in Greece,1 and sulfur, which are responsible for the unsuitability of the fly and the annual lignite production in 2006 was estimated at 62.50 ash in concrete production. For example, the concentration of Mt.2 According to data from the Public Power Corporation, this calcium for fly ash derived from the combustion of Achlada’s lignite ranges from 22% to 34%, while the concentration of lignite was consumed to generate 31977 GWh of electricity. 5 The exploitation of lignite in Greece has a very long history. sulfur fluctuates from 4% to 8%. Significant achievements and a large amount of experience, gained during many years of mining operations, have placed 2. Geological Setting the Greek lignite-mining industry in the leading position in The Achlada region is located in the eastern part of the Florina 2,3 Europe. Basin in northwest Macedonia (Greece), extending in a The Achlada open-cut mine is the most recently opened mine NNW-SSE direction from Monastiri (Former Yugoslav Re- in Greece, having started operation in 2001. Its lignite output public of Macedonia (FYROM)) up to the hills of Kozani ∼ is 2.5 Mt per year, all of which is used by the Meliti (330 through the cities of Florina, Amynteo, and Ptolemais (see 4 MW) power station. The lignite derived from the Achlada mine Figure 1). The basin is almost 100 km wide.6 is higher in rank than the lignite from other mines in the region, The largest lignite deposits of Greece, which were formed giving it a higher heating value for equivalent ash percentages. in the Monastiri-Florina-Ptolemais-Kozani graben, are clas- The objective of the present paper is to examine the sified into two types: Ptolemais-type “earthy” lignite and mineralogical composition of representative lignite samples from Komnina-type xylitic lignite.3 * Author to whom correspondence should be addressed. Tel.: +30 210 The Achlada lignite, which is of the xylitic type, is of Lower 6501771. Fax: +30 210 6501598. E-mail: [email protected]. Neogene age, along with the other lignites of the Florina † Centre for Research and Technology Hellas, Institute for Solid Fuels sedimentary basin (Vegora, Petres, Vevi, and Lofi). The Achlada Technology and Applications. ‡ School of Biological, Earth and Environmental Sciences, University lignite is older than the lignite of the Ptolemais type, which is of New South Wales. (1) Koukouzas, N. Miner. Wealth 1998, 106, 53–68. (5) Koukouzas, N.; Tsikardani, E.; Papanikolaou, D. Fly Ash Utilisation (2) Kavouridis, K.; Koukouzas, N. Energy Policy 2008, 36, 693–703. Programme (FAUP), Technology Information, Forecasting & Assessment (3) Koukouzas, N. Int. J. Coal Geol. 2007, 71, 276–286. Council (TIFAC), Department of Science & Technology (DST), 2005. (4) Koukouzas, N.; Vassilatos, C. J. Chem. Technol. Biotechnol. 2008, (6) Karakatsanis, S.; Koukouzas, N.; Pagonas, M.; Zelilidis, A. Bull. 83, 20–26. Geol. Soc. Greece 2007, Vol. XXXX, (Part 1), 76–84. 10.1021/ef8010993 CCC: $40.75 XXXX American Chemical Society B Energy & Fuels, Vol. xxx, XXXX Koukouzas et al. Figure 1. Geological map of the area studied, modified from the Institute of Geology and Mineral Exploration (IGME) Florina and Vevi geological map. of Upper Neogene age and is found in Ptolemais, Proastio, Perdikas, and Amynteo. The strata beneath the basin include the Pelagonian zone of Figure 2. Column section represented by the seven samples collected Palaeozoic and pre-Palaeozoic crystal schists, a Mesozoic for the study. carbonate cover, and ophiolites. The Neogene sediments that fill the basin contain lignite seams, on top of which fluviotor- Table 1. Thicknesses Represented by Lignite and Rock Samples rential or terrestrial deposits are present.7 The lignite-bearing sample code sample description interval thickness (m) sediments are Late Miocene to Pliocene in age. C1 xylite 3.5 The lowermost Neogene horizon, known as the Basal R1 marl 0.3 Conglomerate, begins the succession of sediments that fill the C2 xylite 5.0 - C3 marly lignite 1.5 basin. The middle horizon (the Vevi Achlada Formation), R2 sand 0.2 which is exposed in the Vevi and Achlada lignite mines, overlies C4 marly lignite 2.0 the Basal Conglomerate and is represented by alternations of C5 lignite 4.0 clayey, sandy, and marly sediments, as well as by lignite seams. Clayey diatomite and phosphatic nodules have also been Subsamples that were taken from the five lignite samples and identified in these sediments.8 The lignite seams and associated the two rock samples were ground to fine powder. Subsequent interseam sediments have a total thickness of ∼35 m. The analysis suggests that some of these were not fully equivalent to uppermost horizon (Lofi Formation), overlying the Vevi-Achlada the samples detailed in Tables 1 and 2, because of inhomogeneities Formation, continues the Neogene succession, with alternations in the bulk material from which they were taken. However, they indicate a similar range of quality variation within the lignite seam. of clays, marly breccias, sandy conglomerates, and lime marl The powdered lignite samples were subjected to low-temperature beds. On the top of this sandy-clay horizon is a marly limestone oxygen-plasma ashing using an IPC four-chamber asher, as outlined bed, which covers the entire basin. A thin cover of limnodeltaic, in Australian Standard 1038, Part 22; the mass percentage of low- fluviotorrential, and terrestrial Quaternary sediments completes temperature ash (LTA) was determined in each case. Each LTA the lithological column in this part of the basin. was further powdered, and then analyzed via powder XRD, using a Philips Model PW1830 diffractometer with Cu KR radiation and a graphite monochromator. Diffractograms were run in a 2θ range 3. Materials and Methods of 2°-60°, with steps of 0.04° and a counting time of 2 s. Seven samples were collected from a mine exposure in the The powdered rock samples were also analyzed in this way, Achlada region, a column section of which is shown in Figure 2. without the low-temperature ashing procedure. Quantitative analyses These included five lignite samples and two rock samples. The total of the mineral phases in each LTA or rock sample were made from thickness of the section studied is 16.5 m, representing the upper the X-ray diffractograms using Siroquant, which is commercial part of the mining succession. The coding of the lignite and rock interpretation software9 that is based on principles originally samples is presented in Table 1. The five lignite samples are C1, developed by Rietveld.10 Further details of the software interpreta- C2, C3, C4, and C5, and the two rock samples are R1 and R2.