O. Onay, E.Atabay, S.H. Beis and O. M. Kockar Department of Chemical Engineering, Faculty of Engineering Anadolu University, 26470, Eskisehir, Turkey World Renewable Energy Congress IX and Exhibition, August 2006, Florence-Italy Anadolu University TURKEY Co-pyrolysis of lignite and biomass in a fixed-bed reactor

ABSTRACT In this study, investigations into the product yields during co-pyrolysis of coal/biomass blends prepared at different ratios have been conducted using a fixed-bed pyrolysis reactor. In this study, investigations into the product yields during co-pyrolysis of coal/biomass blends prepared at different ratios have been conducted using a fixed-bed pyrolysis reactor. The effects of blend ratio for pyrolysis of coal/safflower seed The effects of blend ratio for pyrolysis of coal/safflower seed The final pyrolysis temperature on the pyrolysis products yield The final pyrolysis temperature on the pyrolysis products yield Mixture composition on the chemical compositions of the oil have been investigated. Mixture composition on the chemical compositions of the oil have been investigated. World Renewable Energy Congress IX and Exhibition, August 2006, Florence-Italy

INTRODUCTION The world energy demand is currently mainly met by conventional fossil energy sources such as coal, crude oil and natural gas. The volume of these reserves is limited and fossil fuels are the source of Greenhouse Gases. Attention is now turning towards renewable energy sources. such as solar, wind, tidal energy and biomass. The world energy demand is currently mainly met by conventional fossil energy sources such as coal, crude oil and natural gas. The volume of these reserves is limited and fossil fuels are the source of Greenhouse Gases. Attention is now turning towards renewable energy sources. such as solar, wind, tidal energy and biomass. The co-processing of biomass with coal offers a number of advantages. The thermal utilization of biomass can contribute to the reduction of CO 2 emissions as the same amount of CO 2 is extracted from the atmosphere during the growth period of the plants as is released by combustion (CO 2 balance), as well as beneficial effect on the reduction in SO 2 emissions. The co-processing of biomass with coal offers a number of advantages. The thermal utilization of biomass can contribute to the reduction of CO 2 emissions as the same amount of CO 2 is extracted from the atmosphere during the growth period of the plants as is released by combustion (CO 2 balance), as well as beneficial effect on the reduction in SO 2 emissions. The utilization of a variety of poor coal including, low grade coal and refuse coal as a primary energy source is becoming a subject of utmost importance in many countries, like Turkey, where there is a substantial reserve of such materials. Unlike poor coal, biomass has a low ash and sulphur content, a high volatile matter yield and fixed carbon with high reactivity. Therefore, it could potentially be attractive from the economical, environmental and social points of view that poor coal would be utilized for oil production to make use of expected synergistic effects of mixing biomass waste to it in a co-pyrolysis thus enhancing the added value of the final product. The utilization of a variety of poor coal including, low grade coal and refuse coal as a primary energy source is becoming a subject of utmost importance in many countries, like Turkey, where there is a substantial reserve of such materials. Unlike poor coal, biomass has a low ash and sulphur content, a high volatile matter yield and fixed carbon with high reactivity. Therefore, it could potentially be attractive from the economical, environmental and social points of view that poor coal would be utilized for oil production to make use of expected synergistic effects of mixing biomass waste to it in a co-pyrolysis thus enhancing the added value of the final product. World Renewable Energy Congress IX and Exhibition, August 2006, Florence-Italy

……INTRODUCTION Pyrolysis is considered one way for low-rank coal valorization since high- value gas and liquid products and good quality chars are obtained. An additional improvement of pyrolysis products can be achieved when coal is co-pyrolyzed together with some selected materials. Co-pyrolysis process could have potential for the environmentally friendly transformation of biomass and coal to valuable products. Pyrolysis is considered one way for low-rank coal valorization since high- value gas and liquid products and good quality chars are obtained. An additional improvement of pyrolysis products can be achieved when coal is co-pyrolyzed together with some selected materials. Co-pyrolysis process could have potential for the environmentally friendly transformation of biomass and coal to valuable products. Consequently, the treatment of biomass-coal is a challenge for the future. Pyrolytic processes are suitable to convert coal and biomass materials into valuable feedstock and the specific benefits of this method potentially include: the reduction of the volume of biomass; the recovery of chemicals and the replacement of fossil fuels. Consequently, the treatment of biomass-coal is a challenge for the future. Pyrolytic processes are suitable to convert coal and biomass materials into valuable feedstock and the specific benefits of this method potentially include: the reduction of the volume of biomass; the recovery of chemicals and the replacement of fossil fuels. World Renewable Energy Congress IX and Exhibition, August 2006, Florence-Italy

EXPERIMENTAL The safflower seed (Carthamus tinctorius L.) and lignite sample investigated in this study has been taken from vicinity of Eskisehir and Kutahya-Seyitömer region, was located in central Anatolia, respectively. The safflower seed (Carthamus tinctorius L.) and lignite sample investigated in this study has been taken from vicinity of Eskisehir and Kutahya-Seyitömer region, was located in central Anatolia, respectively. Prior to use, the sample was air dried, grounded in a high-speed rotary cutting mill. Particle size range was between mm for lignite and mm for safflower seed. Prior to use, the sample was air dried, grounded in a high-speed rotary cutting mill. Particle size range was between mm for lignite and mm for safflower seed. The proximate analysis The proximate analysis Elemental analysis (Fisons EA 1108) Elemental analysis (Fisons EA 1108) World Renewable Energy Congress IX and Exhibition, August 2006, Florence-Italy

EXPERIMENTAL Pyrolysis Pyrolysis Safflower seed, lignite and their mixtures were pyrolysed in a Heinze retort. The experiments performed in the Heinze reactor were carried out in two groups. Safflower seed, lignite and their mixtures were pyrolysed in a Heinze retort. The experiments performed in the Heinze reactor were carried out in two groups. In the first, to determine the effect of pyrolysis temperature on the product yields, In the first, to determine the effect of pyrolysis temperature on the product yields, four different pyrolysis temeperature of either 400, 500, 550 or 700°C and the heating rate was taken as 7 °Cmin –1. For these experiments %50 blending ratio of safflower seed (weight of safflower seed in (weight of safflower seed in the blend expressed as a percentage of the total sample weight) was used. In the second group of the experiments, order to establish the effect of blending ratio on the pyrolysis yields, In the second group of the experiments, order to establish the effect of blending ratio on the pyrolysis yields, a range of blending ratios between 0% and 100% (w/w) a range of blending ratios between 0% and 100% (w/w) The final pyrolysis temperature and the heating rate were 550°C and 7°Cmin -1, respectively. World Renewable Energy Congress IX and Exhibition, August 2006, Florence-Italy

EXPERIMENTAL ……..Characterization EXPERIMENTAL ……..Characterization Chemical class compositions of the oils were determined by liquid column chromatographic fractionation. Chemical class compositions of the oils were determined by liquid column chromatographic fractionation. The oil was separated into two fractions as n-pentane soluble and insoluble compounds (asphaltenes) by using n-pentane. The n-pentane soluble material was further separated on activated silica-gel ( mesh). The column was eluted successively with n-pentane, toluene and methanol to produce aliphatic, aromatic and polar fractions, respectively. Each fraction was dried and weighed. The fractions were analyzed by Fourier transform infrared spectroscopy to determine the efficient separation of the chemical class. The fractions were analyzed by Fourier transform infrared spectroscopy to determine the efficient separation of the chemical class. In addition, n-pentane fraction was analyzed by GC/MS (HP 6890 GC/MS 30 m  0.25 mm i.d.; 0.25  m film thickness, HP-5MS column). In addition, n-pentane fraction was analyzed by GC/MS (HP 6890 GC/MS 30 m  0.25 mm i.d.; 0.25  m film thickness, HP-5MS column). World Renewable Energy Congress IX and Exhibition, August 2006, Florence-Italy

RESULTS AND DISCUSSION World Renewable Energy Congress IX and Exhibition, August 2006, Florence-Italy

RESULTS AND DISCUSSION World Renewable Energy Congress IX and Exhibition, August 2006, Florence-Italy Fig.1. Effects of pyrolysis temperature on the co-pyrolysis products at 50%( w/w) blending ratio of safflower seed

RESULTS AND DISCUSSION World Renewable Energy Congress IX and Exhibition, August 2006, Florence-Italy Fig.2. Effects of blending ratio of coal and safflower seed on the production of the co- pyrolysis products at pyrolysis tempera-ture of 550°C. The dashed lines represent the theoretical additive evolutions of the products.

RESULTS AND DISCUSSION World Renewable Energy Congress IX and Exhibition, August 2006, Florence-Italy a b Fig.4 GC/MS of the n-pentane fraction for coal (a), coal/biomass (b) and biomass (c) pyrolysis oils c

CONCLUSION In the present work, mixtures of safflower seed and coal can be radically converted to liquid products by pyrolysis under self pyrolysis atmosphere in Heinze retort. In the present work, mixtures of safflower seed and coal can be radically converted to liquid products by pyrolysis under self pyrolysis atmosphere in Heinze retort. At pyrolysis temperature of 550°C the maximum yield of oil is watched. At pyrolysis temperature of 550°C the maximum yield of oil is watched. At this temperature, the most important parameter for the oil production is the blending ratio in feedstocks. At this temperature, the most important parameter for the oil production is the blending ratio in feedstocks. For the experiments with coal less than 33wt.%, additive phenomena occur, leading to higher oil production. For the experiments with coal less than 33wt.%, additive phenomena occur, leading to higher oil production. The yield of oil goes to a maximum of about 35wt.% for 10% blending ratio of coal in the experimental conditions used. The yield of oil goes to a maximum of about 35wt.% for 10% blending ratio of coal in the experimental conditions used. World Renewable Energy Congress IX and Exhibition, August 2006, Florence-Italy