This thesis describes the production of bio-oils from flash pyrolysis of agricultural residues, using a pyrolysis centrifugal reactor (PCR). By thermal degradation of agricultural residues in the PCR, a liquid oil, char and non-condensable gases are produced. The yield of each fraction is influenced by the reaction temperature and by feedstock ash composition. It have been the objective of the present work to investigate the influence of changed operation conditions on the yield of bio-oil, char and gas; as well as to investigate the composition and storage properties of some of the produced bio-oils. Mainly the influence of feedstock type (wheat straw, rice husk and pine wood), feedstock water content and reactor temperature on the yield of char, bio-oil and gas were investigated. The storage stability of bio-oils with respect to changes in viscosity, water content and pH were investigated for straw and pine wood oil at different temperature and residence times. Temperature plays a major role in the pyrolysis process and it determines to a high degree the fate of the final product yields and also product composition. Higher temperature favors the formation of pyrolysis gas while lower temperatures increase the yield of char. Liquid oil, however increases with temperature up to certain point and thereafter it decreases at still higher temperature due to secondary cracking of the primary products. The presence of moisture in the feed stock may also influences the pyrolysis process. The influence of reaction temperature and the moisture content on the flash pyrolysis product yield has been reported in Paper I (Chapter 2). It was observed that the presence of moisture in the wheat straw with different moisture levels of 1.5 wt. %, 6.2 wt. % and 15.0 wt. % have shown no significant effect on the pyrolysis product distribution. The fraction of bio-oil, char and gases produced from pyrolysis of straw were in the range of 40-60 wt. %, 18-50 wt. % and 5-22 wt. %, respectively, regardless of the straw moisture levels. The optimal reaction temperature for the production of bio-oil was around 525 °C to 550 °C for all straw moisture contents. It was investigated how differences in biomass composition influence pyrolysis products yields and the composition of char and bio-oils. Details about this investigation are explained in Paper II (Chapter 3). The used pine wood had a low ash content (0.5 wt. %), the wheat straw an intermediate ash level (6.0 wt. %) and the rice husk a high ash level (13.6 wt. %). The highest alkali content, potassium (1.53 wt. %) are present in straw and the lowest potassium content level is observed in pine wood (0.04 wt. %). The feedstocks were pyrolyzed at reactor temperatures ranging from 475 to 575 oC. It was observed that the formation of char and gas is affected by the biomass alkali content. Increasing biomass alkali content caused an increased feedstock conversion at low temperature, a lower maximum liquid organic yield temperature and a lower maximum liquid organics yield. In addition, the chemical compositions of the bio-oils and the chars of the investigated feedstocks were also analyzed. The utilization of the pyrolysis oil in static combustion equipments such as boilers and turbine have shown that the suitability of the pyrolysis oil to substitute fossil fuel. However, several limitations still arise due to the instability of the pyrolysis oil that may cause problems with transport and storage. Pyrolysis oil contains more than hundred of chemical compounds and has a wide range of volatility (different boiling points). The stability and aging of bio-oils generated by bench scale pyrolysis of wheat straw and pine wood are discussed in Paper III (Chapter 4). It was found that the bio-oil from wheat straw shows better stability compared to the bio-oil from pine wood. In addition, both bio-oils are fairly stable stored in a closed container at room temperature for up to 130 days, with no phase separation and only small changes in physical properties were observed. The combustion behavior of pyrolysis oils derived from wheat straw and pine wood are investigated and discussed in Paper IV (Chapter 5). The investigation is done in two parts. In the first part, the technique of thermogravimetric analysis (TGA) was applied to study the thermal treatment of the pyrolysis oils under well controlled temperature in an oxidative (O2) and non-oxidative (N2) environment. It was found that the drying phase occurred below 200 °C, evaporation of light components and cracking of heavy fractions occurs at the temperature above 200 up to 500 °C, and finally the char combustion occurs at temperatures above 500 up to 700 °C. In the second part, the combustion of single droplets of pyrolysis oils were investigated and compared with the heavy fossil fuel oil by making experiments in a single droplet combustion chamber. The initial oil droplet diameters were in between 500 μm to 2500 μm. The experiments were performed at a temperature ranging between 1000 and 1400 °C with an initial gas velocity of 1.6 m/s and oxygen concentration of 3%. It was observed that the burning of bio-oil droplet experienced large swelling with swelling factors up to 4 times of the initial droplet diameter. However, the burning of heavy fossil fuel oil droplet showed neither swelling nor bubbling. In addition, the droplet burning lifetimes for bio-oils (droplet size of 1500 μm at a temperature of 1000 °C were found to be longer (13 s and 9 s for straw oil and wood oil, respectively) than the heavy oil (6 s) at the temperature of 1200 oC. It can be concluded that the combustion of bio-oils droplet are different from the combustion of heavy fossil fuel oil in terms of ignition, devolatilisation and char combustion. The bio-oil is difficult to ignite and has a shorter devolatilisation time and a longer char combustion time.
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Jensen, Peter Arendt, Dam-Johansen, Kim
Technical University of Denmark, Department of Chemical Engineering, 2012