Fast pyrolysis of corn residues for energy production.

[摘要] ENGLISH ABSTRACT: Increasing oil prices along with the climate change threat have forced governments, society and the energy sector to consider alternative fuels. Biofuel presents itself as a suitable replacement and has received much attention over recent years. Thermochemical conversion processes such as pyrolysis is a topic of interest for conversion of cheap agricultural wastes into clean energy and valuable products. Fast pyrolysis of biomass is one of the promising technologies for converting biomass into liquid fuels and regarded as a promising feedstock to replace petroleum fuels. Corn residues, corn cob and corn stover, are some of the largest agricultural waste types in South Africa amounting to 8 900 thousand metric tonnes annually (1.7% of world corn production) (Nation Master, 2005).This study looked at the pyrolysis kinetics, the characterisation and quality of by-products from fast pyrolysis of the corn residues and the upgrading of bio-oil. The first objective was to characterise the physical and chemical properties of corn residues in order to determine the suitability of these feedstocks for pyrolytic purposes. Secondly, a study was carried out to obtain the reaction kinetic information and to characterise the behaviour of corn residues during thermal decomposition. The knowledge of biomass pyrolysis kinetics is of importance in the design and optimisation of pyrolytic reactors. Fast pyrolysis experiments were carried out in 2 different reactors: a Lurgi twin screw reactor and a bubbling fluidised bed reactor. The product yields and quality were compared for different types of reactors and biomasses. Finally, a preliminary study on the upgrading of bio-oil to remove the excess water and organics inorder to improve the quality of this liquid fuel was performed.Corn residues biomass are potential thermochemical feedstocks, with the following properties (carbon 50.2 wt. %, hydrogen 5.9 wt. % and Higher heating value 19.14 MJ/kg) for corn cob and (carbon 48.9 wt. %, hydrogen 6.01 wt. % and Higher heating value 18.06 MJ/kg) for corn stover. Corn cobs and corn stover contained very low amounts of nitrogen (0.41-0.57 wt. %) and sulphur (0.03-0.05 wt. %) compared with coal (nitrogen 0.8-1.9 wt. % and sulphur 0.7-1.2 wt. %), making them emit less sulphur oxides than when burning fossil fuels. The corn residues showed three distinct stages in the thermal decomposition process, with peak temperature of pyrolysis shifting to a higher value as the heating rate increased. The activation energies (E) for corn residues, obtained by the application of an iso-conversional method from thermogravimetric tests were in the range of 220 to 270 kJ/mol.The products obtained from fast pyrolysis of corn residues were bio-oil, biochar, water and gas. Higher bio-oil yields were produced from fast pyrolysis of corn residues in a bubbling fluidised bed reactor (47.8 to 51.2 wt. %, dry ash-free) than in a Lurgi twin screw reactor (35.5 to 37 wt. %, dry ash-free). Corn cobs produced higher bio-oil yields than corn stover in both types of reactors. At the optimised operating temperature of 500-530 °C, higher biochar yields were obtained from corn stover than corn cobs in both types of reactors. There were no major differences in the chemical and physical properties of bio-oil produced from the two types of reactors. The biochar properties showed some variation in heating values, carbon content and ash content for the different biomasses. The fast pyrolysis of corn residues produced energy products, bio-oil (Higher heating value = 18.7-25.3 MJ/kg) and biochar (Higher heating value = 19.8-29.3 MJ/kg) comparable with coal (Higher heating value = 16.2-25.9 MJ/kg). The bio-oils produced had some undesirable properties for its application such as acidic (pH 3.8 to 4.3) and high water content (21.3 to 30.5 wt. %). The bio-oil upgrading method (evaporation) increased the heating value and viscosity by removal of light hydrocarbons and water. The corn residues biochar produced had a BET Brynauer-Emmet-Teller (BET) surface area of 96.7 to 158.8 m2/g making it suitable for upgrading for the manufacture of adsorbents. The gas products from fast pyrolysis were analysed by gas chromatography (GC) as CO2, CO, H2, CH4, C2H4, C2H6, C3H8 and C5+ hydrocarbons. The gases had CO2 and CO of more than 80% (v/V) and low heating values (8.82-8.86 MJ/kg).

[发布机构] Stellenbosch University