Thermochemical characterisation of Parinari polyandra Benth fruit shell

The aim of this work is to investigate the thermochemical characteristics of Parinari polyandra Benth fruit shell. An agricultural waste residue is investigated using standard methods including thermogravimetric analysis (TGA), proximate and ultimate analysis, structural composition and bomb calorimeter. The proximate and ultimate analyses were carried out to determine the ash and fixed carbon contents, volatile matter, and elemental compositions. The structural composition analysis determined the hemicellulose, cellulose, and lignin content of the biomass. The measured calorific value obtained was 20.5. MJ/kg. The TGA and DTG profiles indicate the waste fruit shells are viable for pyrolysis reaction. The inorganic contents are relatively low with potassium found to be the most abundant element. The hemicelluloses and cellulose contents are indicative of relatively higher rate of pyrolysis and comparable with established biomass utilised for bio-oil production.

Increase of energy recovery from sewage sludge

The use of the pyrolysis process to obtain valuable products from biomass is amongst the technologies being investigated as a source for renewable energy. The pyrolysis process yields products such as biochar, bio-oil and non condensable gases. The main objective of this project is to increase energy recovery from sewage sludge by utilising the intermediate pyrolysis process. The intermediate pyrolysis has a residence time ranging from 5 to 10 minutes. The main product yields from sewage sludge pyrolysis are 50 wt% biochar, 40 wt% bio-oil and 10 wt% non condensable gases. The project was carried out on a pilot plant scale reactor with a load capacity of 20 kg/h. This enabled a high yield of biochar and bio-oil. The characterisation of the products indicated that the organic phase of the bio-oil had good fuel properties such as having high energy content of 39 MJ/kg, low acid number of 21.5, high flash point of 150 and viscosity of 35 cSt. An increase in pyrolysis experiments enabled large quantities of pyrolysis oil production. Co-pyrolysis of sewage sludge was carried out on laboratory scale with mixed wood, rapeseed and straw. It found that there was an increase in bio-oil quantity with rapeseed while co-pyrolysis with wood helped to mask the smell of the sludge pyrolysis oil. Engine test were successfully carried out in an old Lister engine with pyrolysis oil fractions of 30% and 50% blended with biodiesel. This indicates that these pyrolysis oil fractions can be used in similar engine types without any problems however long term effects in ordinary engines are unknown. An economic evaluation was carried out about the implementation of the intermediate pyrolysis process for electricity production in a CHP using the pyrolysis oil. The prices of electricity per kWh were found to be very high.

Engines for combined heat and power

Spark-ignited (SI) gas engines are for the use of fuel gas only and are limited to the flammable range of the gas; this means the range of a concentration of a gas or vapor that will burn after ignition. Fuel gas like syngas from gasification or biogas must meet high quality and chemical purity standards for combustion in SI gas engines. Considerable effort has been devoted to fast pyrolysis over the years and some of the product oils have been tested in diesel or dual-fuel engines since 1993. For biogas conversion, usually dual-fuel engines are used, while for synthesis gas the use of gas engines is more common. The trials using wood derived pyrolysis oil from fast pyrolysis have not yet been a success story and these approaches have usually failed due to the high corrosivity of the pyrolysis oils.

Thermo-chemical conversion of straw:Haloclean : a performance enhanced low temperature pyrolysis

Haloclean a performance enhanced low temperature pyrolysis for biomass developed by Forschungszentrum Karlsruhe and Sea Marconi Is closing the gap between classical and fast pyrolysis approaches. For pyrolysis of straw (chaffed-, finely ground and pellets) temperature ranges between 320 to 420°C and residence times of only 1 to 5 minutes can be realized. Liquid yields of up to 45 wt-% and 35 wt-% of solids are possible. Solid yields can be increased up to 73 wt-% while loosing 4.5 % of the feed energy by pyrolysis gases only. Toxicity tests of the fractions do not show relevant numbers.

Reactor design and its impact on performance and products

This chapter discusses engineering design and performance of various types of biomass transformation reactors. These reactors vary in their operating principle depending on the processing capacity and the nature of the desired end product, that is, gas, chemicals or liquid bio-oil. Mass balance around a thermal conversion reactor is usually carried out to identify the degree of conversion and obtain the amount of the various components in the product. The energy balance around the reactors is essential for determining the optimum reactor temperature and the amount of heat required to complete the overall reactions. Experimental and pilot-plant testing is essential for proper reactor design. However, it is common practice to use correlation and valid parameter values in determining the realistic reactor dimensions and configurations. Despite the recent progress in thermochemical conversion technology, reactor performance and scale up potential are the subjects of continuing research.

Green preparation of tuneable carbon-silica composite materials from wastes

Bio-oil has successfully been utilized to prepare carbon-silica composites (CSCs) from mesoporous silicas, such as SBA-15, MCM-41, KIT-6 and MMSBA frameworks. These CSCs comprise a thin film of carbon dispersed over the silica matrix and exhibit porosity similar to the parent silica. The surface properties of the resulting materials can be simply tuned by the variation of preparation temperatures leading to a continuum of functionalities ranging from polar hydroxyl rich surfaces to carbonaceous aromatic surfaces, as reflected in solid state NMR, XPS and DRIFT analysis. N2 porosimetry, TEM and SEM images demonstrate that the composites still possess similar ordered mesostructures to the parent silica sample. The modification mechanism is also proposed: silica samples are impregnated with bio-oils (generated from the pyrolysis of waste paper) until the pores are filled, followed by the carbonization at a series of temperatures. Increasing temperature leads to the formation of a carbonaceous layer over the silica surface. The complex mixture of compounds within the bio-oil (including those molecules containing alcohols, aliphatics, carbonyls and aromatics) gives rise to the functionality of the CSCs.

Eulerian model for the condensation of pyrolysis vapors in a water condenser

The paper presents the simulation of the pyrolysis vapors condensation process using an Eulerian approach. The condensable volatiles produced by the fast pyrolysis of biomass in a 100 g/h bubbling fluidized bed reactor are condensed in a water cooled condenser. The vapors enter the condenser at 500 °C, and the water temperature is 15 °C. The properties of the vapor phase are calculated according to the mole fraction of its individual compounds. The saturated vapor pressure is calculated for the vapor mixture using a corresponding states correlation and assuming that the mixture of the condensable compounds behave as a pure fluid. Fluent 6.3 has been used as the simulation platform, while the condensation model has been incorporated to the main code using an external user defined function. © 2011 American Chemical Society.

Effects of resource limitation on the essential oil production in Ledum palustre ssp decumbens (Ait.) Hultén

To understand the relationship between resource limitation and essential oil production of the widely-distributed boreal/arctic shrub, Ledum palustre ssp decumbens, I documented naturally occurring variation of essential oils over a growing season withfield collections along a latitudinal transect spanning boreal forest to arctic tundra. Collections from a long-term resource manipulation experiment at a single tundra site served as a means of teasing apart those factors that might be influencing the essential oil production of the species. The essential oil composition varied significantly along thetransect in the number of detectable components, but the relationships among resources and essential oil production were complex. In the manipulation experiment, essential oil components varied greatly among the treatments, with significant differences in the qualitative expression of the specific essential oil components. Both studies suggest that future climate changes have the potential for large changes in production and quality of essential oils.

Dissociative adsorption of methane on the Cu and Zn doped (111) surface of CeO2

The development of economical heterogeneous catalysts for the activation of methane is a major challenge for the chemical industry. Screening potential candidates becomes more feasible using rational catalyst design to understand the activity of potential catalysts for CH4 activation. The focus of the present paper is the use of density functional theory to examine and elucidate the properties of doped CeO2. We dope with Cu and Zn transition metals having variable oxidation state (Cu), and a single oxidation state (Zn), and study the activation of methane. Zn is a divalent dopant and Cu can have a +1 or +2 oxidation state. Both Cu and Zn dopants have an oxidation state of +2 after incorporation into the CeO2 (111) surface; however a Hubbard +U correction (+U = 7) on the Cu 3d states is required to maintain this oxidation state when the surface interacts with adsorbed species. Dissociation of methane is found to occur locally at the dopant cations, and is thermodynamically and kinetically more favorable on Zn-doped CeO2 than Cu-doped CeO2. The origins of this lie with the Zn(II) dopant moving towards a square pyramidal geometry in the sub surface layer which facilitates the formation of two-coordinated surface oxygen atoms, that are more beneficial for methane activation on a reducible oxide surface. These findings can aid in rational experimental catalyst design for further exploration in methane activation processes.

Low valence cation doping of bulk Cr2O3: Charge compensation and oxygen vacancy formation

The different oxidation states of chromium allow its bulk oxide form to be reducible, facilitating the oxygen vacancy formation process, which is a key property in applications such as catalysis. Similar to other useful oxides such as TiO2, and CeO2, the effect of substitutional metal dopants in bulk Cr2O3 and its effect on the electronic structure and oxygen vacancy formation are of interest, particularly in enhancing the latter. In this paper, density functional theory (DFT) calculations with a Hubbard + U correction (DFT+U) applied to the Cr 3d and O 2p states, are carried out on pure and metal-doped bulk Cr2O3 to examine the effect of doping on the electronic and geometric structure. The role of dopants in enhancing the reducibility of Cr2O3 is examined to promote oxygen vacancy formation. The dopants are Mg, Cu, Ni, and Zn, which have a formal +2 oxidation state in their bulk oxides. Given this difference in host and, dopant oxidation states, we show that to predict the correct ground state two metal dopants charge compensated with an oxygen vacancy are required. The second oxygen atom removed is termed "the active" oxygen vacancy and it is the energy required to remove this atom that is related to the reduction process. In all cases, we find that substitutional doping improves the oxygen vacancy formation of bulk Cr2O3 by lowering the energy cost.

Essential scientific mapping of the value chain of thermochemical converted second-generation bio-fuels

As the largest contributor to renewable energy, biomass (especially lignocellulosic biomass) has significant potential to address atmospheric emission and energy shortage issues. The bio-fuels derived from lignocellulosic biomass are popularly referred to as second-generation bio-fuels. To date, several thermochemical conversion pathways for the production of second-generation bio-fuels have shown commercial promise; however, most of these remain at various pre-commercial stages. In view of their imminent commercialization, it is important to conduct a profound and comprehensive comparison of these production techniques. Accordingly, the scope of this review is to fill this essential knowledge gap by mapping the entire value chain of second-generation bio-fuels, from technical, economic, and environmental perspectives. This value chain covers i) the thermochemical technologies used to convert solid biomass feedstock into easier-to-handle intermediates, such as bio-oil, syngas, methanol, and Fischer-Tropsch fuel; and ii) the upgrading technologies used to convert intermediates into end products, including diesel, gasoline, renewable jet fuels, hydrogen, char, olefins, and oxygenated compounds. This review also provides an economic and commercial assessment of these technologies, with the aim of identifying the most adaptable technology for the production of bio-fuels, fuel additives, and bio-chemicals. A detailed mapping of the carbon footprints of the various thermochemical routes to second-generation bio-fuels is also carried out. The review concludes by identifying key challenges and future trends for second-generation petroleum substitute bio-fuels.

Pyrolyysiöljyn käyttökohteet ja -teknologiat Suomessa

Tässä kandidaatintyössä käsitellään pyrolyysiöljyn käyttökohteita Suomessa. Tarkoitus on luoda katsaus suomalaisen pyrolyysiöljyn ominaisuuksista, käytöstä sekä näihin liittyvistä haasteista. Työssä tarkastellaan myös pyrolyysiöljyn tutkittuja käyttömuotoja ja -tekniikoita. Lisäksi selvitetään missä ja miten pyrolyysiöljyä Suomessa tällä hetkellä käytetään. Pyrolyysiöljyä valmistetaan kaasuttamalla ja sen jälkeen lauhduttamalla biomassaa hapettomissa olosuhteissa. Suomessa pyrolyysiöljyä valmistetaan ainoastaan Fortumin Joensuun voimalaitokseen integroidussa bioöljylaitoksessa. Vuosituotantokapasiteetti on noin 50 000 tonnia. Fortum käyttää pyrolyysiöljyä kahdella eri laitoksella: Joensuussa voimalaitosalueella sekä Espoon Vermossa. Lisäksi Savon Voima ostaa pyrolyysiöljyä Fortumilta käyttääkseen sitä Iisalmen Kivirannankujan lämpökeskuksessa. Fortum on modifioinut fossiilisia polttoaineita käyttäneet kattilat pyrolyysiöljylle sopiviksi. Savon Voiman pyrolyysiöljyä käyttävä kattila on rakennettu alun perin kyseisen polttoaineen käyttämiseen. Myös Ruotsissa on testattu Fortumin pyrolyysiöljyä E.ON:in Karlshamnin voimalaitoksessa. Suomen tavoite siirtyä fossiilisten polttoaineiden käytöstä yhä enemmän uusiutuvaan energiaan edistää biopolttoaineiden yleistymistä. Maailmanmarkkinahinnan lisäksi raskaan ja kevyen polttoöljyn verotus vaikuttaa niiden käytön kustannuksiin. Biomassasta valmistettu pyrolyysiöljy on osoittautunut toimivaksi vaihtoehdoksi näille polttoaineille.

Enhanced oxidation activity from modified ceria: MnOx-ceria, CrOx-ceria and Mg doped VOx-ceria

Ceria is an important component of catalysts for oxidation reactions that proceed through the Mars-van Krevelen mechanism, promoting activity. A paradigm example of this is the VOx–CeO2 system for oxidative dehydrogenation reactions, where vanadium oxide species are supported on ceria and a special synergy between them is behind the enhanced activity: reduction of the catalyst is promoted by ceria undergoing reduction. This leads to favourable oxygen vacancy formation and hydrogen adsorption energies—useful descriptors for the oxidation activity of VOx–CeO2 catalysts. In this paper, we examine if this promoting effect on ceria-based catalysts holds for other metal oxide modifiers and we investigate MnOn– and CrOn–CeO2(111) (n = 0 − 4) as examples. We show, combining density functional theory calculations and statistical thermodynamics that similarly to the vanadia modifier, the stable species in each case is MnO2– and CrO2–CeO2. Both show favourable energetics for oxygen vacancy formation and hydrogen adsorption, indicating that VO2–CeO2 is not the only system of this type that can have an enhanced activity for oxidation reactions. However, the mechanism involved in each case is different: CrO2–CeO2 shows similar properties to VO2–CeO2 with ceria reduction upon oxygen removal stabilising the 5+ oxidation state of Cr. In contrast, with MnO2–CeO2, Mn is preferentially reduced. Finally, a model system of VO2–Mg:CeO2 is explored that shows a synergy between VO2 modification and Mg doping. These results shed light on the factors involved in active oxidation catalysts based on supported metal oxides on ceria that should be taken into consideration in a rational design of such catalysts.

Development of a thermochemical/biological process to convert waste biomass into new resources

The increasing attention to environmental issues of recent times encourages us to find new methods for the production of energy from renewable sources, and to improve existing ones, increasing their energy yield. Most of the waste and agricultural residues, with a high content of lignin and non-hydrolysable polymers, cannot be effectively transformed into biofuels with existing technology. The purpose of the study was to develop a new thermochemical/ biological process (named Py-AD) for the valorization of scarcely biodegradable substances. A complete continuous prototype was design built and run for 1 year. This consists into a slow pyrolysis system coupled with two sequential digesters and showed to produce a clean pyrobiogas (a biogas with significant amount of C2-C3 hydrocarbons and residual CO/H2), biochar and bio-oil. Py-AD yielded 31.7% w/w biochar 32.5% w/w oil and 24.8% w/w pyrobiogas. The oil condensate obtained was fractionated in its aqueous and organic fraction (87% and 13% respectively). Subsequently, the anaerobic digestion of aqueous fraction was tested in a UASB reactor, for 180 days, in increasing organic loading rate (OLR). The maximum convertible concentration without undergoing instability phenomena and with complete degradation of pyrogenic chemicals was 1.25 gCOD L digester-1 d-1. The final yield of biomethane was equal to 40% of the theoretical yield and with a noticeable additional production equal to 20% of volatile fatty acids. The final results confirm that anaerobic digestion can be used as a useful tool for cleaning of slow pyrolysis products (both gas and condensable fraction) and the obtaining of relatively clean pyrobiogas that could be directly used in internal combustion engine.

Avaliação da auto-suficiência energética na indústria nacional arrozeira

Trabalho Final de Mestrado para obtenção do grau de Mestre em Engenharia mecânica