Mozambique has vast forestry resources and also considerable biomass waste material such as bagasse, rice husks, sawdust, coconut husks and shells, cashew nut shell and lump charcoal waste. The potential of the total residues from the agricultural sector and the forest industry is estimated to be approximately 13 PJ. This amount of energy covers totally the production of charcoal which amounted to approximately 12.7 PJ in 2006. Although biomass is an attractive renewable source of energy, it is generally difficult to handle, transport, storage and use due to its lower homogeneity, its lower energy density and the presence of non-combustible inorganic constituents, which leads to different problems in energy conversion units such as deposition, sintering, agglomeration, fouling and corrosion. Therefore, a pretreatment of the biomass to solve these problems could lead to a change of current biomass utilization situation. The aim of this study is to convert Mozambican woody biomass residue into a solid biochar that resembles low-grade coal. In this work the current energy situation in Mozambique has been reviewed, and the available and potential renewable sources including residues from agricultural crops and forest industry as energy have been assessed. It was found that the country is endowed with great potential for biofuel, solar, hydro and wind energy production. However, the production today is still far from fulfilling the energy needs of the country, and the majority of people are still not benefiting from these resources. Charcoal and firewood are still the main sources of energy and will continue to play a very important role in the near future. Additionally, enormous amounts of energy resources are wasted, especially in the agricultural sector. These residues are not visible on national energy statistics. The chemical composition and the fuelwood value index (FVI) showed that by failing to efficiently utilise residues from Afzelia quanzensis, Millettia stuhlmannii and Pterocarpus angolensis, an opportunity to reduce some of the energy related problems is missed. An evaluation of effect of a mild wet torrefaction pretreatment showed that the chemical composition of the biochar is substantially different than the feedstock. The use of diluted acid as catalysts improves the biochar quality, namely in terms of the energy density and ash characteristics; however, the increment of the S content in the final product should be considered for market acceptance (because the fuels have a maximum allowance for S concentration). The thermal behaviour of the untreated and treated biomass was also investigated. The pyrolytic products of umbila and spruce were affected by the treatment and catalyst in terms of yield and composition of the vapours. / <p>QC 20150202</p>

Of the many thermochemical conversion pathways for utilizing biomass as a renewable energy source, fast pyrolysis is a promising method for converting and upgrading carbonaceous feedstocks into a range of liquid fuels for use in heat, electricity and transportation applications. Experimental trials have been carried out to assess the impact of operational parameters on process yields. However, dealing with larger-scale experimental systems comes at the expense of lengthy and resource-intensive experiments. Luckily, the advances in computing technology and numerical algorithm solvers have allowed reactor modelling to be an attractive opportunity for reactor design, optimization and experimental data interpretation in a cost-effective fashion. In this work, a fluidized bed reactor model for biomass fast pyrolysis was developed and applied to the Bell’s Corners Complex (BCC) fluidized bed fast pyrolysis unit located at NRCan CanmetENERGY (Ottawa, Canada) for testing and validation. The model was programmed using the Microsoft Visual Basic for Applications software with the motivation of facilitating use and accessibility as well as minimizing runtime and input requirements. The application of different biomass devolatilization schemes within the model was conducted, not only for biomass fast pyrolysis product quantity but also liquid product composition (quality), to examine the effect of variable reaction kinetic sub-models on product yields. The model predictions were in good agreement with the results generated from the experimental work and mechanism modifications were proposed which further increased the accuracy of model predictions. Successively, the formulation of the modelled fluid dynamic scheme was adapted to study the effect of variable hydrodynamic sub-models on product yields for which no significant effect was observed. The work also looked into effect of the dominant process variables such as feedstock composition, bed temperature, fluidizing velocity and feedstock size on measurable product outputs (bio-oil, gas and biochar) and compared the results to those generated from the experimental fast pyrolysis unit. The ideal parameters for maximizing bio-oil yield have been determined to be those which: minimize the content of lignin and inorganic minerals in the feedstock, maintain the dense-bed temperature in a temperature range of 450-520 ºC, maximize the fluidization velocity without leading to bed entrainment, and limit the feedstock particle size to a maximum of 2000 μm.

Increased research efforts have recently been accelerated to develop liquid transportation fuels from bio-oil produced by fast pyrolysis. However, these bio-oils contain high levels of oxygenated compounds that require removal to produce viable transportation fuels. A variety of upgrading technologies have been proposed, of which catalytic hydroprocessing of the raw bio-oil has appears to have the best potential due to the fact that no fractionation of the bio-oil is required prior to treatment. The objective of this research was to apply two-stage catalytic hydroprocessing to bio-oil with heterogeneous catalysts to produce hydrocarbon fuels. To achieve this objective seven catalysts were initially compared in first-stage hydrotreating reactions. The result of the comparison of the seven hydrotreating catalysts showed that the MSU-1 catalyst had the significantly highest yield at 38 wt%, had the highest H/C ratio, and reduced oxygen adequately. The MSU-1 catalyst had an energy efficiency of 80%, reduced acid value by 45% and water content by 78%. Higher heating value was doubled by the hydrotreating process of raw bio-oil. Three catalysts were compared as second-stage hydrocracking catalysts. All liquid organic products produced by the catalytic reactions were compared with regard to yield and chemical and physical qualities. Results from these experiments showed that the MSU-2 catalyst had the significantly highest yield at 68 wt%; oxygen value was significantly lower than for the compared catalysts at zero percent. MSU-2 also produced the lowest amount of char at 3.5 wt%. Additionally, MSU-2 produced a high volume of methane gas as a byproduct, with a high value for utilization for production of process heat. A study of reaction time optimization found that best results from application of MSU-2 were for the shortest reaction time of 1 h. This short reaction time is important to reduce hydroprocessing costs. Simulated distillation of hydrocarbon mix results in distribution of these by fuel weights with gasoline comprising 37%, jet fuel 27%, diesel 25% and heavy fuel oil 11%.The energy efficiency of the hydrocracking of first-stage stabilized bio-oil with MSU-2 catalyst was 93.61%.

<div>Biomass-derived fuels have long been considered as a possible replacement for traditional liquid fuels derived from petroleum. However, biomass as a feedstock requires significant refinement prior to application as a liquid fuel. The H2Bioil process has previously been proposed in which biomass is pyrolyzed and the resulting vapors are passed over a catalyst bed for upgrading to hydrocarbon products in a hydrogen environment [1]. A PtMo catalyst has been developed for the complete hydrodeoxygenation (HDO) of biomass pyrolysis vapors to hydrocarbons [2]. However, the product hydrocarbons contain a large fraction of molecules smaller than C4 which would not be suitable as liquid fuels. In fast hydropyrolysis of poplar followed by hydrodeoxygenation over a PtMo/MWCNT catalyst at 25 bar H2 and 300oC, only 32.1% of carbon is captured in C4 – C8 products; 21.7% of carbon is captured in C1 – C3 hydrocarbons [2]. Here, approaches are examined to increase selectivity of H2Bioil to desired products. Aldol condensation catalysts could be used prior to the HDO catalyst in order to increase the carbon number of products. These products would then be hydrodeoxygenated to hydrocarbons of greater average carbon number than with an HDO catalyst alone. Application of a 2% Cu/TiO2 catalyst to a classic aldehyde model compound, butanal, shows high selectivity towards aldol condensation products at low H2 pressures. In more complex systems which more closely resemble biomass pyrolysis vapors, this catalyst also shows significant yields to aldol condensation products, but substantial carbon losses presumed to be due to coke formation are observed. Both glycolaldehyde, a significant product of biomass pyrolysis, and cellulose, a component polymer of biomass, have been pyrolyzed and passed through aldol condensation followed by hydrodeoxygenation in a pulsed fixed-bed microreactor. Glycolaldehyde aldol condensation resulted in the formation of products in the C2-C¬9 range, while the major aldol condensation products observed from cellulose were C7 and C8 products. Carbon losses in glycolaldehyde aldol condensation were reduced under operation at increased hydrogen partial pressures, supporting the hypothesis that increasing selectivity to hydrogenation products can reduce coke formation from primary aldol condensation products. </div><div>The use of feeds which have undergone genetic modification and/or pretreatment by other catalytic processes may also lead to improvements in overall product selectivity. The influence of genetic modifications to poplar lignin on the pyrolysis plus HDO process are investigated, and it is found that these materials have no effect on the final product distribution. The product distribution from a poplar sample which has had lignin catalytically removed is also examined, with the conclusion that the product distribution strongly resembles that of cellulose, however the lignin-removed sample shows high selectivity towards char which is not seen from cellulose. </div><div><br></div>

A residential micro-cogeneration system based on a Stirling engine unit was modified to operate with wood derived fast pyrolysis liquid (bio-oil)-ethanol blend. A pilot stabilized swirl combustion chamber was designed to replace the original evaporative burner due to bio-oil’s nondistillable nature. This also required modifications of the engine’s control systems. Efficiencies for the bio-oil/ethanol blend were found be higher than those of diesel due to the higher heat loss incurred with diesel. Based on a modified efficiency, which disregarded the heat loss through the combustion chamber, power efficiencies were found to be comparable. The maximum time of operation with the bio-oil/ethanol blend was approximately 97 minutes due to the clogging of the narrow passages. Carbon monoxide emissions were higher for the bio-oil/ethanol blend due to the operation conditions of the combustion chamber. Oxides of nitrogen emissions were also higher for the bio-oil/ethanol blend due to its inherent nitrogen content.

A residential micro-cogeneration system based on a Stirling engine unit was modified to operate with wood derived fast pyrolysis liquid (bio-oil)-ethanol blend. A pilot stabilized swirl combustion chamber was designed to replace the original evaporative burner due to bio-oil’s nondistillable nature. This also required modifications of the engine’s control systems. Efficiencies for the bio-oil/ethanol blend were found be higher than those of diesel due to the higher heat loss incurred with diesel. Based on a modified efficiency, which disregarded the heat loss through the combustion chamber, power efficiencies were found to be comparable. The maximum time of operation with the bio-oil/ethanol blend was approximately 97 minutes due to the clogging of the narrow passages. Carbon monoxide emissions were higher for the bio-oil/ethanol blend due to the operation conditions of the combustion chamber. Oxides of nitrogen emissions were also higher for the bio-oil/ethanol blend due to its inherent nitrogen content.

The hardwood Eucalyptus grandis has been shown to be an important commodity for forestry-related industries as it has significantly faster specific growth rates per annum when compared with other types of tree species. It has therefore been suggested that residues from E. grandis may be a useful source of biomass for use in the production of biofuels for the transportation industry. Notably, E. grandis plantations within the Southern Hemisphere have some of the fastest growth rates worldwide. Due to the inherent nature of biomasses, such as lignocellulosic types having a significant amount of oxygen present, upgrading of biofuels produced from E. grandis is necessary. Several approaches were therefore evaluated to upgrade pyrolysis oils produced from E. grandis so as to increase their calorific values by decreasing oxygen content and subsequently increasing the hydrogen ratio. The hydrogen-to-carbon (H/C) and oxygen-to-carbon (O/C) ratios may be used successfully to evaluate the performances of catalyst-based upgrading techniques for either in situ or ex situ pyrolysis. In this regard the van Krevelen diagram, in which biofuels can be compared for their suitability as transportation fuels, along with their respective calorific values, is useful. The pyro-gas chromatography/mass spectroscopy (GC/MS) equipment is useful for the rapid and accurate evaluation of different catalysts for fast pyrolysis applications, and it was used here to evaluate the performances of the catalysts bentonite and ZSM-5 zeolite for upgrading pyrolysis oil produced from E. grandis biomass. A van Krevelen diagram was used to evaluate the performance of these catalysts, in conjunction with calorific values, based on the higher heating values v for the pyrolysis oils. Further studies were completed for microwave pyrolysis as it is a less harsh form of pyrolysis based on energy-transfer mechanisms. Mass balances were done and demonstrated good repeatability, with more stable pyrolysis oils being produced. This stability may be attributed to similarities between microwave pyrolysis and hydrothermal liquefaction as microwave pyrolysis induces conditions comparable to those of hydrothermal liquefaction within the wood cells, and both methods produce a stable product called bio-crude. Furthermore, it was found that these pyrolysis oils could be distilled so as to remove some of the water content and improve the higher heating value (HHV) from 13.80 to 23.30 MJ/kg. However, this was not as high as the theoretical yield of 26.70 MJ/kg, and better performance was obtained for fast pyrolysis catalysed with ZSM-5 zeolite at 300 °C, which achieved an HHV of 34.54 MJ/kg. It is recommended that ZSM-5 zeolite catalysis be used in microwave-assisted vacuum pyrolysis to determine whether a similar improvement may be realised. Microwave-assisted pyrolysis should also be investigated as a possible technology for inducing conditions similar to hydrothermal liquefaction processes within the cells that make up the biomass. / Dissertation (MEng)--University of Pretoria, 2015. / Chemical Engineering / Unrestricted

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Biomassa innehåller oorganiska ämnen som bl.a. alkalimetaller och alkaliska jordartsmetaller, vilket bidrar till ett minskat utbyte av pyrolysolja och ökar istället utbytet av gaser och lågvärdiga produkter. Detta sker p.g.a. att oorganiska ämnen agerar som krackningkatalysatorer. [1] Pyrolysolja har även en hög syrehalt vilket t.ex. gör den oblandbar med fossil olja. Genom att använda lakning som förbehandlingsmetod kan biomassans innehåll av oorganiska ämnen minska och pyrolysoljans sammansättning ändras. Detta sker genom bl.a. jonbytesreaktioner som uppstår mellan joner i lakningsmedlet och biomassans oorganiska ämnen. [2]        En katalysator kan användas för att minska syrehalten i pyrolysoljan och erhålla högvärdiga produkter som aromater. Detta sker genom katalytiska reaktioner som bl.a. krackning, aromatisering, ketoniserings- och aldolkondensation samt avspjälkning av vatten. [3] [4] I detta arbete har kombinationen av att förbehandla biomassa samt att låta pyrolysångor reagera över en katalysator undersökts. Fyra olika experiment har utförts för att kunna jämföra produktfördelningen mellan vätska, gas och kolrest, vätskefördelningen mellan H2O och olja samt olje-sammansättningen i de olika fallen. Experimenten utfördes med förbehandlad/icke-förbehandlad biomassa med och utan katalysator. Som lakningsmedel vid förbehandlingen användes en blandning av ättiksyra och avjoniserat vatten som biomassan behandlades med och sedan separerades ifrån. Som katalysator användes zeoliten HZSM-5 och utvärderades ex-bed i pyrolysören.        Resultaten visar att halten oorganiska ämnen minskar efter behandling. Förbehandlad biomassa utan katalysator ger ett ökat utbyte av vätska där vätskefördelningen mellan H2O och olja visar en större mängd olja jämfört med icke-förbehandlad biomassa utan katalysator. I fallet förbehandlad biomassan med katalysator visar resultatet att en större mängd gas bildas jämfört med icke-förbehandlad biomassa med katalysator, vilket tyder på att katalysatorn reagerar starkare mot sammansättningen av pyrolysångor från förbehandlad biomassa i det fallet. Vätskefördelningen vid icke-förbehandlad biomassan med katalysator visar en större mängd olja jämfört med förbehandlad biomassa med katalysator.       Olje-sammansättningen visar att den största mängden högvärdiga produkter, i detta fall polyaromatiska kolväten, bildas vid närvaro av katalysator. / Biomass generally contains inorganic substances such as alkali metals and alkaline earth metals, which reduce the yield of pyrolysis oil and increases the yield of gases and low-value products due to inorganic substances acting as cracking catalysts. [1] Pyrolysis oil also has a high oxygen content, making it im-miscible with fossil oil. Using leaching as a pretreatment method, the content of inorganic substances in biomass can decrease which changes the composition of the pyrolysis oil. Among other things, this occurs through ion-exchange reactions that occur when ions between the leachant and the ionically bonded inorganic elements in biomass change site. [2] A catalyst can be used to reduce oxygen content in the pyrolysis oil and obtain high-quality products such as aromatics. This is done through reactions such as cracking, aromatization, ketonization and aldol condensation as well as hydro-deoxygenation that arise in the presence of a catalyst. [3] [4]            In this work, four different experiments have been conducted to compare the product distribution between liquid, gas and char, the liquid distribution between H2O and oil and the oil composition in the different cases. The experiments were performed with pre-treated/untreated biomass with and without catalyst. As leachant, a mixture of acetic acid and deionized water was used with which the biomass was boiled and then separated. As catalyst, The zeolite HZSM-5 was used. HZSM-5 was evaluated ex-bed in the process. The results show that the content of inorganic substances decreases after treatment. Pre-treated biomass without catalytic upgrading leads to increase in the liquid yield in which the liquid distribution between H2O and oil shows a greater amount of oil compares to untreated biomass with without catalytic upgrading, indicating a decrease of inorganic substances. In the case of pre-treated biomass with catalyst, the result shows that a larger amount of gas is formed compared to untreated biomass with catalyst, which indicates that the catalyst reacts more strongly to the composition of pyrolysis vapors from a pre-treated biomass in that case. The liquid distribution of the untreated biomass with catalyst shows a greater amount of oil compared to pre-treated biomass with catalyst.       The oil composition shows that the largest amount of high-value products, in this case polyaromatic hydrocarbons, is formed in the presence of the catalyst.

A pirólise rápida é uma tecnologia promissora para a conversão de biomassa. O principal produto desse processo é o bio-óleo, um líquido com elevada densidade energética, com potencialidades para a aplicação na produção de combustíveis e compostos renováveis. No entanto, existem ainda algumas barreiras para a sua utilização direta e um pós-processamento pode ser necessário. O uso de catalisadores no pós-processamento de bio-óleo, ou durante o processo de pirólise rápida, configura-se como alternativa para a produção direta de combustíveis e de produtos químicos com valor agregado, pois o processamento catalítico, além de elevar o rendimento, melhora a qualidade do bio-óleo produzido. O presente trabalho apresenta uma contribuição para o desenvolvimento do processo de pirólise rápida como uma rota viável de processamento de biomassas residuais, visando a obtenção de bio-óleo com propriedades adequadas a sua aplicação direta como combustível ou ainda para o fracionamento em produtos de interesse na indústria química. Este estudo compreende a síntese e avaliação do desempenho de diferentes catalisadores para o processo de pirólise rápida, bem como o projeto de uma unidade flexível para o processamento de biomassas através do processo de pirólise rápida catalítica. Catalisadores foram sintetizados através de diferentes metodologias e a sua atividade para a pirólise rápida foi avaliada através de ensaios utilizando moléculas representativas dos produtos da pirólise. O emprego de catalisadores a base de HZSM-5 modificada por metais permitiu, em alguns casos, o aumento na eficiência da reação de pirólise. A incorporação de zinco, gálio e nióbio resultou em aumento da atividade, elevando a produção de compostos aromáticos a partir da conversão catalítica de furanos. Os catalisadores de zinco apresentaram melhores resultados, possivelmente devido à maior incorporação do zinco nos sítios ácidos da zeólita, produzindo novos sítios capazes de elevar a taxa da reação de aromatização. Uma avaliação das alterações superficiais dos catalisadores permitiu correlacionar algumas propriedades do catalisador com sua atividade para a pirólise rápida e distribuição de produtos, permitindo também, em alguns casos, a identificação de possíveis rotas reacionais. As variáveis de processo, tais como temperatura de reação, velocidade espacial e presença de diferentes teores de água, simulando teores de água presentes em biomassas típicas, foram avaliadas. Verificou-se a importância da co-alimentação de água nos ensaios padrão para verificação da atividade de catalisadores para aplicação em pirólise rápida de biomassa. A água produz uma nova rota reacional na presença de HZSM-5 (reação de hidrólise), o que altera significativamente a distribuição de produtos da pirólise. / Fast pyrolysis is a promising technology for converting biomass into liquid fuels and chemicals. The main product of this process is bio-oil, a liquid with high energy density, which enables its use as a renewable source for the production of energy, fuels and chemicals. However, there are some barriers to its direct use as a fuel, and a post-processing may be needed. The use of catalysts for bio-oil upgrading or combined with the fast pyrolysis process is an alternative to the direct production of fuels, since the catalyst improves the quality and stability of bio-oil, as well as improving the pyrolysis yield. This work presents a contribution to the development of the fast pyrolysis process as a viable processing route for biomass conversion into fuels and chemicals. This study involves the synthesis and evaluation of different catalysts for the fast pyrolysis process, as well as the design of a flexible unit for the processing of biomass by catalytic fast pyrolysis. Catalysts were synthesized using different methods and their activity was evaluated by using furans as representative compounds of pyrolysis-derived products. Studies were conducted to identify catalysts with desirable properties for biofuel production. The incorporation of metals on HZSM-5 resulted in a promoting effect on catalytic conversion of furans. Zinc, niobium and gallium showed better activity than unmodified HZSM-5, increasing the aromatics production. Zinc catalysts presented the best result among samples, possibly due to a greater incorporation of zinc in the zeolite acid sites, producing new sites that are capable of increasing the rate of the aromatization reaction. An evaluation of the catalyst surface changes allowed the determination of the correlation between certain catalyst properties and their activity. It also allowed the identification of possible reaction pathways. Process variables such as reaction temperature, space velocity and water vapour pressure were also evaluated. The importance of water co-feeding in standard tests for catalysts activity evaluation was studied. Water produces a new reaction pathway in the presence of HZSM-5 (hydrolysis reaction), which significantly changes the distribution of pyrolysis products.