>Magister Scientiae - MSc / The global dependence on non-renewable fossil fuels to meet energy needs cannot be sustained for a long time and it is already evident in the escalation of fuel prices over the past decade. This research was performed towards renewable energy production from agricultural and food waste. The use of agricultural and food waste has benefits such as being grown in a land that is not in competition with food crops protein, all year round availability, and having high lipid content. The produced bio-crude oil can be upgraded to remove moisture and acidity level, and can be used as a substitute for heavy oils such as diesel to power static appliances or can be used as petrol distillate fuel alternative. Hydrothermal liquefaction (HTL) process is one of the commonly used technologies for converting agricultural and food waste into liquid biofuels.

This thesis evaluates the possibility to use a iron-based catalyst as a pyrolysis vapour conversion catalyst. The iron catalyst was also compared with the mineral dolomite. The experiments were facilitated at Cortus Energy's demonstration plant in Koping, Sweden, by in situ instal- lation of the experimental setup to an outlet of the pyrolyser unit. The pyrolysis vapour from Cortus Energy was converted for a total of 8 hours by passing it through a packed bed reactor containing the iron-based catalyst while sampling gas and oil from the feed for analysis. The outset for the operation on the dolomite catalyst bed was the same as for the iron catalyst with a resulting collapse of the bed when the pyrolysis vapour was introduced. The permanent gases were analysed on site with a µ-GC unit while oil samples were condensed and analysed with GC-MS, H-NMR and Karl Ficher titration. The carbon laydown and surface area of the catalyst was determined as well as the phase changes of the catalyst surface with XRD. The results showed clear indications of bio-crude conversion with an eightfold increase of the H2 concentration of the synthetic gas from 3.38 % to 26.69 % on a dry gas basis. The oxygen to carbon (O:C) ratio decreased in the treated pyrolysis oil compared to the untreated oil while the hydrogen to carbon (H:C) ratio showed indications of dehydration of the oil. The gas and water content of the stream increased while 57.2 % of the oil was converted in the process. Lastly, the iron-based catalyst did not seem to favour the conversion of alkylated phenols.

Reliable energy supply is a major concern and crucial for development of the global society. To address the dependency on fossil fuel and the negative effects of this reliance on climate, there is a need for a transition to cleaner sources. An attractive solution for replacing fossil-based products is renewable substitutes produced from biomass. Gasification and pyrolysis are two promising thermochemical conversion technologies, facing challenges before large-scale commercialization becomes viable. In case of biomass gasification, tar is often and undesired by-product. An attractive option to convert tar into syngas is nickel-based catalytic steam reforming (SR). For biomass pyrolysis, catalytic SR is in early stages of investigation as a feasible option for bio-crude conversion to syngas. The focus of the thesis is partly dedicated to describe research aimed at increasing the knowledge around tar reforming mechanisms and effect of biomass-derived impurities on Ni-based tar reforming catalyst downstream of gasifiers. The work focuses on better understanding of gas-phase alkali interaction with Ni-based catalyst surface under realistic conditions. A methodology was successfully developed to enable controlled investigation of the combined sulfur (S) and potassium (K) interaction with the catalyst. The most striking result was that K appears to lower the sulfur coverage and increases methane and tar reforming activity. Additionally, the results obtained in the atomistic investigations are discussed in terms of naphthalene adsorption, dehydrogenation and carbon passivation of nickel. Furthermore, the thesis describes research performed on pyrolysis gas pre-conditioning at a small-industrial scale, using an iron-based catalyst. Findings showed that Fe-based materials are potential candidates for application in a pyrolysis gas pre-conditioning step before further treatment or use, and a way for generating a hydrogen-enriched gas without the need for bio-crude condensation. / Tillförlitlig energiförsörjning är en stor utmaning och avgörande för utvecklingen av det globala samhället. För att ta möta beroendet av fossil råvara och de negativa effekter som detta beroende medför för klimatet finns ett stort behov av en övergång till renare energiråvaror. En attraktiv lösning är att ersätta nuvarande fossil råvara med produkter från biomassa. Förgasning och pyrolys är två lovande teknologier för termokemisk omvandling av biomassa. Kommersialisering av dessa teknologier är inte helt problemfritt. I fallet förgasning så behöver, bl.a. oönskade tyngre kolväten (tjära) hanteras innan den producerade orenade produktgasen kan användas i syntesgastillämpningar. Ett effektivt alternativ för detta är gaskonditionering vid höga temperaturer, baserade på katalytisk ångreformering med en nickelkatalysator. Katalytisk ångreformering är en möjlig teknik för omvandling av bioråvara, producerad från pyrolys av biomassa, till syntesgas. Avhandlingen fokuserar delvis på att beskriva den forskning som utförts för att öka kunskapen kring mekanismer för tjärreformering och effekterna av föroreningar från biomassan på en nickelkatalysator nedströms förgasare. Arbetet bidrar till en bättre förståelse av hur alkali i form av kalium (K) i gasfasen upptas, jämviktas och växelverkar med ytan hos nickelkatalysatorn under fullt realistiska förhållanden. Inledningsvis utvecklades en metod för att möjliggöra kontrollerade studier av den kombinerade effekten av S och K, vilken inkluderar exakt dosering av alkali till en produktgas, eliminering av transienter i katalysatoraktiviteten samt katalysatorkarakterisering. Det mest lovande resultatet är att K både sänker ytans svavelinnehåll och ökar aktiviteten för omvandlingen av metan och tjära. För att ytterligare fördjupa kunskaperna i mekanismerna för tjärnedbrytning utfördes experimentella och teoretiska ytstudier på en enkristallnickelyta med naftalen som modellförening. Resultat avseende naftalenadsorption, dehydrogenering av naftalen och kolpassivering av nickelytan diskuteras. Därutöver så beskriver avhandlingen den forskning som utförts inom förkonditionering av pyrolysgas med en järnkatalysator för varsam deoxygenering av biooljan och vätgasproduktion. Detta utfördes vid en småskalig industriell anläggning. De experimentella studierna visar att den undersökta järnkatalysatorn resulterar i en vätgasberikad gas och att den är en potentiell kandidat för tillämpning i ett förkonditioneringssteg. / <p>QC 20170830</p>

Recently, there has been a surge in the research and application of "Green energy" in the United States. This has been driven by the following three objectives: (1) to reduce the nation's reliance on foreign oil, (2) to mitigate emission of greenhouse gas, and (3) to create an economic stimulus within the United States. Switchgrass is the biomass of choice for the Southeastern United States. In this dissertation, we address a feedstock logistics problem associated with the delivery of switchgrass for conversion into biofuel. In order to satisfy the continual demand of biomass at a bioenergy plant, production fields within a 48-km radius of its location are assumed to be attracted into production. The bioenergy plant is expected to receive as many as 50-400 loads of biomass per day. As a result, an industrialized transportation system must be introduced as early as possible in order to remove bottlenecks and reduce the total system cost. Additionally, we assume locating multiple bioenergy plants within a given region for the production of biofuel. We develop mixed integer programming formulations for the feedstock logistics problem that we address and for some related problems, and we solve them either through the use of decomposition-based methods or directly through the use of CPLEX 12.1.0. The feedstock logistics problem that we address spans the entire system-from the growing of switchgrass to the transporting of bio-crude oil, a high energy density intermediate product, to a refinery for conversion into a final product. To facilitate understanding, we present the reader with a case study that includes a preliminary cost analysis of a real-life-based instance in order to provide the reader appropriate insights of the logistics system before applying optimization techniques for its solution. First, we consider the benefits of active versus passive ownership of the production fields. This is followed by a discussion on the selection of baler type, and then, a discussion of contracts between various business entities. The advantages of storing biomass at a satellite storage location (SSL) and interactions between the operations performed at the production field with those performed at the storage locations are then established. We also provide a detailed description of the operations performed at a SSL. Three potential equipment options are presented for transporting biomass from the SSLs to a utilization point, defined in this study as a Bio-crude Plant (BcP). The details of the entire logistics chain are presented in order to highlight the need for making decisions in view of the entire chain rather than basing them on its segments. We model the feedstock logistics problem as a combination of a 2-level facility location-allocation problem and a multiple traveling salesmen problem (mATSP). The 2-level facility location-allocation problem pertains to the allocation of production fields to SSLs and SSLs to one of the multiple bioenergy plants. The mATSP arises because of the need for scheduling unloading operations at the SSLs. To this end, we provide a detailed study of 13 formulations of the mATSP and their reformulations as ATSPs. First, we assume that the SSLs are always full, regardless of when they are scheduled to be unloaded. We, then, relax this assumption by providing precedence constraints on the availability of the SSLs. This precedence is defined in two different ways and, is then, effectively modeled utilizing all the formulations for the mATSP and ATSP. Given the location of a BcP for the conversion of biomass to bio-crude oil, we develop a feedstock logistics system that relies on the use of SSLs for temporary storage and loading of round bales. Three equipment systems are considered for handling biomass at the SSLs, and they are either placed permanently or are mobile, and thereby, travel from one SSL to another. We use a mathematical programming-based approach to determine SSLs and equipment routes in order to minimize the total cost incurred. The mathematical program is applied to a real-life production region in South-central Virginia (Gretna, VA), and it clearly reveals the benefits of using SSLs as a part of the logistics system. Finally, we provide a sensitivity analysis on the input parameters that we used. This analysis highlights the key cost factors in the model, and it emphasizes areas where biggest gains can be achieved for further cost reduction. For a more general scenario, where multiple BcPs have to be located, we use a nested Benders' decomposition-based method. First, we prove the validity of using this method. We, then, employ this method for the solution of a potential real-life instance. Moreover, we successfully solve problems that are more than an order of magnitude larger than those solved directly by CPLEX 12.1.0. Finally, we develop a Benders' decomposition-based method for the solution of a problem that gives rise to a binary sub-problem. The difficulty arises because of the sub-problem being an integer program for which the dual solution is not readily available. Our approach consists of first solving the integer sub-problem, and then, generating the convex hull at the optimal integer point. We illustrate this approach for an instance for which such a convex hull is readily available, but otherwise, it is too expensive to generate for the entire problem. This special instance is the solution of the mATSP (using Benders' decomposition) for which each of the sub-problems is an ATSP. The convex hull for the ATSP is given by the Dantzig, Fulkerson, and Johnson constraints. These constraints at a given integer solution point are only polynomial in number. With the inclusion of these constraints, a linear programming solution and its corresponding dual solution can now be obtained at the optimal integer points. We have proven the validity of using this method. However, the success of our algorithm is limited because of a large number of integer problems that must be solved at every iteration. While the algorithm is theoretically promising, the advantages of the decomposition do not seem to outweigh the additional cost resulting from solving a larger number of decomposed problems. / Ph. D.