abstract: The project aims at utilization of hydrothermal liquefaction (HTL) byproducts like biochar to grow microalgae. HTL is a promising method to convert wet algal biomasses into biofuels. The initial microalgae liquefaction at a temperature of 300 °C for 30 minute, converted 31.22 % of the Galdieria sulphuraria and 41.00 % of the Kirchneriella cornutum into biocrude. Upon changing the reactor from a 100 ml to a 250 ml reactor, the yield in biocrude increased to 31.48 % for G. sulphuraria and dropped to 38.05 % for K. cornutum. Further, energy recoveries based on calorific values of HTL products were seen to drop by about 5 % of the 100 ml calculated values in the larger reactor. Biochar from HTL of G. sulphuraria at 300 °C showed 15.98 and 5.27 % of phosphorous and nitrogen, respectively. HTL products from the biomass were analyzed for major elements through ICP-OES and CHNS/O. N and P are macronutrients that can be utilized in growing microalgae. This could reduce the operational demands in growing algae like, phosphorous mined to meet annual national demand for aviation fuel. Acidic leaching of these elements as phosphates and ammoniacal nitrogen was studied. Improved leaching of 49.49 % phosphorous and 95.71 % nitrogen was observed at 40 °C and pH 2.5 over a period of 7 days into the growth media. These conditions being ideal for growth of G. sulphuraria, leaching can be done in-situ to reduce overhead cost. Growth potential of G. sulphuraria in leached media was compared to a standard cyanidium media produced from inorganic chemicals. Initial inhibition studies were done in the leached media at 40 °C and 2-3 vol. % CO2 to observe a positive growth rate of 0.273 g L-1 day-1. Further, growth was compared to standard media with similar composition in a 96 well plate 50 μL microplate assay for 5 days. The growth rates in both media were comparable. Additionally, growth was confirmed in a 240 times larger tubular reactor in a Tissue Culture Roller drum apparatus. A better growth was observed in the leached cyanidium media as compared to the standard variant. / Dissertation/Thesis / Masters Thesis Chemical Engineering 2017

abstract: The continued reliance on fossil fuel for energy resources has proven to be unsustainable, leading to depletion of world reserves and emission of greenhouse gases during their combustion. Therefore, research initiatives to develop potentially carbon-neutral biofuels were given the highest importance. Hydrothermal liquefaction (HTL, a thermochemical conversion process) of microalgae is recognized as a favorable and efficient technique to produce liquid biofuels from wet feedstocks. In this work, three different microalgae (Kirchneriella sp., Galdieria sulphuraria, Micractinium sp.) grown and harvested at Arizona State University were hydrothermally liquefied to optimize their process conditions under different temperatures (200-375 °C), residence times (15-60 min), solids loadings (10-20 wt.%), and process pressures (9-24 MPa). A one-factor-at-a-time approach was employed, and comprehensive experiments were conducted at 10 % solid loadings and a residence time of 30 min. Co-liquefaction of Salicornia bigelovii Torr. (SL), Swine manure (SM) with Cyanidioschyzon merolae (CM) was tested for the presence of synergy. A positive synergistic effect was observed during the co-liquefaction of biomasses, where the experimental yield (32.95 wt.%) of biocrude oil was higher than the expected value (29.23 wt.% ). Co-liquefaction also led to an increase in the energy content of the co-liquefied biocrude oil and a higher energy recovery rate ( 88.55 %). The HTL biocrude was measured for energy content, elemental, and chemical composition using GC-MS. HTL aqueous phase was analyzed for potential co-products by spectrophotometric techniques and is rich in soluble carbohydrates, dissolved ammoniacal nitrogen, and phosphates. HTL biochar was studied for its nutrient content (nitrogen and phosphorous) and viability of its recovery to cultivate algae without any inhibition using the nutrient leaching. HTL biochar was also studied to produce hydrogen via pyrolysis using a membrane reactor at 500 °C, 1 atm, for 24 h to produce 5.93 wt.% gas. The gaseous product contains 45.7 mol % H2, 44.05 ml % CH4, and 10.25 mol % of CO. The versatile applications of HTL biochar were proposed from a detailed physicochemical characterization. The metal impurities in the algae, bio-oil, and biochar were quantified by ICP-OES where algae and biochar contain a large proportion of phosphorous and magnesium. / Dissertation/Thesis / Doctoral Dissertation Chemical Engineering 2020

O processo de liquefação hidrotermal (HTL) pode converter diversos tipos de biomassa em óleo bruto. Além do produto principal, é gerado um efluente (PHWW) com elevada carga orgânica, quantidades altas de nutrientes e compostos tóxicos. Para lidar com este tipo efluente tem-se sugerido a combinação de tratamentos físico-químicos e biológicos. O objetivo deste estudo foi avaliar a aplicação de processos oxidativos (por H2O2 e fotocatálise com TiO2) e digestão anaeróbia no tratamento do efluente da liquefação hidrotermal de Spirulina. Inicialmente caracterizou-se o efluente em termos de carga orgânica, nutrientes e compostos nitrogenados cíclicos (CNC). Posteriormente, avaliou-se a concentração de oxidante e o tempo de reação no processo de oxidação com H2O2. O tratamento fotocatalítico foi então avaliada no tratamento do efluente em questão, isoladamente, em sequência e combinada ao processo de oxidação por ação de H2O2. Finalmente combinaram-se os processos de oxidação por ação de H2O2 e digestão anaeróbia no tratamento de efluente de PHWW. O efluente da liquefação hidrotermal de Spirulina apresentou elevada carga orgânica, pH alcalino e concentrações altas de nutrientes (nitrogênio e fósforo). Verificou-se também a presença de CNC como pirazinas, δ-valerolactama, caprolactama e butirolactama. A aplicação do processo oxidativo por H2O2 no tratamento de PHWW apresentou efeitos positivos, principalmente para a descoloração que atingiu 93,8 %. A eficiência máxima de remoção de DQO foi de 15,3%. Foi percebida também redução nas concentrações dos CNC. A eficiência do processo de oxidação avançada por fotocatálise e H2O2 foi maior do que obtida quando estes processos foram aplicados separadamente. A aplicação dos processos combinados apresentou eficiência de remoção de cor e DQO semelhante às obtidas quando os processos foram aplicados em sequência, propiciando economia de tempo de reação. Por fim, verificou-se que a digestão anaeróbia do efluente pré-tratado com H2O2 apresentou maior produção de CH4 e remoção de matéria orgânica quando comparada com a digestão anaeróbia que o efluente in natura. Assim, conclui-se a utlização de processos oxidativos avançados ou a combinação da oxidação por H2O2 com a digestão anaeróbia são alternativas promissoras para o tratamento da PHWW. / The hydrothermal liquefaction process (HTL) can convert various types of biomass into bio-crude oil. In addition to the main product, wastewater (PHWW) is generated with high organic content, high amounts of nutrients and toxic compounds. To cope with this type of wastewater the combination of physicochemical and biological treatments has been suggested. The aim of this study was to evaluate the application of oxidative processes (using H2O2 and photocatalysis with TiO2) and anaerobic digestion in the treatment of hydrothermal liquefaction of Spirulina wastewater. Firstly, PHWW was characterized in terms of organic matter, nutrients and nitrogen heterocyclic compounds (CNC) concentrations. Secondly, the oxidant concentration and the reaction time in the oxidation process using H2O2 was evaluated. Photocatalytic treatment was then tested isolated, in sequence and combinated with the oxidation processo using H2O2. Finally, oxidation with H2O2 and anaerobic digestion were combinated and evaluated. The PHWW showed high organic load, alkaline pH and high concentrations of nutrients (nitrogen and phosphorus). The presence of CNC as pyrazines, δ-valerolactam, caprolactam and butyrolactam was also verified. The application of the oxidative process using H2O2 showed positive effects mainly for color removal, which reached 93.8%. The maximum efficiency of COD removal was 15.3%. Reduction in CNC concentrations was also observed . The efficiency of the advanced oxidation process (by combining photocatalysis and H2O2) was greater than that obtained when these processes were applied separately. The application of the combined process presented color and COD removal efficiencies similar to those obtained when the processes were applied in sequence, allowing reaction time savings. Finally, the anaerobic digestion of pre-treated (with H2O2) PHWW showed a greater CH4 production and higher organic matter removal, compared to anaerobic digestion of in natura PHWW. Thus it is possible to conclude that the utlization of advanced oxidation processes or the combination of oxidation with H2O2 and anaerobic digestion are promising alternatives for the treatment of PHWW.

[pt] Com aumento da preocupação político-ambiental, torna-se imperativo desenvolver processos eficientes em termos econômicos e energéticos para a produção sustentável de combustíveis e produtos químicos. A liquefação hidrotérmica (HTL) é um processo para a transformação de materiais orgânicos, tais como bio-resíduos ou biomassa, em óleo bruto, em temperaturas usualmente inferiores a 400 graus Celsius sob altas pressões na presença de água, e, dependendo do processo, de um catalisador. Nesse contexto, é importante entender o comportamento de degradação térmica do material em atmosfera inerte, no sentido de se investigar a possibilidade de quebra das cadeias poliméricas inicias em moléculas menores, que, mediante pressão, poderão ser convertidas em novos produtos. Assim sendo, os objetivos do presente trabalho estão associados ao estudo termogravimétrico (TG) da degradação térmica da fibra do coco verde na presença de ferrita de cobalto (Fe2CoO4), utilizada no intuito de gerar um efeito catalítico, acelerando a degradação térmica das estruturas poliméricas presentes, e, que possa ser usada posteriormente em uma rota HTL. Os catalisadores foram produzidos a 1000 graus Celsius em diferentes tempos de calcinação (3h, 6h e 9h), sendo, nas misturas com a fibra, a fração mássica de óxido igual a 50 por cento. As amostras de interesse para a pesquisa foram caracterizadas mediante diferentes técnicas, tais como, a microscopia eletrônica de varredura, para o estudo da morfologia e composição elementar, difração de raios X, para a quantificação das fases presentes nas amostras de ferrita, e espectroscopia de infravermelho, visando à identificação das principais ligações químicas nas fibras, tanto antes quanto durante o tratamento térmico. Dentre todos os ensaios de TG realizados, os experimentos com o catalisador calcinado durante 9h homogeneizado com gral de ágata foi o que mostrou uma melhor resposta com relação à degradação térmica das fibras. Os resultados sugerem ainda que, tanto o tempo de calcinação, quanto a natureza do processo de mistura apresentam efeitos significativos sobre a cinética de degradação. / [en] With increasing political-environmental concern, it becomes imperative to develop efficient processes in economic and energy terms for the sustainable production of fuels and chemical products. Hydrothermal liquefaction (HTL) is a process for the transformation of organic materials such as bio-waste or biomass into crude oil at temperatures usually below 400 degrees Celsius under high pressures in the presence of water and, depending on the process, of a catalyst. In this context, it is important to understand the behavior of thermal degradation of the material under inert atmosphere, in order to investigate the possibility of breaking the initial polymer chains into smaller molecules, which, under pressure, can be converted into new products. The objectives of the present work are associated to the thermogravimetric study (TG) in the thermal degradation of the green coconut fiber in the presence of a cobalt ferrite (Fe2CoO4), used to generate a catalytic effect, accelerating the thermal degradation of the polymeric structures present, and which can be used later on an HTL route. The catalysts were produced at 1000 degrees Celsius at different calcination times (3h, 6h and 9h) and in the fiber mixtures, the oxide mass fraction was equal to 50 percent. The samples of interest for the research were characterized by different techniques, such as scanning electron microscopy, for the study of the morphology and elemental composition, X-ray diffraction, for the quantification of the phases present in the ferrite samples, and spectroscopy of Infrared, in order to identify the main chemical bonds in the fibers, both before and during the heat treatment. Among all the TG assays performed, the experiments with the catalyst calcined for 9h homogenized with mortar and pestle showed the best to the thermal degradation of the fibers. The results further suggest that both the calcination time and the nature of the blending process have significant effects on the degradation kinetics.

O processo de liquefação hidrotermal (HTL) pode converter diversos tipos de biomassa em óleo bruto. Além do produto principal, é gerado um efluente (PHWW) com elevada carga orgânica, quantidades altas de nutrientes e compostos tóxicos. Para lidar com este tipo efluente tem-se sugerido a combinação de tratamentos físico-químicos e biológicos. O objetivo deste estudo foi avaliar a aplicação de processos oxidativos (por H2O2 e fotocatálise com TiO2) e digestão anaeróbia no tratamento do efluente da liquefação hidrotermal de Spirulina. Inicialmente caracterizou-se o efluente em termos de carga orgânica, nutrientes e compostos nitrogenados cíclicos (CNC). Posteriormente, avaliou-se a concentração de oxidante e o tempo de reação no processo de oxidação com H2O2. O tratamento fotocatalítico foi então avaliada no tratamento do efluente em questão, isoladamente, em sequência e combinada ao processo de oxidação por ação de H2O2. Finalmente combinaram-se os processos de oxidação por ação de H2O2 e digestão anaeróbia no tratamento de efluente de PHWW. O efluente da liquefação hidrotermal de Spirulina apresentou elevada carga orgânica, pH alcalino e concentrações altas de nutrientes (nitrogênio e fósforo). Verificou-se também a presença de CNC como pirazinas, δ-valerolactama, caprolactama e butirolactama. A aplicação do processo oxidativo por H2O2 no tratamento de PHWW apresentou efeitos positivos, principalmente para a descoloração que atingiu 93,8 %. A eficiência máxima de remoção de DQO foi de 15,3%. Foi percebida também redução nas concentrações dos CNC. A eficiência do processo de oxidação avançada por fotocatálise e H2O2 foi maior do que obtida quando estes processos foram aplicados separadamente. A aplicação dos processos combinados apresentou eficiência de remoção de cor e DQO semelhante às obtidas quando os processos foram aplicados em sequência, propiciando economia de tempo de reação. Por fim, verificou-se que a digestão anaeróbia do efluente pré-tratado com H2O2 apresentou maior produção de CH4 e remoção de matéria orgânica quando comparada com a digestão anaeróbia que o efluente in natura. Assim, conclui-se a utlização de processos oxidativos avançados ou a combinação da oxidação por H2O2 com a digestão anaeróbia são alternativas promissoras para o tratamento da PHWW. / The hydrothermal liquefaction process (HTL) can convert various types of biomass into bio-crude oil. In addition to the main product, wastewater (PHWW) is generated with high organic content, high amounts of nutrients and toxic compounds. To cope with this type of wastewater the combination of physicochemical and biological treatments has been suggested. The aim of this study was to evaluate the application of oxidative processes (using H2O2 and photocatalysis with TiO2) and anaerobic digestion in the treatment of hydrothermal liquefaction of Spirulina wastewater. Firstly, PHWW was characterized in terms of organic matter, nutrients and nitrogen heterocyclic compounds (CNC) concentrations. Secondly, the oxidant concentration and the reaction time in the oxidation process using H2O2 was evaluated. Photocatalytic treatment was then tested isolated, in sequence and combinated with the oxidation processo using H2O2. Finally, oxidation with H2O2 and anaerobic digestion were combinated and evaluated. The PHWW showed high organic load, alkaline pH and high concentrations of nutrients (nitrogen and phosphorus). The presence of CNC as pyrazines, δ-valerolactam, caprolactam and butyrolactam was also verified. The application of the oxidative process using H2O2 showed positive effects mainly for color removal, which reached 93.8%. The maximum efficiency of COD removal was 15.3%. Reduction in CNC concentrations was also observed . The efficiency of the advanced oxidation process (by combining photocatalysis and H2O2) was greater than that obtained when these processes were applied separately. The application of the combined process presented color and COD removal efficiencies similar to those obtained when the processes were applied in sequence, allowing reaction time savings. Finally, the anaerobic digestion of pre-treated (with H2O2) PHWW showed a greater CH4 production and higher organic matter removal, compared to anaerobic digestion of in natura PHWW. Thus it is possible to conclude that the utlization of advanced oxidation processes or the combination of oxidation with H2O2 and anaerobic digestion are promising alternatives for the treatment of PHWW.

No description available.

L'objectif de cette thèse est d'étudier la valorisation de la liqueur noire non soufrée par deux procédés hydrothermaux : la gazéification en eau supercritique et la liquéfaction hydrothermale. Ceux-ci seront comparés au procédé actuel de valorisation (évaporation puis combustion dans chaudière Tomlinson) selon 3 critères : le rendement énergétique, la récupération du sodium et la production de molécules aromatiques biosourcées.Lors de la gazéification, il a été montré que la formation de gaz est compétitive à celle de char. Une chauffe rapide et des températures élevées vont favoriser le rendement gaz et donc le rendement énergétique. Cependant les rendements énergétiques sont plus faibles que le procédé actuel car la conversion des composés aromatiques provenant de la lignine est faible dans la gamme de température étudiée. Lors d'un procédé en continu, à plus haute température (700°C) avec une chauffe rapide, le rendement énergétique peut être le double au procédé actuel (simulé à l'équilibre thermodynamique). La préhydrolyse du bois et l'utilisation de bois de résineux vont défavoriser la conversion de la liqueur noire en gaz.La liquéfaction quant-à-elle permet la formation composés phénoliques et d'un biocrude dont la combustion permettant de meilleur rendements énergétique que le procédé actuel. En effet, la lignine de la liqueur noire est hydrolysée en fragments réactifs, pouvant être soit dégradés soit se recombiner pour former le biocrude. Cette dernière est favorisée par la présence des carbohydrates. L'utilisation de bois de feuillus et la préhydrolyse vont améliorer le rendement énergétique.La récupération du sodium est satisfaisante pour les deux procédés, validant la faisabilité de la substitution de la chaudière par ces procédés hydrothermaux. / This thesis aims to study sulfur free black liquor valorization through two hydrothermal processes: supercritical water gasification and hydrothermal liquefaction. These processes will be compared to the industrial process (evaporation and Tomlinson boiler) with 3 mains criteria: energetic yield, sodium recovery and phenolic molecules production.In supercritical conditions, gas formation is competitive with char formation. Fast heating and high temperature permit to increase gas yield, thus energetic yield. However, conversion of phenolic compounds from lignin is low below 500°C, leading to a lower energetic yield than reference. In a continuous process, at high temperatures (700°C) and fast heating, energetic yield should be 2 times higher than industrial process (simulation at thermodynamic equilibrium). Wood prehydrolysis and softwood lead to a lower conversion of black liquor.Hydrothermal liquefaction produces a biocrude which can be burnt and phenolic platform compounds. Indeed, lignin is depolymerized into reactive fragments which can be degraded into platform phenolic molecules. Moreover, the recombination of these fragments, leading to biocrude formation, is favored by the carbohydrates derivatives in black liquor. Wood prehydrolysis and hardwood lead to better energetic and phenolic molecules yields.Sodium recovery is satisfactory for both processes. Substitution of Tomlinson recovery by a hydrothermal process is then possible.

[pt] A necessidade mundial de energia tem aumentado exponencialmente, no entanto, as reservas de combustíveis fósseis, além de produzirem sérios impactos ambientais, estão se esgotando ao longo dos anos. Por estas razões, muitos estudos vêm sendo feitos na busca de novas fontes renováveis de energia, como o reaproveitamento de resíduos de biomassa. Desta forma, o objetivo deste trabalho é estudar o processo de liquefação hidrotérmica (HTL) do bagaço de malte, gerado ao final do processo cervejeiro, para a produção de bio-óleo e biocarvão como potenciais combustíveis renováveis. A caracterização inicial da biomassa apresentou significativa quantidade de celulose e hemicelulose, alto teor de umidade e pequeno tamanho de partícula, sendo ideal para o processo. A HTL foi conduzida em um reator sob alta pressão em diferentes faixas de temperatura e tempos de residência. Uma modelagem cinética e termodinâmica foi realizada para a etapa inicial da liquefação, apresentando 62,08 kJ.mol−1 de energia de ativação e caráter endotérmico. Bio-óleo apresentou melhor rendimento, 18,2 por cento, a 300 C e 30 min, já o biocarvão atingiu 21,0 por cento de rendimento a 250 C e 5 min. A pequena diferença de valores, ao longo do tempo, comprovou que a maior produtividade ocorre sempre em 5 min, sendo este o tempo ótimo de reação. A análise do poder calorífico superior (PCS) demonstrou que altas temperaturas elevam a energia produzida. Em 5 min e a 300 C, melhores condições de operação, a HTL gerou um bio-óleo com PCS de 33,6 MJ.kg−1, sendo 27,8 por cento inferior a gasolina e um biocarvão com 26,7 MJ.kg−1, sendo 11,4 por cento superior ao carvão tradicional. Através das caracterizações finais, foi possível observar alta degradação da estrutura lignocelulósica da biomassa e identificar os compostos presentes no bio-óleo, indicando que os produtos da HTL apresentam alto potencial de utilização como combustíveis renováveis. / [en] The global energy needs have increased exponentially; however, fossil fuel reserves, in addition to producing serious environmental impacts, are running out over the years. For these reasons, many studies have been done in the search for new renewable energy sources, such as the reuse of biomass wastes. In this way, the purposes of this study are associated with the hydrothermal liquefaction process (HTL) of the malt bagasse, generated at the end of the brewing process, for the production of bio-oil and biochar as potential renewable fuels. The initial biomass characterization presented a significant amount of cellulose and hemicellulose, high moisture content and small particle size, ideal for the process. The HTL was conducted in a high pressure reactor in different temperature ranges and residence times. A kinetic and thermodynamic modeling was performed for the initial stage of liquefaction, presenting 62.08 kJ.mol−1 of activation energy and endothermic behavior. Bio-oil presented a better yield, 18.2 percent, at 300 C and 30 min, while the biochar reached 21.0 percent yield at 250 C and 5 min. The small distintion between values, over time, proved that the highest productivity always occurs at 5 min, which is the optimal reaction time. The higher heating value analysis (HHV) showed that high temperatures increase the energy produced. At 5 min and 300 C, better operating conditions, HTL generated a bio-oil with HHV of 33.6 MJ.kg−1, with 27.8 percent less than gasoline and a biochar with 26.7 MJ.kg−1, being 11.4 percent higher than traditional coal. Through the final characterization, it was possible to observe high degradation of the lignocellulosic structure of the biomass and to identify the compounds present in the bio-oil, indicating that the HTL products present high potential for use as renewable fuels.

Microalgae are a diverse group of oxygenic photosynthetic microorganisms which show great promise as a source of biofuel. However, significant challenges still remain before microalgae can be considered a viable source of biofuel. The main current challenges are nutrient sourcing and recycling as well as downstream processing. The algal cell wall and especially the presence of an algaenan cell wall in some Chlorophyte algae could be an important variable in determining downstream processing costs but not much comparative research has been done to elucidate this. The first part of the present study focuses on the recently isolated alga Pseudochoricystis ellipsoidea (Trebouxiophyceae) and its improvement and assessment for biofuel production. Random mutagenesis and FACS screening protocols were developed for the isolation of pigment and cell wall mutants but despite considerable efforts no suitable mutants could be identified in the first half of this project. Two 500 L raceway ponds as well as an algal growth room and bubble column bioreactors were set up to facilitate algal research at the University of Bath and assess the performance of P. ellipsoidea in realistic culture conditions. P. ellipsoidea showed a maximum growth of 1.53 divisions day-1 in semi-open raceway ponds, resistance to contamination and a 30% lipid content, making it particularly suitable for raceway pond cultures. In the second part of this project six species of Chlorophyte (“green”) algae, three of which produced algaenan, were compared for suitability to growth in anaerobic digestate and municipal wastewater as well as cell wall strength, permeability and suitability to hydrothermal liquefaction. We found that anaerobic digestate was a good medium for the growth of all species independently of autoclaving and that non-autoclaved wastewater was a very challenging medium. Algaenan production did not affect cell disruption by ultrasonication but growth stage and cell wall thickness did. Lipid extraction kinetics by chloroform/methanol were greatly affected by algaenan, meaning that this material is relatively impermeable to organic solvents. Cell wall thickness, cell volume and lipid content also had an effect on lipid extraction kinetics but this was only measurable after 180 minutes of extraction. 8 Hydrothermal liquefaction showed high solid and low oil yields, very low sulphur (≤0.1 %) as well as a 1.1 % -1.8 % nitrogen content which is significantly lower than most algal HTL studies to date. This suggests that stationary stage algae are more difficult to process but give a cleaner biocrude and reduce the loss of nitrogen through incorporation in the oil. Significant opportunities for optimisation still exist in the HTL process.