The demand for the efficient utilisation of straw biomass requires detailed analyses of its fundamental chemical structures, morphological complexity, individual cell wall components and the correlation of physicochemical to mechanical properties. The study involved two main areas: understanding the details of microstructure and characterisation/differentiation of properties of various profiled wheat straw. Comprehensive and systematic experimental programmes were therefore designed in order to thoroughly investigate the node and internode of wheat straw with quantitative appraisals and qualitative interpretations. This could contribute towards its valorisation in bio-refinery pathways. The sophisticated morphology of node and internode, inner and outer surface was investigated. It was found that the morphology across node area has a great variety when the longitudinal profile is investigated in the upwards direction to grain head. A 3D image of nodes illustrated the dense core with elliptical shaped rings organised in order to provide the echanical strength to the overall stem. The variation of cell wall composition across wheat straw node and internode showed that node yielded slightly higher Klason lignin, extractives and ash content than internode, which could be related to their morphology, precisely the higher ash and extractives content in the node are explained by thicker epidermis tissue. The physicochemical and mechanical properties of node and internode were differentiated and the effects of a combination of mild physical pre-treatment were monitored. The results indicated: i) the reduction of waxes from the outer surface, ii) significantly lower (P < 0.05) extractives and iii) the dissolution of silicon (Si weight %) on the outer surface of node and internode. The tensile strength of nodes and internodes after pre-treatments also resulted in a significant increase (P < 0.05). The accumulated characteristic data enabled the investigation of interfacial properties and bonding mechanisms of the inner and outer surface of wheat straw with thermosetting resins. Different surface functionalities and anatomical sections, altered the bonding performance, i.e. waxes and silica concentrated on the outer surface inhibited the quality of the interface. Nevertheless, the treatment improved interface (P < 0.05) between resins and the micro-porous surface of wheat straw by causing the microcellular structure of straw to expand and hence inspire the mechanical entanglement on a micro level upon resin solidification.

Mitigation of climate change and energy security are major driving forces for increased biomass utilization. The pulp and paper industry consumes a large proportion of the biomass worldwide including bark, wood residues, and black liquor. Due to the fact that modern mills have established infrastructure for handling and processing biomass, it is possible to lay foundation for future gasification based bio-refineries to poly-produce electricity, chemicals or bio-fuels together with pulp and paper products. There is a potential to export electricity or bio-fuels by improving energy systems of existing chemical pulp mills by integrating gasification technology. The present study investigates bio-fuel alternatives from the dry black liquor gasification (BLG) system with direct causticization and direct methane production from the catalytic hydrothermal gasification (CHG) system. The studied systems are compared with bio-fuel alternatives from the Chemrec BLG system and the improvements in the energy systems of the pulp mill are analyzed. The results are used to identify the efficient route based on system performance indicators e.g. material and energy balances to compare BLG systems and the conventional recovery boiler system, potential biofuel production together with biomass to biofuel conversion efficiency, energy ratios, potential CO2 mitigation combining on-site CO2 reduction using CO2 capture and potential CO2 offsets from biofuel use, and potential motor fuel replacement. The results showed that the dry BLG system for synthetic natural gas (SNG) production offers better integration opportunities with the chemical pulp mill in terms of overall material and energy balances. The biofuel production and conversion efficiency are higher in the CHG system than other studied configurations but at a cost of larger biomass import. The dry BLG system for SNG production achieved high biomass to biofuel efficiency and considerable biofuel production. The energy ratio is significant in the dry BLG (SNG) system with less biomass demand and considerable net steam production in the BLG island. The elimination of the lime kiln in the dry BLG systems resulted in reduced consequences of incremental biomass import and associated CO2 emissions. Hydrogen production in the dry BLG system showed the highest combined CO2 mitigation potential i.e. on-site CO2 capture potential and CO2 offset from biofuel replacing fossil fuel. The results also showed that the motor fuel replacement potential with SNG as compressed natural gas (CNG) replacing gasoline in the transport sector is significantly high in countries with large pulp industry. / QC 20120528

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

Orientador: Isaias de Carvalho Macedo / Tese (doutorado) - Universidade Estadual de Campinas, Faculdade de Engenharia Mecanica / Made available in DSpace on 2018-08-11T15:17:55Z (GMT). No. of bitstreams: 1 Seabra_JoaquimEugenioAbel_D.pdf: 2147529 bytes, checksum: e9ebd63f7d029f2346cd2c026285a2cf (MD5) Previous issue date: 2008 / Resumo: O objetivo deste trabalho foi investigar, no cenário prospectivo, as opções tecnológicas que deverão permitir o melhor aproveitamento da biomassa da cana e suas possíveis implicações no contexto das usinas. Além das possibilidades envolvendo o uso mais diversificado da sacarose, este estudo investigou o aproveitamento do bagaço e palha da cana considerando quatro tecnologias: geração de. energia elétrica através da cogeração com ciclos a vapor (opção atualmente comercial); produção de etanol através da hidrólise (opções para curto, médio e longo prazo); geração de energia elétrica a partir da gasificação da biomassa integrada a ciclos combinados (BIG/GT -C C) (opções para médio-longo prazo); e a produção de combustíveis de síntese a partir da gasificação da biomassa (opções para médio-longo prazo). Para cada uma destas opções, foram discutidos os aspectos tecnológicos mais importantes e estimados os rendimentos e custos de sistemas integradps a uma usina de cana, além de terem sido avaliados seus efeitos nos balanços de energia e emissões de GEE. Neste trabalho ficou evidenciado o grande benefício econômico que pode representar o uso diversificado dos açúcares da cana para a produção de produtos de maior valor agregado, como aminoácidos, por exemplo. No caso da fibra da cana, foi avaliado que opções atualmente comerciais já propiciariam a geração de excedentes de energia elétrica superiores a 140 kWh/tc, com custos em tomo de 100 R$/MWh, para os casos de cogeração com alta pressão e uso de alguma palha em conjunto com o bagaço. Para o futuro, sistemas de cogeração com ciclos combinados deverão permitir que os níveis de excedentes ultrapassem os 200 kWh/tc, mas com custos também superiores (> 140 R$/MWh). Pensando na produção de combustíveis, as opções de curto prazo para a conversão bioquímica do bagaço possibilitariam um aumento na produção de etanol de cerca de 20 L/tc (a um custo de ~680 R$/m / Abstract: The objective of the present work was to investigate, in the prospective scenario, the technology options that might lead to a better use of sugar cane biomass and their possible implications in the mills' context. Besides the possibilities involving the diversified use of cane's sugars, this study evaluated the use of bagasse and cane trash considering four technologies: power generation with c~nventional steam cycles (current options); ethanol production through biomass hydrolysis (options for short, middle and long term); power generation through biomass gasification integrated to combined cycles (BIG/GT -CC) (options for middle-Iong term); and the production of synthetic fuels through biomass gasification (options for middle-Iong term). For each one of these options, were discussed the main technological aspects and estimated the yields and costs for systems integrated to cane mills; their effects over energy and GHG emission balances were assessed as well. In this work was evidenced the great economical benefit which would represent the díversífied use of cane's sugars for the production of higher value products, such as amino acids, for example. For the fiber fraction, it was concluded that current commercial options could already lead to electricity surpluses as high as 140 kWh/tc, with costs around 100 R$/MWh, for those configurations with high pressure boilers and using some amount of trash in addition to bagasse. For the future, combined cycles systems might lead to electricity surpluses higher than 200 kWh/tc, but also with higher costs (> 140 R$/MWh). Regarding fuels production, the short term options for biochemical conversion would allow 20 L/tc ethanol production increasing (produced at ~680 R$/m3), while the long term yields could reach 40 L/tc, with costs at 270 R$/m3. For thermochemical conversion, in the middle-Iong term, Fischer- Tropsch liquids, for instance, could be produced with yields closed to 490 MJ/tc, at costs around 30 R$/GJ. As for energy and GHG emission balances, for the current situation the energy ratio of ethanol production was evaluated as 9.4, with a life cycle net avoided emission of 1.8 t C02eq/m3 anhydrous. But for 2020, considering the expectations about the evolution on cane production and the availability of advanced technologies for biomass use, the energy ratio might rise to 14.2, while net avoided emissions would reach 2.9 t C02eq/m3 anhydrous, based on the adoption ofBIG/GT-CC systems for biomass use. Bearing all these aspects in mind, a broader comparison of the effects of these technology options utilization on the overall mill performance is presented in the end of the study, pointing out their implications for the establishment of the future sugar cane bio-refineries / Doutorado / Doutor em Planejamento de Sistemas Energéticos

La bioconversion des biomasses lignocellulosiques est actuellement un grand défi pour le développement de technologies de bio-raffinage. Le manque de connaissances des mécanismes de liquéfaction et de saccharification est l’un des principaux facteurs qui pénalisent le développement des procédés de bio-raffinage. Ce travail est centré sur le développement d’analyses physiques et biochimiques in-situ (viscosimétrie, focus beam reflectance measurement) et ex-situ (rhéometrie, granulométrie laser, morphogranulométrie, sédimentation…) pour améliorer la compréhension des mécanismes de déstructuration desfibres lignocellulosiques et caractériser les cinétiques de libération de carbone fermentescible. Des substrats modèles (cellulose microcristalline, papier Whatman) et industriels (pâte à papier, bagasse de canne à sucre) ont été utilisés avec différentes conditions d'hydrolyse (1% à 30%w/v, 0.1 à 0.5mL enzyme/ g cellulose). Les résultats obtenus ont permis:- de proposer et de valider les mesures in-situ de la viscosité de la suspension et de la distribution des longueurs de corde des particules, ainsi que sa conversion en distribution de diamètre.- de montrer l'impact de la nature et de la concentration de substrat et des ratios enzyme/substrat sur les évolutions des paramètres physico-biochimiques lors de l'hydrolyse. Ces effets ont été quantifiés sur les limitations de transfert.- d'établir un modèle phénoménologique de comportement rhéologique des suspensions initiales- de montrer que les cinétiques physico et bio-chimiques sont des cinétiques du second ordre- de montrer que, pour des hydrolyses à haute teneur en matière sèche, on peut réduire considérablement la limitation des transferts liée aux hautes concentrations et contrôler la cinétique de production de glucose par une stratégie d’ajouts cumulés desubstrat. / In the context of biofuels and chemicals production of petroleum substitutes from renewable carbon, bioconversion of lignocellulose biomasses is currently a major challenge. The limited knowledge of liquefaction and saccharification mechanisms stands as the main factor which penalizes bio-refinery progress. The present work is centred on the development of in-situ(viscosimetry, focus beam reflectance measurement) and ex-situ (rheometry, diffraction light scattered, morphometry, decantation…) physical and biochemical analysis to expand our understanding of the destructuration mechanisms of lignocellulose fibres and to characterise the release kinetics of fermentable cellulosic carbon. Model (microcrystalline cellulose,Whatman paper) and industrial (paper-pulp, sugarcane bagasse) lignocellulose matrices under a large range of hydrolysis conditions (1% up to 30%w/v and 0.1 up to 0.5mL enzyme/g cellulose) were studied during 24h hydrolysis experiments (pertinent period to appreciate transfer limitations). Our scientific results allow:- to propose and validate the in-situ measurements of the suspension viscosity and chord length distribution together with its conversion into particle size distribution.- to demonstrate the impact of the substrate nature and concentration and of the enzymatic ratios on the evolution of physical- and biochemical parameters during hydrolysis. Their impacts on transfer phenomena were quantified.- to establish phenomenological models for rheological behaviour of initial suspensions.- to describe all physical (viscosity, particle size) and biochemical (substrate and product) kinetics by second order reaction models.- to demonstrate that, for high dry matter concentration hydrolysis, a cumulative feeding substrate strategy allows considerably reducing the transfer limitations linked to high concentrations and to control the glucose production kinetics.