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The problems of rape seed methyl ester (RME) production process by-products utilization were analyzed, statistical data for the capacities of biodiesel production and by-products generation were presented, the prospects of biodiesel production expansion, properties and environmental impact, main production technologies, Lithuanian and foreign countries experience were described, the main aims and tasks of work were defined. The investigation of glycerol – major by-product of RME production process – utilization was accomplished. One of the new possible utilization methods was researched, when combusting glycerol with highly sulphurous (~ 2.0 %) heavy fuel oil to reduce SO2 emissions, which limit value in the flue gas can not exceed 1700 mg/Nm3 (according to EU Directive 1999/32EC and LAND 43-2001 „Norms for the exhaust of pollutants from large fuel burning equipment“). The heavy fuel oil – glycerol emulsion was prepared in the pilot plant operating in the laboratory conditions, the most optimal ratio (1:1) for heavy fuel oil emulsification was estimated, the dispersivity investigation of heavy fuel oil - glycerol emulsion samples was performed. The experimental heavy fuel oil and obtained emulsion combustion investigations were carried out in VGTU Institute of Thermal Insulation pilot plant and in the thermal oxidation boiler „UMISA-CR/11,9 (13)“ at JCS „Rietavo veterinarinė sanitarija“. The CO, NOx, SO2 and particulate matter concentration values for heavy fuel oil and... [to full text] / Baigiamajame darbe išnagrinėtos rapso aliejaus metilo esterio (RME) gamybos proceso šalutinių produktų utilizacijos problemos, pateikti statistiniai duomenys apie biodyzelino gamybos bei susidarančių šalutinių produktų apimtis, aprašytos biodyzelino gamybos plėtros perspektyvos, savybės bei poveikis aplinkai, pagrindinės gamybos technologijos, Lietuvos bei užsienio šalių patirtis šioje srityje, apibrėžti pagrindiniai darbo tikslai ir uždaviniai. Atliktas RME gamybos proceso pagrindinio šalutinio produkto – glicerolio – utilizacijos tyrimas. Išanalizuotas vienas iš naujų galimų utilizavimo būdų - deginti glicerolį kartu su sieringu (~ 2,0 %) mazutu, siekiant sumažinti SO2 emisijas, kurių nustatyta ribinė vertė dūmuose negali būti didesnė kaip 1700 mg/Nm3 (pagal ES Direktyvą 1999/32EC ir LAND 43-2001 „Išmetamų teršalų ir didelių kurą deginančių įrenginių normos“). Laboratorinėmis sąlygomis stendiniame įrenginyje paruošta mazuto-glicerolio emulsija, nustatytas optimaliausias mazuto emulgavimo gliceroliu santykis (1:1), atlikti mazuto emulsijos bandinių homogeniškumo tyrimai. Eksperimentiniai mazuto bei gautų emulsijų deginimo bandymai buvo atlikti VGTU Termoizoliacijos instituto eksperimentiniame stende bei UAB „Rietavo veterinarinė sanitarija“ termooksidaciniame katile „UMISA-CR/11,9 (13)“. Išmatuotos mazuto ir mazuto-glicerolio emulsijos CO, NOx, SO2 ir kietųjų dalelių emisijos bei palygintos su jų didžiausiomis leistinoms vertėmis. Remiantis gautais rezultatais pateiktos... [toliau žr. visą tekstą]

La recherche de sources d’énergie fiables ayant un faible coût environnemental est en plein essor. L’hydrogène, étant un transporteur d’énergie propre et simple, pourrait servir comme moyen de transport de l’énergie de l’avenir. Une solution idéale pour les besoins énergétiques implique une production renouvelable de l’hydrogène. Parmi les possibilités pour un tel processus, la production biologique de l’hydrogène, aussi appelée biohydrogène, est une excellente alternative. L’hydrogène est le produit de plusieurs voies métaboliques bactériennes mais le rendement de la conversion de substrat en hydrogène est généralement faible, empêchant ainsi le développement d’un processus pratique de production d’hydrogène. Par exemple, lorsque l’hydrogène est produit par la nitrogénase sous des conditions de photofermentation, chaque molécule d’hydrogène constituée requiert 4 ATP, ce qui rend le processus inefficace. Les bactéries photosynthétiques non sulfureuses ont la capacité de croître sous différentes conditions. Selon des études génomiques, Rhodospirillum rubrum et Rhodopseudomonas palustris possèdent une hydrogénase FeFe qui leur permettrait de produire de l’hydrogène par fermentation anaérobie de manière très efficace. Il existe cependant très peu d’information sur la régulation de la synthèse de cette hydrogénase ainsi que sur les voies de fermentation dont elle fait partie. Une surexpression de cette enzyme permettrait potentiellement d’améliorer le rendement de production d’hydrogène. Cette étude vise à en apprendre davantage sur cette enzyme en tentant la surexpression de cette dernière dans les conditions favorisant la production d’hydrogène. L’utilisation de résidus organiques comme substrat pour la production d’hydrogène sera aussi étudiée. / The search for alternative energy sources with low environmental impact is in great expansion. Hydrogen, an elegant and simple energy transporter, could serve as means of transporting energy in the future. An ideal solution to the increasing energy needs would imply a renewable production of hydrogen. Out of all the existing possibilities for such a process, the biological production of hydrogen, also called biohydrogen, is an excellent alternative. Hydrogen is the end result or co-product of many pathways in bacterial metabolism. However, such pathways usually show low yields of substrate to hydrogen conversion, which prevents the development of efficient production processes. For example, when hydrogen is produced via nitrogenase under photofermentation conditions, each hydrogen molecule produced requires 4 molecules of ATP, rendering the process very energetically inefficient. Purple non-sulfur bacteria are highly adaptive organisms that can grow under various conditions. According to recent genomic analyses, Rhodospirillum rubrum and Rhodopseudomonas palustris possess, within their genome, an FeFe hydrogenase that would allow them to produce hydrogen via dark fermentation quite efficiently. Unfortunately, very little information is known on the regulation of the synthesis of this enzyme or the various pathways that require it. An overexpression of this hydrogenase could potentially increase the yields of substrate to hydrogen conversion. This study aims to increase our knowledge about this FeFe hydrogenase by overexpressing it in conditions that facilitate the production of hydrogen. The use of organic waste as substrate for hydrogen production will also be studied.

Compliance mismatch is a significant hurdle to long-term patency in small-diameter arterial bypass grafts. Vascular tissue engineering has the potential to produce compliant, non-thrombogenic small-diameter grafts. However, current engineered grafts are relatively non-compliant, resulting in intimal hyperplasia and graft occlusion when subjected to arterial pressures. This research investigates the mechanical and biological properties of engineered constructs based on a biodegradable synthetic elastomer, poly(glycerol sebacate) (PGS). Several methods for fabricating porous PGS scaffolds in a tubular geometry were developed and compared. Adult baboon vascular cells were cultured in the scaffolds under various in vitro experimental conditions, including variations in initial cell seeding density, the type of scaffold used for culture, culture time, scaffold material, and hydrostatic pressure, and properties of the resultant constructs were compared. Scaffold fabrication using heat-shrinkable mandrels and glass tubes coated with hyaluronic acid significantly decreased tolerances of wall thickness and mechanical properties, improved handling, and decreased culture time required to reach luminal cellular confluence compared to scaffolds made with other fabrication techniques. Altering scaffold material from PGS to poly(lactide-co-glycolide) (PLGA), a benchmark biomaterial, did not affect scaffold yield, porosity, or luminal cellular confluence. Extracellular matrix (ECM) deposition increased with SMC-only culture time, and ECM deposition and remodeling during culture influenced construct compliance. Compared to PLGA scaffolds, PGS scaffolds promoted elastin crosslinking by SMCs and elastic tissue properties but attenuated collagen deposition. Hydrostatic pressure promoted ECM synthesis and deposition by SMCs and decreased construct compliance. Collagen and crosslinked elastin content in constructs correlated positively with construct burst pressure, and a negative correlation dependent on scaffold type was found between collagen content and construct compliance at low pressures. The systematic investigation of culture conditions in this research provides insights into the control of engineered blood vessel properties. The central hypothesis of this work, that grafts engineered from PGS scaffolds and adult vascular cells under biomimetic in vitro culture conditions can possess compliance comparable to autologous vessels, is true at pressures below 60 mmHg and demonstrates potential for PGS-based vascular tissue engineering. Overall, this work provides tools for engineering tubular soft tissues based on porous PGS scaffolds.

Στην παρούσα διατριβή μελετήθηκε η δυνατότητα αξιοποίησης της γλυκερόλης η οποία αποτελεί ένα σημαντικό παραπροϊόν της βιομηχανίας του βιοντήζελ. Συνήθως αντιστοιχεί στο 10% της παραγόμενης ποσότητας του βιοντήζελ. Αυτό το γεγονός συντέλεσε στην υπερβολική αύξηση της παραγωγής της γλυκερόλης σε παγκόσμιο επίπεδο. Η περίσσεια της γλυκερόλης δε μπορεί να απορροφηθεί από τους συνηθισμένους βιομηχανικούς κλάδους που τη χρησιμοποιούν. Επομένως θα πρέπει να βρεθεί τρόπος αξιοποίησης αυτού του συσσωρευμένου παραπροϊόντος. Η κλασική μέθοδος επεξεργασίας αφορά τη χημική οδό μέσω της οποίας η γλυκερόλη μπορεί να μετατραπεί σε άλλα χημικά μόρια. Από την άλλη πλευρά βιοχημικές διεργασίες όπως η αναερόβια χώνευση, η ζύμωση αλλά και η μικροβιακή κυψελίδα καυσίμου μπορούν να μετατρέψουν τη γλυκερόλη σε μεθάνιο, υδρογόνο και ηλεκτρικό ρεύμα αντίστοιχα. Οι διεργασίες αυτές, οι οποίες αποτέλεσαν και το αντικείμενο έρευνας της διατριβής, είναι λιγότερο δαπανηρές από τις χημικές και επιβαρύνουν λιγότερο το περιβάλλον. Η διεργασία της αναερόβιας χώνευσης διεξήχθη σε συμβατικό αντιδραστήρα τύπου CSTR και σε ταχύρυθμο τύπου PABR. Στα πειράματα μελετήθηκε η επίδραση της συγκέντρωσης της γλυκερόλης στο ρυθμό παραγωγής του μεθανίου. Από τα αποτελέσματα που λήφθησαν φάνηκε ότι ο CSTR δεν άντεχε οργανική φόρτιση πέραν των 0.25 g COD/L/d, ενώ από την άλλη πλευρά ο PABR λειτούργησε σε υπερ 10-πλάσια φόρτιση της τάξης των 3 g COD/L/d με παραγωγή μεθανίου 0.982 ± 0.089 L/L/d. Με το πέρας της πειραματικής διαδικασίας ακολούθησε μοντελοποίηση της διεργασίας, αρχικά για την περίπτωση του CSTR και κατόπιν χρησιμοποιήθηκε το ίδιο μοντέλο με τροποποίηση για την περίπτωση του PABR. Η ζυμωτική παραγωγή του υδρογόνου διεξήχθη επιτυχώς σε αντιδραστήρες διαλείποντος έργου. Μελετήθηκε η επίδραση της αρχικής συγκέντρωσης της γλυκερόλης και η επίδραση του αρχικού pH στην παραγωγή του υδρογόνου. Βρέθηκε ότι η μέγιστη παραγωγή υδρογόνου, 27.3 mL H2/ g COD γλυκερόλης, προήθλε όταν η αρχική συγκέντρωση είχε τεθεί στα 8.3 g COD/L. Η ζυμωτική παραγωγή υδρογόνου φάνηκε να ευνοείται σε pH γύρω από το 6.5. Εν συνεχεία, εξετάστηκε η ζυμωτική παραγωγή υδρογόνου σε συνεχή αντιδραστήρα. Η παραγωγή του υδρογόνου ήταν υπερβολικά ασταθής, γεγονός που πιθανότατα να οφείλεται στην απομάκρυνση της υδρογονοπαραγωγού βιομάζας από τον αντιδραστήρα σε συνδυασμό με την παρουσία υδρογονοκαταναλωτών μικροοργανισμών. Για την παραγωγή ηλεκτρικού ρεύματος από γλυκερόλη χρησιμοποιήθηκε μικροβιακή κυψελίδα καυσίμου διάταξης Η-type σε συνθήκες διαλείποντος έργου. Μελετήθηκε η επίδραση της αρχικής συγκέντρωσης της γλυκερόλης στην παραγωγή ηλεκτρικού ρεύματος. Παρατηρήθηκε ότι η συγκέντρωση των 3.2 g COD/L απέφερε τη μέγιστη απόδοση Coulomb (CE) 34.09 %. Η περαιτέρω αύξηση της συγκέντρωσης οδήγησε σε μείωση της CE. Αυτό ίσως να οφείλεται σε κινητικό περιορισμό που υπέστησαν οι ηλεκτροχημικά ενεργοί μικροοργανισμοί όταν εκτέθηκαν σε υψηλές συγκεντρώσεις γλυκερόλης. / This study focused on the valorization of glycerol which is an important by-product of the biodiesel industry corresponding to 10 % of the produced biodiesel amount. This fact contributed to the increase of the global production of biodiesel, to a point at which the industries which traditionally consumed glycerol could not absorb. This situation should be overcome through new outlets on glycerol exploitation. Usually, glycerol is treated by chemical processes in order to form new chemical compounds. On the other side, biochemical processes like anaerobic digestion and fermentation or the technology of microbial fuel cells could potentially transform glycerol into methane, hydrogen and electric current respectively. These processes, which are the subject of this Ph.d, are preferable to their chemical counterparts due to the low energy demand and reduced environmental pollution. The anaerobic digestion process was conducted in a conventional CSTR reactor and in a high rate reactor, the PABR. The experiments dealt with the effect of glycerol concentration on the methane production rate. The obtained results showed that the CSTR could not withstand organic loadings above 0.25 g COD/L/d, however PABR operated at organic loading 10 times higher than CSTR such as 3 g COD/L/d and resulted to a methane production rate of 0.982 ± 0.089 L/L/d. A model was developed for both the CSTR and the PABR digesters. Fermentative hydrogen production was conducted successfully in batch reactors. The effect of the initial glycerol concentration and initial pH on hydrogen production was studied. A maximum yield, 27.3 mL H2/ g COD glycerol, was obtained when glycerol concentration was 8.3 g COD/L and the pH 6.5. Moreover, the fermentation of glycerol took place in a CSTR in order to investigate the continuous production of hydrogen. Hydrogen production was unstable, possibly due to the washout of proper biomass from the reactor. For electricity generation from glycerol, an H-type microbial fuel cell was used in batch mode. The effect of the initial glycerol on the electric current was studied. A maximum Coulombic efficiency (CE) 34.09% was obtained at a glycerol concentration of 3.2 g COD/L. A further increase of glycerol drove to a drop of the CE. Probably, this happened since the electrochemical microorganisms were inhibited by the high glycerol concentration.

118 f. / Submitted by Ana Hilda Fonseca (anahilda@ufba.br) on 2013-04-11T17:50:31Z No. of bitstreams: 1 Dissertação de Mestrado - PDF[1].pdf: 2378495 bytes, checksum: 988193a81cd9a137da1f1458daa95968 (MD5) / Approved for entry into archive by Ana Hilda Fonseca(anahilda@ufba.br) on 2013-05-14T17:22:34Z (GMT) No. of bitstreams: 1 Dissertação de Mestrado - PDF[1].pdf: 2378495 bytes, checksum: 988193a81cd9a137da1f1458daa95968 (MD5) / Made available in DSpace on 2013-05-14T17:22:34Z (GMT). No. of bitstreams: 1 Dissertação de Mestrado - PDF[1].pdf: 2378495 bytes, checksum: 988193a81cd9a137da1f1458daa95968 (MD5) Previous issue date: 2011 / CAPES / Devido aos inúmeros incentivos governamentais que impulsionam a produção do Biodiesel no mundo, tal combustível está sendo produzido largamente, e um fator preocupante frente a esse crescimento é o destino do glicerol excedente, já que seu uso é condicionado ao seu grau de pureza, que deve estar usualmente acima de 95%. No caso do glicerol bruto, resultante do processo de transesterificação do biodiesel, são necessários processos complexos e onerosos para que essa matéria-prima alcance as exigências em grau de pureza necessária para seu emprego. Além disso, os mercados tradicionais que o consomem (indústria de cosméticos, resinas, indústria farmacêutica, têxtil e alimentícia) têm uma capacidade limitada de absorção de quantidades maiores desse sub-produto. Sendo assim, esse trabalho tem como objetivo promover modificações estruturais na molécula do glicerol (comercial, alcalino e bruto), utilizando como agentes oxidantes os sais de bismuto (Zn(BiO3)2 e NaBiO3), NaClO e KBrO3/NaHSO3. As reações foram realizadas em ácido acético , ácido lático, acetona, água, com variação de tempo, temperatura, concentração dos reagentes e catalisadores. Essa metodologia sintética tem como finalidade gerar produtos com maior valor agregado tornando o glicerol um sub-produto mais reaproveitado e competitivo no mercado. Os melhores resultados na conversão do glicerol para os produtos mono, di e triacetilados foram alcançados utilizando 1mol% do catalisador NaBiO3 em diferentes concentrações de ácido acético glacial. Na ausência do catalisador a reação também ocorre, porém com tempo elevado. Em nenhum dos experimentos ocorreu à oxidação do glicerol. O modelo experimental realizado mostrou que é necessário excesso de ácido a fim de promover o equilíbrio na direção da conversão do glicerol e seletividade para os produtos mais valiosos comercialmente, o di e triacetilados. / Salvador

Le glycérol est un coproduit de la filière des biocarburants obtenu par transestérification destriglycérides. Avec le développement des biocarburants, la production de glycérol est en pleine croissance.La consommation de glycérol comme additif dans les industries cosmétique, pharmaceutique et agroalimentairen’augmentant pas de manière aussi significative, l’excédent doit être valorisé. L’une des voies devalorisation est la synthèse du carbonate de glycérol qui est un intermédiaire intéressant pour la chimie fine.La méthode de synthèse utilisée au sein de l’industrie Novance est la carbonylation du glycérol par l’urée enprocédé discontinu. Cette réaction produit, en plus du carbonate de glycérol, une grande quantitéd’ammoniac gazeux extrait du milieu réactionnel par dépression. L’ampleur de ce dégagement gazeux ainsique son irrégularité au cours du temps représente la limitation de production du procédé discontinu. Le sujetde cette étude est de développer le procédé continu de cette synthèse afin de pallier ce problème. Pourréaliser le suivi de la réaction, des méthodes analytiques ont été développées dans un premier temps. Avecces outils, les connaissances du système discontinu ont été approfondies pour déterminer les critères dechoix du procédé continu. Une unité de désorption réactive a été ensuite conçue pour créer un systèmebiphasique gaz-liquide à contre-courant. Une série d’essais préliminaires a permis le développement duprocédé qui a été optimisé par un plan de Doehlert. / Glycerol is a by-product of biofuels obtained by transesterification of triglycerides. With developmentof biofuel, glycerol production is growing. The use of glycerol in cosmetic, pharmaceutical and food industriesis not increasing in the same way, so the surplus should be preferable to market. One way of development isthe synthesis of glycerol carbonate which is an interesting intermediate for fine chemistry. The synthesisused by Novance is carbonylation of glycerol by urea with a batch process. This reaction produces, as wellas glycerol carbonate, a high quantity of gaseous ammonia extracted from reactive mixture in a vacuum. Thescale of this gaseous emission and its irregularity during synthesis show the limits of production using abatch process. The aim of this study is to develop the continuous process of the synthesis to solve thisproblem. To carry out the monitoring of the reaction, at first, analytical methods were used. With suchmethods, knowledge of the batch process was improved in order to determine the best criteria for acontinuous process. A unit of reactive desorption was then elaborated to create a liquid-gas biphasic systemin a counter-flow configuration. A series of preliminary experiments were performed to develop the processwhich was optimised by a Doehlert plan.

Made available in DSpace on 2016-06-02T19:56:50Z (GMT). No. of bitstreams: 1 4994.pdf: 4218201 bytes, checksum: 2533718bb0a463f333c6c34f4b0357b9 (MD5) Previous issue date: 2013-02-15 / Universidade Federal de Sao Carlos / An alternative of renewable fuel is the anhydrous ethanol from biomass. Its production has to aim the minimum consumption of hydric and energetic resources. The bottleneck of the process is located in the downstream that requires technological development with thermodynamics reasoning. This master s degree seeks to address this aspect by studying the dehydration of ethanol by extractive distillation making use of liquid solvent glycerol, salts of potassium acetate and calcium chloride, or both kinds of resources. These resources, called separation agents, can "break" the barrier of azeotropy and have advantages such as no top product contamination and lower energy consumption. The rectification column plus the conventional dehydration system are replaced by a single extractive distillation column which is itself the rectification column, adding the separating agents in the reflux stream. The simulation is performed in steady state using a rigorous model for calculating the column. For non-electrolytic systems UNIFAC model was used, and for systems involving electrolytes UNIFAC model with the addition of the Debye-Hückel term and UNIFAC-Dortmund model. Maximum values for the mean of absolute deviations of temperature and of ethanol molar fraction in vapor phase were 5,51 K and 0,0646 respectively. Though, it was observed that the deviations were higher in the region of least ethanol concentration. The simulation of extractive column with glycerol converged generating anhydrous ethanol following the specification, being a proof of the concept that the application of the proposed process was successful. The simulation of the saline extractive distillation presented difficulties of convergence which will need to be studied in future works. / Uma alternativa de combustível renovável é o etanol anidro a partir da biomassa. Sua produção deve visar o consumo mínimo de recursos hídricos e energéticos. O gargalo do processo está localizado no downstream que necessita de desenvolvimento tecnológico com fundamentação da termodinâmica. Este mestrado busca trabalhar neste aspecto estudando a desidratação do etanol pela destilação extrativa fazendo uso do solvente líquido glicerol, dos sais acetato de potássio e cloreto de cálcio, ou de ambos os tipos de recursos. Esses recursos, chamados de agentes de separação, conseguem quebrar a barreira da azeotropia e possuem vantagens como não contaminação do produto de topo e menor consumo de energia. A coluna de retificação mais o sistema de desidratação convencional são substituídos por uma única coluna de destilação extrativa que é a própria coluna de retificação, adicionando os agentes de separação na corrente de refluxo. A simulação é realizada no estado estacionário utilizando modelo rigoroso de cálculo da coluna. Para sistemas não eletrolíticos foi utilizado o modelo UNIFAC, e para sistemas envolvendo eletrólitos os modelos UNIFAC com adição do termo de Debye-Hückel e UNIFAC-Dortmund. Valores máximos para os desvios absolutos médios de temperatura e de fração molar de etanol na fase vapor foram de 5,51 K e 0,0646, respectivamente. Apesar disso, observou-se que os desvios foram maiores na região de menor concentração de etanol. A simulação da coluna extrativa com glicerol convergiu gerando etanol anidro conforme a especificação, mostrando ser uma prova do conceito de que a aplicação do processo proposto foi bem sucedida. A simulação da destilação extrativa salina apresentou dificuldades de convergência que deverão ser estudadas em futuros trabalhos.

Made available in DSpace on 2016-06-02T19:56:56Z (GMT). No. of bitstreams: 1 6181.pdf: 2281247 bytes, checksum: ab77d4d6451a6d9054abc19310067ed2 (MD5) Previous issue date: 2014-03-25 / Financiadora de Estudos e Projetos / This study aimed to evaluate the influence of the hydraulic retention time (HRT) on hydrogen production using crude glycerol as a substrate in an anaerobic fluidized bed reactor (AFBR ) . The reactor had a volume of 1979 cm3, which was varied HDT in eight stages: Stage I, II, III, IV, V, VI , VII, VIII with HDT of 14, 12 , 10,8 , 6, 4 , 2 and 1 hour. The temperature was controlled at 55 °C, fixing the substrate concentration in the amount of 5 gL -1 . The inoculum used was granular sludge from the thermophilic anaerobic reactor and upflow sludge blanket ( UASB ) for the treatment of vinasse, located at Usina São Martinho , Pradópolis - SP . The results showed that the yield of hydrogen (HY) remained constant between the HDT of 2h to 14h (1.2 H2.mol glycerol and 1.4 mol -1) HRT of 1h and the yield was higher ( 3 moles H2 . glycerol mol -1). The volumetric H2 production was increased with decreasing HRT , with its maximum value of 1508.7 mL.h - 1.L - 1 in lower applied TDH (1h) . The biogas produced was composed of CO2 and H2. The composition varied with the decrease in HRT from 14 to 2h (Step IVII ) in the first seven stages (14 to 2 h ), reaching a mean rate between 50 and 60%. In the last phase, which HRT was 1h , the percentage of H2 biogas reached the maximum value of 70 % . The major metabolites obtained during the first seven stages of operation of the reactor were: Acetic acid (4.5 to 18%), butyric acid (4.3 to 21% ), ethanol (14 to 29%) and 1,3-propanediol (34 to 50%). As for 1h note the HDT of the presence of propionic acid (56%), acetic acid ( 11.5%) and 1,3- propanediol ( 30%). / Este estudo teve como objetivo avaliar a influência do tempo de detenção hidráulica (TDH) sobre a produção de hidrogênio, utilizando glicerol bruto como substrato em reator anaeróbio de leito fluidizado (RALF). O reator possuía um volume de 1979 cm3, no qual se variou o TDH em oitos fases: Fase I, II, III, IV, V, VI, VII, VIII com os respectivos TDH de 14, 12, 10,8, 6, 4, 2, e 1 hora. A temperatura foi controlada à 55 oC, fixando a concentração no valor de 5 g.L-1 de DQO. O inóculo utilizado foi proveniente de lodo granulado do reator termofílico anaeróbio de fluxo ascendente e manta de lodo (UASB) para o tratamento de vinhaça, localizado na Usina São Martinho, Pradópolis-SP. Os resultados mostraram que o rendimento de hidrogênio (HY) permaneceu constante entre os TDH de 14h à 2h (1,2 e 1,4 mol H2.mol glicerol-1) e no TDH de 1h o rendimento foi maior (3 mol H2.mol glicerol-1). Já a produção volumétrica de H2, sob a pressão de à 1 atm e temperatura de 55 oC, teve aumento com a diminuição do TDH, sendo seu valor máximo de 1508,7 mL.h-1.L-1 no menor TDH aplicado (1h). O biogás teve como principias compostos CO2 e H2. A composição de H2 no biogás variou com a diminuição do TDH de 14 para 2h (Fase I a VII) nas sete primeiras fases (14 a 2 h) atingindo um valor médio percentual entre 50 e 60 %. Na última fase, cujo TDH foi de 1h, o percentual de H2 biogás atingiu o valor máximo de 70%. Os principais metabólitos obtidos durante as sete primeiras fases de operação dos reatores foram: ácido acético (4,5 a 18%), ácido butírico (4,3 a 21%), etanol (14 a 29%) e 1,3-propanodiol (34 a 50%). Já para o TDH de 1h nota-se a presença de ácido propiônico (56%), ácido acético (11,5%) e 1,3-propanodiol (30%).

Submitted by Izabel Franco (izabel-franco@ufscar.br) on 2016-09-30T18:55:37Z No. of bitstreams: 1 DissTCN.pdf: 1750863 bytes, checksum: 7f270955d14599a5df96c67c05642037 (MD5) / Approved for entry into archive by Ronildo Prado (ronisp@ufscar.br) on 2016-09-30T19:05:44Z (GMT) No. of bitstreams: 1 DissTCN.pdf: 1750863 bytes, checksum: 7f270955d14599a5df96c67c05642037 (MD5) / Approved for entry into archive by Ronildo Prado (ronisp@ufscar.br) on 2016-09-30T19:05:52Z (GMT) No. of bitstreams: 1 DissTCN.pdf: 1750863 bytes, checksum: 7f270955d14599a5df96c67c05642037 (MD5) / Made available in DSpace on 2016-09-30T19:11:43Z (GMT). No. of bitstreams: 1 DissTCN.pdf: 1750863 bytes, checksum: 7f270955d14599a5df96c67c05642037 (MD5) Previous issue date: 2015-04-24 / Fundação de Amparo à Pesquisa do Estado do Amazonas (FAPEAM) / This study aimed to produce propionic acid, 1,3-propanediol and hydrogen in anaerobic fluidized bed reactor with grounded tire as support material for immobilization of biomass. The experiment took place during 278 days in six distinct phases distributed according to the hydraulic retention time (HRT), which ranged between 8 and 0.5 h. The reactor was maintained at mesophilic conditions (30 ° C) with controlled pH between 4.5 and 5.5 and crude glycerol as carbon source at a concentration of 5 g L-1. The inoculum used in the experiment was derived from the processing of poultry slaughterhouse wastewater station. The results show that the consumption of substrate conversion reached the highest value (89.8 %) in HRT of 6 hours. The biogas produced was composed of H2 and CO2 and the greatest recorded content of H2 has been reached (81.2%) in HRT of 4 hours. The principal soluble metabolite produced were propionic acid and 1,3-propanediol, with maximum yields of 1,77 and 0,82 mol.molglicerol -1, respectively. Both maximum yields were achieved in HRT of 8 h. At all stages of this work occurred predominantly propionic acid, with maximum molar percentage (96,9 %) achieved in HRT of 0,5 h. The second predominant metabolite obtained was 1,3- propanediol, achieving greater molar percentage (29.4%) in HRT of 6 hours. / O presente trabalho teve por objetivo produzir ácido propiônico, 1,3-propanodiol e hidrogênio em reator anaeróbio de leito fluidizado com pneu triturado como material suporte para adesão da biomassa. O experimento ocorreu durante 278 dias, em seis fases distintas distribuídas em função do tempo de detenção hidráulica (TDH), que variou entre 8 e 0,5 h. O reator foi mantido em condições mesofílicas (30 °C), com pH controlado entre 4,5 e 5,5 e possuía glicerol bruto como fonte de carbono na concentração de 5 g L-1. O inóculo utilizado no experimento foi proveniente de estação de tratamento de efluente de abatedouro de aves. Os resultados obtidos mostram que o consumo de substrato atingiu o maior valor de conversão (89,8 %) no TDH de 6 h. O biogás produzido foi composto de H2 e CO2, tendo o maior conteúdo de H2 registado (81,2 %) no TDH de 4 h. Os principais metabólitos solúveis obtidos foram ácido propiônico e 1,3-propanodiol com rendimentos máximos de 1,77 e 0,82 mol.molglicerol -1, respectivamente. Ambos os rendimentos máximos foram atingidos no TDH de 8 h. Em todas as fases apresentadas, ocorreu a predominância de ácido propiônico, sendo a maior porcentagem molar (96,9 %) atingida no TDH de 0,5 h. O segundo metabólito mais produzido foi o 1,3-propanodiol, alcançando maior porcentagem molar (29,4 %) no TDH de 6 h.