Algal wastewater treatment and biomass producing potential: nutrient removal efficiency and cell physiological responses

Microalgae are sun - light cell factories that convert carbon dioxide to biofuels, foods, feeds, and other bioproducts. The concept of microalgae cultivation as an integrated system in wastewater treatment has optimized the potential of the microalgae - based biofuel production. These microorganisms contains lipids, polysaccharides, proteins, pigments and other cell compounds, and their biomass can provide different kinds of biofuels such as biodiesel, biomethane and ethanol. The algal biomass application strongly depends on the cell composition and the production of biofuels appears to be economically convenient only in conjunction with wastewater treatment. The aim of this research thesis was to investigate a biological wastewater system on a laboratory scale growing a newly isolated freshwater microalgae, Desmodesmus communis, in effluents generated by a local wastewater reclamation facility in Cesena (Emilia Romagna, Italy) in batch and semi - continuous cultures. This work showed the potential utilization of this microorganism in an algae - based wastewater treatment; Desmodesmus communis had a great capacity to grow in the wastewater, competing with other microorganisms naturally present and adapting to various environmental conditions such as different irradiance levels and nutrient concentrations. The nutrient removal efficiency was characterized at different hydraulic retention times as well as the algal growth rate and biomass composition in terms of proteins, polysaccharides, total lipids and total fatty acids (TFAs) which are considered the substrate for biodiesel production. The biochemical analyses were coupled with the biomass elemental analysis which specified the amount of carbon and nitrogen in the algal biomass. Furthermore photosynthetic investigations were carried out to better correlate the environmental conditions with the physiology responses of the cells and consequently get more information to optimize the growth rate and the increase of TFAs and C/N ratio, cellular compounds and biomass parameter which are fundamental in the biomass energy recovery.

Fermentative processes for environmental remediation

The growing interest in environmental protection has led to the development of emerging biotechnologies for environmental remediation also introducing the biorefinery concept. This work mainly aimed to evaluate the applicability of innovative biotechnologies for environmental remediation and bioenergy production, throught fermentative processes. The investigated biotechnologies for waste and wastewater treatment and for the valorisation of specific feedstocks and energy recovery, were mainly focused on four research lines. 1. Biotechnology for textile wastewater treatment and water reuse that involving anaerobic and aerobic processes in combination with membrane technologies. Combinations of different treatments were also implemented for water reuse in a textile company. 2. Biotechnology for the treatment of solid waste and leachate in landfill and for biogas production. Landfill operated as Bioreactor with recirculation of the generated leachate was proposed for organic matter biostabilisation and for ammonia removal from leachate by favouring the Anammox process. 3. An innovative two-stage anaerobic process for effective codigestion of waste from the dairy industry, as cheese whey and dairy manure, was studied by combining conventional fermentative processes with a simplified system design for enhancing biomethanisation. 4) The valorisation of the glycerol waste as surplus by-product of the biodiesel industry was investigated via microbial conversion to value-added chemicals, as 1,3-propanediol. The investigated fermentative processes have been successfully implemented and reached high yields of the produced bio-chemical. The studied biotechnological systems proved to be feasible for environmental remediation and bioenergy and chemicals production.

Nuovi catalizzatori per la trasformazione diretta di glicerolo ad acido acrilico

Alla luce delle improrogabili necessità ambientali, le prospettive di crescita del mercato dei bio-combustibili e quindi del biodiesel, sono molto ampie; si rende quindi necessario lo sviluppo di nuovi processi chimici in grado di valorizzare il co-prodotto della sintesi del biodiesel, ovvero il glicerolo. Tra le varie opzioni proposte dalla recente letteratura scientifica e brevettuale, la trasformazione one-pot del glicerolo ad acido acrilico può rappresentare una soluzione. All’interno di questa tematica, durante il periodo di tesi ho eseguito uno studio di catalizzatori a base di ossidi misti contenenti tungsteno, molibdeno e/o vanadio. Tali ossidi presentano sia funzionalità acida, necessaria per il primo stadio di disidratazione del glicerolo ad acroleina, sia funzionalità redox, necessaria all’ossidazione dell’acroleina ad acido acrilico. I sistemi tri-componente W-V-Mo si sono rivelati catalizzatori attivi e selettivi per la sintesi diretta di glicerolo ad acido acrilico. La miglior performance catalitica di questa classe di catalizzatori ha consentito di ottenere selettività in acido acrilico del 31%, con selettività totale ad acido acrilico ed acroleina superiore al 38% (valori tra i più elevati rispetto a quelli riportati in letteratura). Infine, si è dimostrato che i catalizzatori a base di W-V-Mo sono sistemi potenzialmente sfruttabili anche in impianti a doppio stadio per la produzione di acido acrilico con alimentazioni miste propilene/glicerolo. Ulteriori studi sono attualmente in corso per approfondire le capacità catalitiche degli ossidi misti studiati.

Oxidation and pyrolysis of methane and methyl formate in a plug flow reactor: computational and experimenal studies

Biodiesel represents a possible substitute to the fossil fuels; for this reason a good comprehension of the kinetics involved is important. Due to the complexity of the biodiesel mixture a common practice is the use of surrogate molecules to study its reactivity. In this work are presented the experimental and computational results obtained for the oxidation and pyrolysis of methane and methyl formate conducted in a plug flow reactor. The work was divided into two parts: the first one was the setup assembly whilst, in the second one, was realized a comparison between the experimental and model results; these last was obtained using models available in literature. It was started studying the methane since, a validate model was available, in this way was possible to verify the reliability of the experimental results. After this first study the attention was focused on the methyl formate investigation. All the analysis were conducted at different temperatures, pressures and, for the oxidation, at different equivalence ratios. The results shown that, a good comprehension of the kinetics is reach but efforts are necessary to better evaluate kinetics parameters such as activation energy. The results even point out that the realized setup is adapt to study the oxidation and pyrolysis and, for this reason, it will be employed to study a longer chain esters with the aim to better understand the kinetic of the molecules that are part of the biodiesel mixture.

Valutazione della sostenibilità ambientale tramite metodologia LCA di sistemi per lo sfruttamento di fonti alternative di energia e materiali

La dissertazione ha riguardato l’analisi di sostenibilità di un sistema agronomico per la produzione di olio vegetale a fini energetici in terreni resi marginali dall’infestazione di nematodi. Il processo indagato ha previsto il sovescio di una coltura con proprietà biofumiganti (brassicacea) coltivata in precessione alla specie oleosa (soia e tabacco) al fine di contrastare il proliferare dell’infestazione nel terreno. Tale sistema agronomico è stato confrontato attraverso una analisi di ciclo di vita (LCA) ad uno scenario di coltivazione della stessa specie oleosa senza precessione di brassica ma con l’utilizzo di 1-3-dicloropropene come sistema di lotta ai nematodi. Allo scopo di completare l’analisi LCA con una valutazione dell’impatto sull’uso del suolo (Land use Impact) generato dai due scenari a confronto, sono stati costruiti due modelli nel software per il calcolo del Soil Conditioning Index (SCI), un indicatore quali-quantitativo della qualità del terreno definito dal Dipartimento per l’Agricoltura degli Stati Uniti d’America (USDA).

Synthesis and characterisation of hydrotalcite-like compounds for transesterification reaction

A series of templated [Mg(1-x)Alx(OH)2]x+(CO3)x/n2- with different structural properties have been synthesised using an alkali-free coprecipitation route. The macroporous materials were been obtained using two different kind of templating agents, polymeric materials, in order to cover a bigger size range (750-70 nm). All the materials have been characterized by different techniques: porosimetry, SEM-EDX, TEM-EDX, MP-AES, XRD, CO2 titration before and after the calcinations process. All the materials have been tested for transesterification reaction of C4-C8 triglycerides with methanol for biodiesel production.

Glycerol oxidehydration to acrylic acid on complex mixed-metal oxides

The project of this Ph.D. thesis is based on a co-supervised collaboration between Università di Bologna, ALMA MATER STUDIORUM (Italy) and Instituto de Tecnología Química, Universitat Politècnica de València ITQ-UPV (Spain). This Ph.D. thesis is about the synthesis, characterization and catalytic testing of complex mixed-oxide catalysts mainly related to the family of Hexagonal Tungsten Bronzes (HTBs). These materials have been little explored as catalysts, although they have a great potential as multifunctional materials. Their peculiar acid properties can be coupled to other functionalities (e.g. redox sites) by isomorphous substitution of tungsten atoms with other transition metals such as vanadium, niobium and molybdenum. In this PhD thesis, it was demonstrated how it is possible to prepare substituted-HTBs by hydrothermal synthesis; these mixed-oxide were fully characterize by a number of physicochemical techniques such as XPS, HR-TEM, XAS etc. They were also used as catalysts for the one-pot glycerol oxidehydration to acrylic acid; this reaction might represent a viable chemical route to solve the important issue related to the co-production of glycerin along the biodiesel production chain. Acrylic acid yields as high as 51% were obtained and important structure-reactivity correlations were proved to govern the catalytic performance; only fine tuning of acid and redox properties as well as the in-framework presence of vanadium are fundamental to achieve noteworthy yields into the acid monomer. The overall results reported herein might represent an important contribution for future applications of HTBs in catalysis as well as a general guideline for a multifaceted approach for their physicochemical characterization.

Studio delle caratteristiche di catalizzatori per la sintesi diretta di acido acrilico da glicerolo

La saturazione del mercato del glicerolo, co-prodotto del biodiesel, ha portato allo sviluppo di nuovi processi che permettessero la sua trasformazione in composti a maggiore valore aggiunto. Uno dei principali processi di interesse è la sintesi diretta di acido acrilico, che prevede uno step di disidratazione, catalizzato da siti acidi, con l’ottenimento dell’acroleina, e un successivo step di ossidazione dell’aldeide insatura, mediato da siti redox, ad acido acrilico. Il compimento di entrambi gli step catalitici può essere effettuato mediante l’utilizzo di catalizzatori bifunzionali. I sistemi più promettenti sono costituiti da bronzi di tungsteno/vanadio con struttura esagonale. Per sviluppare ulteriormente tali sistemi è necessario determinare l’influenza di alcune loro caratteristiche, come l’acidità e le caratteristiche dello ioni vanadio, sulle prestazioni catalitiche. Lo scopo di questo lavoro ha riguardato lo studio dell’influenza dei centri acidi presenti nei bronzi esagonali di tungsteno/vanadio, e del ruolo dello ione vanadio, analizzando il comportamento catalitico di bronzi di tungsteno e di alluminofosfati.

Influenza di un co-sustrato sulla biodegradabilità anaerobica (mesofilica) dei fanghi di stazioni di depurazione delle acque residuali

La presente tesi di laurea magistrale si è elaborata nell'ambito del Dipartimento di Tecnologie Ambientali dell'Università di Cadice (Spagna). Tratta lo studio dell'influenza di un co-substrato sulla biodegradabilità anaerobica, in condizioni mesofiliche, dei fanghi di depurazione delle acque residuali. Il co-substrato utilizzato per il miglioramento dei trattamenti dei fanghi è il glicerolo, un sottoprodotto di lavorazione del biodiesel. Le prove realizzate mirano a ottimizzare l'eliminazione della materia organica e la produzione di biogas (idrogeno e metano). Come imminente prospettiva futura, avremo l'avviamento nelle migliori condizioni di processo dell'impianto pilota di depurazione fanghi ubicato presso la stazione di trattamento delle acque reflue urbane di Cadice - San fernando.

La raccolta e la gestione degli oli esausti domestici

Obiettivo della tesi è riconoscere i fattori di successo e i principali limiti legati all’implementazione dei progetti di recupero degli oli domestici sul territorio italiano. Il problema nasce dall’ esigenza di gestire in modo efficiente la raccolta differenziata di questo rifiuto che, se gettato nello scarico di casa o nel lavandino, provoca impatti ambientali rilevanti rendendo particolarmente difficoltoso e dispendioso il trattamento delle acque reflue e causa gravi danni agli ecosistemi naturali. La questione è da tempo inquadrata e disciplinata dalle direttive comunitarie in materia di rifiuti e dalla strategia “Europa2020” che ha come obiettivo principale una crescita intelligente, sostenibile ed inclusiva. A livello nazionale, invece, il Testo Unico Ambientale assolve alla funzione principale di riordino e coordinamento della disciplina, dando attuazione ai principi comunitari in materia e conformando l’ordinamento nazionale agli obiettivi e alle priorità individuate dal legislatore europeo. Gli oli esausti domestici sono un rifiuto scomodo e complesso da gestire ma la valorizzazione energetica può essere una valida alternativa ai sistemi di smaltimento classici. Infatti, attraverso un semplice processo chimico l’olio da cucina usato può essere trasformato in biodiesel. Questo particolare biocombustibile rispetta tutti i criteri di sostenibilità imposti dalla Comunità Europea e riduce, inoltre, l’impatto della produzione di biocarburanti sull’agricoltura.

LIFE CYCLE ASSESSMENT OF BIOFUEL PRODUCED FROM ALGAE

Algae are considered a promising source of biofuels in the future. However, the environmental impact of algae-based fuel has high variability in previous LCA studies due to lack of accurate data from researchers and industry. The National Alliance for Advanced Biofuels and Bioproducts (NAABB) project was designed to produce and evaluate new technologies that can be implemented by the algal biofuel industry and establish the overall process sustainability. The MTU research group within NAABB worked on the environmental sustainability part of the consortium with UOP-Honeywell and with the University of Arizona (Dr. Paul Blowers). Several life cycle analysis (LCA) models were developed within the GREET Model and SimaPro 7.3 software to quantitatively assess the environment viability and sustainability of algal fuel processes. The baseline GREET Harmonized algae life cycle was expanded and replicated in SimaPro software, important differences in emission factors between GREET/E-Grid database and SimaPro/Ecoinvent database were compared, and adjustments were made to the SimaPro analyses. The results indicated that in most cases SimaPro has a higher emission penalty for inputs of electricity, chemicals, and other materials to the algae biofuels life cycle. A system-wide model of algae life cycle was made starting with preliminary data from the literature, and then progressed to detailed analyses based on inputs from all NAABB research areas, and finally several important scenarios in the algae life cycle were investigated as variations to the baseline scenario. Scenarios include conversion to jet fuel instead of biodiesel or renewable diesel, impacts of infrastructure for algae cultivation, co-product allocation methodology, and different usage of lipid-extracted algae (LEA). The infrastructure impact of algae cultivation is minimal compared to the overall life cycle. However, in the scenarios investigating LEA usage for animal feed instead of internal recycling for energy use and nutrient recovery the results reflect the high potential variability in LCA results. Calculated life cycle GHG values for biofuel production scenarios where LEA is used as animal feed ranged from a 55% reduction to 127% increase compared to the GREET baseline scenario depending on the choice of feed meal. Different allocation methods also affect LCA results significantly. Four novel harvesting technologies and two extraction technologies provided by the NAABB internal report have been analysis using SimaPro LCA software. The results indicated that a combination of acoustic extraction and acoustic harvesting technologies show the most promising result of all combinations to optimize the extraction of algae oil from algae. These scenario evaluations provide important insights for consideration when planning for the future of an algae-based biofuel industry.

Advanced Nanostructured Electro-Catalysts for Electricity Generation and Biorenewable Alcohol Conversion

In my Ph.D research, a wet chemistry-based organic solution phase reduction method was developed, and was successfully applied in the preparation of a series of advanced electro-catalysts, including 0-dimensional (0-D) Pt, Pd, Au, and Pd-Ni nanoparticles (NPs), 1-D Pt-Fe nanowires (NWs) and 2-D Pd-Fe nanoleaves (NLs), with controlled size, shape, and morphology. These nanostructured catalysts have demonstrated unique electro-catalytic functions towards electricity production and biorenewable alcohol conversion. The molecular oxygen reduction reaction (ORR) is a long-standing scientific issue for fuel cells due to its sluggish kinetics and the poor catalyst durability. The activity and durability of an electro-catalyst is strongly related with its composition and structure. Based on this point, Pt-Fe NWs with a diameter of 2 - 3 nm were accurately prepared. They have demonstrated a high durability in sulfuric acid due to its 1-D structure, as well as a high ORR activity attributed to its tuned electronic structure. By substituting Pt with Pd using a similar synthesis route, Pd-Fe NLs were prepared and demonstrated a higher ORR activity than Pt and Pd NPs catalysts in the alkaline electrolyte. Recently, biomass-derived alcohols have attracted enormous attention as promising fuels (to replace H2) for low-temperature fuel cells. From this point of view, Pd-Ni NPs were prepared and demonstrated a high electro-catalytic activity towards ethanol oxidation. Comparing to ethanol, the biodiesel waste glycerol is more promising due to its low price and high reactivity. Glycerol (and crude glycerol) was successfully applied as the fuel in an Au-anode anion-exchange membrane fuel cell (AEMFC). By replacing Au with a more active Pt catalyst, simultaneous generation of both high power-density electricity and value-added chemicals (glycerate, tartronate, and mesoxalate) from glycerol was achieved in an AEMFC. To investigate the production of valuable chemicals from glycerol electro-oxidation, two anion-exchange membrane electro-catalytic reactors were designed. The research shows that the electro-oxidation product distribution is strongly dependent on the anode applied potential. Reaction pathways for the electro-oxidation of glycerol on Au/C catalyst have been elucidated: continuous oxidation of OH groups (to produce tartronate and mesoxalate) is predominant at lower potentials, while C-C cleavage (to produce glycolate) is the dominant reaction path at higher potentials.

Jatropha mahafalensis oil from Madagascar: properties and suitability as liquid biofuel

Access to affordable and renewable sources of energy is crucial to reducing poverty and enhancing rural development in countries of the global South. Straight vegetable oil was recently identified as a possible alternative to conventional biomass for rural energy supply. In this context, the Jatropha curcas Linn. species has been extensively investigated with regard to its potential as a biofuel feedstock. In contrast, only little is known about Jatropha mahafalensis Jum. & H. Perrier, which is an indigenous and endemic representative of the Jatropha genus in Madagascar. This paper explores the potential and suitability of J. mahafalensis as a biofuel feedstock. Seed samples were collected in the area of Soalara in south-western Madagascar in February and September 2011. Two agro-ecological zones (coastal area and calcareous plateau) and two plant age groups (below and above 10 years) were considered. These four sample groups were analyzed with regard to oil properties, element contents, and fatty acid profiles. Measured values differed greatly between the two harvests, probably owing to different climatic or storage conditions. No direct relation between age of trees or location and oil quality could be established. The analyses indicate that J. mahafalensis oil can be used in oil lamps, cooking stoves and stationary combustion engines for electrification or for biodiesel production. However, modifications in storage and extraction methods, as well as further processing steps are necessary to enable its utilization as a straight vegetable oil and feedstock for biodiesel production. If these technical requirements can be met, and if it turns out that J. mahafalensis oil is economically competitive in comparison with firewood, charcoal, paraffin and petroleum, it can be considered as a promising feedstock for rural energy supply.

Comparison of the toxicity of diesel exhaust produced by bio- and fossil diesel combustion in human lung cells in vitro

Alternative fuels are increasingly combusted in diesel- and gasoline engines and the contribution of such exhausts to the overall air pollution is on the rise. Recent findings on the possible adverse effects of biodiesel exhaust are contradictive, at least partly resulting from the various fuel qualities, engine types and different operation conditions that were tested. However, most of the studies are biased by undesired interactions between the exhaust samples and biological culture media. We here report how complete, freshly produced exhausts from fossil diesel (B0), from a blend of 20% rapeseed-methyl ester (RME) and 80% fossil diesel (B20) and from pure rapeseed methyl ester (B100) affect a complex 3D cellular model of the human airway epithelium in vitro by exposing the cells at the air–liquid interface. The induction of pro-apoptotic and necrotic cell death, cellular morphology, oxidative stress, and pro-inflammatory responses were assessed. Compared to B0 exhaust, B20 exhaust decreased oxidative stress and pro-inflammatory responses, whereas B100 exhaust, depending on exposure duration, decreased oxidative stress but increased pro-inflammatory responses. The effects are only very weak and given the compared to fossil diesel higher ecological sustainability of biodiesel, it appears that – at least RME – can be considered a valuable alternative to pure fossil diesel.

Beyond biofuels: jatropha’s multiple uses for farmers in East Africa

The jatropha plant produces seeds containing 25–40% oil by weight. This oil can be made into biodiesel. During the recent global fuel crisis, the price of crude oil peaked at over USD 130 per barrel. Jatropha attracted huge interest – it was touted as a wonder crop that could generate biodiesel oil on “marginal lands” in semi-arid areas. Its promise appeared especially great in East Africa. Today, however, jatropha’s value in East Africa appears to lie primarily in its multipurpose use by small-scale farmers, not in large-scale biofuel production.