Liquid-phase alcohol promoted methanol synthesis from CO2 and H2

Methanol is an important and versatile compound with various uses as a fuel and a feedstock chemical. Methanol is also a potential chemical energy carrier. Due to the fluctuating nature of renewable energy sources such as wind or solar, storage of energy is required to balance the varying supply and demand. Excess electrical energy generated at peak periods can be stored by using the energy in the production of chemical compounds. The conventional industrial production of methanol is based on the gas-phase synthesis from synthesis gas generated from fossil sources, primarily natural gas. Methanol can also be produced by hydrogenation of CO2. The production of methanol from CO2 captured from emission sources or even directly from the atmosphere would allow sustainable production based on a nearly limitless carbon source, while helping to reduce the increasing CO2 concentration in the atmosphere. Hydrogen for synthesis can be produced by electrolysis of water utilizing renewable electricity. A new liquid-phase methanol synthesis process has been proposed. In this process, a conventional methanol synthesis catalyst is mixed in suspension with a liquid alcohol solvent. The alcohol acts as a catalytic solvent by enabling a new reaction route, potentially allowing the synthesis of methanol at lower temperatures and pressures compared to conventional processes. For this thesis, the alcohol promoted liquid phase methanol synthesis process was tested at laboratory scale. Batch and semibatch reaction experiments were performed in an autoclave reactor, using a conventional Cu/ZnO catalyst and ethanol and 2-butanol as the alcoholic solvents. Experiments were performed at the pressure range of 30-60 bar and at temperatures of 160-200 °C. The productivity of methanol was found to increase with increasing pressure and temperature. In the studied process conditions a maximum volumetric productivity of 1.9 g of methanol per liter of solvent per hour was obtained, while the maximum catalyst specific productivity was found to be 40.2 g of methanol per kg of catalyst per hour. The productivity values are low compared to both industrial synthesis and to gas-phase synthesis from CO2. However, the reaction temperatures and pressures employed were lower compared to gas-phase processes. While the productivity is not high enough for large-scale industrial operation, the milder reaction conditions and simple operation could prove useful for small-scale operations. Finally, a preliminary design for an alcohol promoted, liquid-phase methanol synthesis process was created using the data obtained from the experiments. The demonstration scale process was scaled to an electrolyzer unit producing 1 Nm3 of hydrogen per hour. This Master’s thesis is closely connected to LUT REFLEX-platform.

FluxEngine: A flexible processing system for calculating atmosphere-ocean carbon dioxide gas fluxes and climatologies

The air-sea flux of greenhouse gases (e.g. carbon dioxide, CO2) is a critical part of the climate system and a major factor in the biogeochemical development of the oceans. More accurate and higher resolution calculations of these gas fluxes are required if we are to fully understand and predict our future climate. Satellite Earth observation is able to provide large spatial scale datasets that can be used to study gas fluxes. However, the large storage requirements needed to host such data can restrict its use by the scientific community. Fortunately, the development of cloud-computing can provide a solution. Here we describe an open source air-sea CO2 flux processing toolbox called the ‘FluxEngine’, designed for use on a cloud-computing infrastructure. The toolbox allows users to easily generate global and regional air-sea CO2 flux data from model, in situ and Earth observation data, and its air-sea gas flux calculation is user configurable. Its current installation on the Nephalae cloud allows users to easily exploit more than 8 terabytes of climate-quality Earth observation data for the derivation of gas fluxes. The resultant NetCDF data output files contain >20 data layers containing the various stages of the flux calculation along with process indicator layers to aid interpretation of the data. This paper describes the toolbox design, the verification of the air-sea CO2 flux calculations, demonstrates the use of the tools for studying global and shelf-sea air-sea fluxes and describes future developments.

Síntese de ß-cetoésteres graxos a partir do ácido de Meldrum usando DCC e DMAP

Neste trabalho desenvolveu-se a síntese de -cetoésteres, a partir da acilação do ácido de Meldrum usando diferentes ácidos graxos, com cadeias saturadas e insaturadas. Inicialmente, foi realizado o experimento utilizando o ácido palmítico (1e) como modelo para obtenção de cloreto de ácido graxo, usando ácido de Meldrum e piridina como catalisador. Porém, após um longo tempo de reação, o -cetoéster palmítico (4e) foi obtido com baixo rendimento, não ultrapassando os 20%. Posteriormente, os experimentos foram realizados utilizando o ácidos graxos 1e, ácido de Meldrum (2), DCC, DMAP, e piridina à temperatura ambiente sob a atmosfera de nitrogênio. No entanto, o protocolo utilizado resultou no β-cetoéster 4e com rendimentos moderados. Em seguida examinou-se o efeito da adição do ácido de Meldrum após a adição dos ácido graxos e DCC. Neste caso, após a adição do DCC aos ácido graxos 1a-j foi observada a formação imediata das O-aciluréias graxas. A seguir a adição de 2,0 equiv de ácido de Meldrum (2) em diclorometano, revelou a formação dos respectivos enol graxos 3a-j. Posteriormente, os β- cetoésteres 4a-j foram obtidos a partir da reação do enol com o metanol. Este protocolo modificado proporcionou o aumento nos rendimentos (74 a 84%) dos β-cetoéster 4a-j. Após, o β-cetoéster 4k foi sintetizado em 75% utilizando o ácido de Meldrum (2) e ácido ricinoléico (1k), obtido a partir do biodiesel de mamona, à temperatura ambiente e sob a atmosfera de nitrogênio. Portanto, foi desenvolvido um método simples para obter β-cetoésteres graxos, a partir do ácido de Meldrum com cadeias graxas diversificadas utilizando DCC e DMAP. Além disso, o presente trabalho relata pela primeira vez a síntese de novos β-cetoésteres graxos derivados dos ácidos oléico, elaídico, ricinoléico, linoléico e linolênico.

Influência das espécies ativas na absorção de intersticiais durante a carbonitretação a plasma do TI

Physical-chemical properties of Ti are sensible to the presence of interstitial elements. In the case of thermochemical treatments plasma assisted, the influence of different active species is not still understood. In order to contribute for such knowledge, this work purposes a study of the role played by the active species atmosphere into the Ar N2 CH4 carbonitriding plasma. It was carried out a plasma diagnostic by OES (Optical Emission Spectroscopy) in the z Ar y N2 x CH4 plasma mixture, in which z, y and x indexes represent gas flow variable from 0 to 4 sccm (cm3/min). The diagnostic presents abrupt variations of emission intensities associated to the species in determined conditions. Therefore, they were selected in order to carry out the chemical treatment and then to investigate their influences. Commercial pure Ti disks were submitted to plasma carbonitriding process using pre-established conditions from the OES measurements while some parameters such as pressure and temperature were maintained constant. The concentration profiles of interstitial elements (C and N atoms) were determined by Resonant Nuclear Reaction Analysis (NRA) resulting in a depth profile plots. The reactions used were 15N(ρ,αγ)12C and 12C(α,α)12C. GIXRD (Grazing Incidence X-Ray Diffraction) analysis was used in order to identify the presence of phases on the surface. Micro-Raman spectroscopy was used in order to qualitatively study the carbon into the TiCxN1 structure. It has been verified which the density species effectively influences more the diffusion of particles into the Ti lattice and characteristics of the layer formed than the gas concentration. High intensity of N2 + (391,4 nm) and CH (387,1 nm) species promotes more diffusion of C and N. It was observed that Hα (656,3 nm) species acts like a catalyzer allowing a deeper diffusion of nitrogen and carbon into the titanium lattice.

Synthesis of active Belite-Alite-Ye'elimite clinker (BAY)

Ordinary Portland cement (OPC) is an environmentally contentious material, as for every ton of OPC produced, on average, 0.97 tons of CO2 are released. Ye'elimite-rich cements are considered as eco-cements because their manufacturing process releases less CO2 into the atmosphere than OPC; this is due to the low calcite demand. Belite-Alite-Ye’elimite (BAY) cements are promising eco-friendly building materials as OPC substitutes at a large scale. The reaction of alite and ye´elimite with water should develop cements with high mechanical strengths at early ages, while belite will contribute to later curing times. However, they develop lower mechanical strengths at early-medium ages than OPC. It is known that the presence of different polymorphs of ye'elimite and belite affects the hydration due to the different reactivity of those phases. Thus, a solution to this problem may be well the activation of BAY clinkers by preparing them with 'H-belite and pseudo-cubic-ye'elimite, jointly with alite. The aim of this work is the preparation and characterization of active-BAY clinkers which contain high percentages of coexisting 'H-belite and pseudo-cubic-ye'elimite, jointly with alite to develop, in a future step, comparable mechanical strengths to OPC. The parameters evolved in the preparation of the clinker have been optimized, including the selection of raw materials (mineralizers and activators) and clinkering conditions. Finally, the clinker was characterized through laboratory X-ray powder diffraction, in combination with the Rietveld methodology, and scanning electron microscopy.

Non chemical natural organic matter removal with a contact TiO2 process

Dissertação de Mestrado, Tecnologia dos Alimentos, Instituto Superior de Engenharia, Universidade do Algarve, 2014

Bimetallic PtSn/C catalysts obtained via SOMC/M for glycerol steam reforming

A detailed study on the preparation of bimetallic PtSn/C catalysts using surface-controlled synthesis methods, and on their catalytic performance in the glycerol steam reforming reaction has been carried out. In order to obtain these well-defined bimetallic phases, techniques derived from Surface Organometallic Chemistry on Metals (SOMC/M) were used. The preparation process involved the reaction between an organometallic compound ((C4H9)4Sn) and a supported transition metal (Pt) in a H2 atmosphere. Catalysts with Sn/Pt atomic ratios of 0.2, 0.3, 0.5, and 0.7 were obtained, and characterized using several techniques: ICP, H2 chemisorption, TEM and XPS. These systems were tested in the glycerol steam reforming varying the reaction conditions (glycerol concentration and reaction temperature). The best performance was observed for the catalysts with the lowest tin contents (PtSn0.2/C and PtSn0.3/C). It was observed that the presence of tin increased the catalysts’ stability when working under more severe reaction conditions.

Hydrothermal carbonization of lignocellulosic biomass: Effect of process conditions on hydrochar properties

Although hydrothermal carbonization of biomass components is known to be mainly governed by reaction temperature, consistent reports on the effect and statistical significance of process conditions on hydrochar properties are still lacking. The objective of this research was to determine the importance and significance of reaction temperature, retention time and solid load on the properties of hydrochar produced from an industrial lignocellulosic sludge residue. According to the results, reaction temperature and retention time had a statistically significant effect on hydrochar ash content, solid yield, carbon content, O/C-ratio, energy densification and energy yield as reactor solid load was statistically insignificant for all acquired models within the design range. Although statistically significant, the effect of retention time was 3–7 times lower than that of reaction temperature. Predicted dry ash-free solid yields of attained hydrochar decreased to approximately 40% due to the dissolution of biomass components at higher reaction temperatures, as respective oxygen contents were comparable to subbituminous coal. Significant increases in the carbon contents of hydrochar led to predicted energy densification ratios of 1–1.5 with respective energy yields of 60–100%. Estimated theoretical energy requirements of carbonization were dependent on the literature method used and mainly controlled by reaction temperature and reactor solid load. The attained results enable future prediction of hydrochar properties from this feedstock and help to understand the effect of process conditions on hydrothermal treatment of lignocellulosic biomass.

Chemical Reaction Dynamics of the Liquid/Vapor Interface Studied by Mass Spectrometry

This thesis presents investigations of chemical reactions occurring at the liquid/vapor interface studied using novel sampling methodologies coupled with detection by mass spectrometry. Chapters 2 and 3 utilize the recently developed technique of field-induced droplet ionization mass spectrometry (FIDI-MS), in which the application of a strong electric field to a pendant microliter droplet results in the ejection of highly charged progeny droplets from the liquid surface. In Chapter 2, this method is employed to study the base-catalyzed dissociation of a surfactant molecule at the liquid/vapor interface upon uptake of ammonia from the gas phase. This process is observed to occur without significant modulation of the bulk solution pH, suggesting a transient increase in surface pH following the uptake of gaseous ammonia. Chapter 3 presents real-time studies of the oxidation of the model tropospheric organic compound glycolaldehyde by photodissociation of iron (III) oxalate complexes. The oxidation products of glycolaldehyde formed in this process are identified, and experiments in a deoxygenated environment identify the role of oxygen in the oxidation pathway and in the regeneration of iron (III) following photo-initiated reduction. Chapter 4 explores alternative methods for the study of heterogeneous reaction processes by mass spectrometric sampling from liquid surfaces. Bursting bubble ionization (BBI) and interfacial sampling with an acoustic transducer (ISAT) generate nanoliter droplets from a liquid surface that can be sampled via the atmospheric pressure interface of a mass spectrometer. Experiments on the oxidation of oleic acid by ozone using ISAT are also presented. Chapters 5 and 6 detail mechanistic studies and applications of free-radical-initiated peptide sequencing (FRIPS), a technique employing gas-phase free radical chemistry to the sequencing of peptides and proteins by mass spectrometry. Chapter 5 presents experimental and theoretical studies on the anomalous mechanism of dissociation observed in the presence of serine and threonine residues in peptides. Chapter 6 demonstrates the combination of FRIPS with ion mobility-mass spectrometry (IM-MS) for the separation of isomeric peptides.

Development of a continuous process for α-thio-β-chloroacrylamide synthesis with enhanced control of a cascade transformation

A continuous process strategy has been developed for the preparation of α-thio-β chloroacrylamides, a class of highly versatile synthetic intermediates. Flow platforms to generate the α-chloroamide and α-thioamide precursors were successfully adopted, progressing from the previously employed batch chemistry, and in both instances afford a readily scalable methodology. The implementation of the key α-thio-β-chloroacrylamide casade as a continuous flow reaction on a multi-gram scale is described, while the tuneable nature of the cascade, facilitated by continuous processing, is highlighted by selective generation of established intermediates and byproducts.

Integration of process planning and scheduling using mobile-agent based approach in a networked manufacturing environment

Effective and efficient implementation of intelligent and/or recently emerged networked manufacturing systems require an enterprise level integration. The networked manufacturing offers several advantages in the current competitive atmosphere by way to reduce, by shortening manufacturing cycle time and maintaining the production flexibility thereby achieving several feasible process plans. The first step in this direction is to integrate manufacturing functions such as process planning and scheduling for multi-jobs in a network based manufacturing system. It is difficult to determine a proper plan that meets conflicting objectives simultaneously. This paper describes a mobile-agent based negotiation approach to integrate manufacturing functions in a distributed manner; and its fundamental framework and functions are presented. Moreover, ontology has been constructed by using the Protégé software which possesses the flexibility to convert knowledge into Extensible Markup Language (XML) schema of Web Ontology Language (OWL) documents. The generated XML schemas have been used to transfer information throughout the manufacturing network for the intelligent interoperable integration of product data models and manufacturing resources. To validate the feasibility of the proposed approach, an illustrative example along with varied production environments that includes production demand fluctuations is presented and compared the proposed approach performance and its effectiveness with evolutionary algorithm based Hybrid Dynamic-DNA (HD-DNA) algorithm. The results show that the proposed scheme is very effective and reasonably acceptable for integration of manufacturing functions.

Theoretical and experimental study on the role of benzoquinone in the Guerbet reaction catalyzed by a ruthenium complex

The benzoquinone was found as an effective co-catalyst in the ruthenium/NaOEt-catalyzed Guerbet reaction. The co-catalyst behavior has therefore been investigated through experimental and computational methods. The reaction products distribution shows that the reaction speed is improved by the benzoquinone supplement since the beginning of the process, having a minimal effect on the selectivity toward alcoholic species. DFT calculations were performed to investigate two hypotheses for the kinetic effects: i) a hydrogen storage mechanism or ii) a basic co-catalysis of 4-hydroxiphenolate. The most promising results were found for the latter hypothesis, where a new mixed mechanism for the aldol condensation step of the Guerbet process involves the hydroquinone (i.e. the reduced form of benzoquinone) as proton source instead of ethanol. This mechanism was found to be energetically more favorable than an aldol condensation in absence of additive, suggesting that the hydroquinone derived from benzoquinone could be the key species affecting the kinetics of the overall process. To verify this theoretical hypothesis, new phenol derivatives were tested as additives in the Guerbet reaction. The outcomes confirmed that an aromatic acid (stronger than ethanol) could improve the reaction kinetics. Lastly, theoretical products distributions were simulated and compared to the experimental one, using the DFT computations to build the kinetic models.

Fractalkine (cx3cl1) Is Involved In The Early Activation Of Hypothalamic Inflammation In Experimental Obesity.

Hypothalamic inflammation is a common feature of experimental obesity. Dietary fats are important triggers of this process, inducing the activation of toll-like receptor-4 (TLR4) signaling and endoplasmic reticulum stress. Microglia cells, which are the cellular components of the innate immune system in the brain, are expected to play a role in the early activation of diet-induced hypothalamic inflammation. Here, we use bone marrow transplants to generate mice chimeras that express a functional TLR4 in the entire body except in bone marrow-derived cells or only in bone marrow-derived cells. We show that a functional TLR4 in bone marrow-derived cells is required for the complete expression of the diet-induced obese phenotype and for the perpetuation of inflammation in the hypothalamus. In an obesity-prone mouse strain, the chemokine CX3CL1 (fractalkine) is rapidly induced in the neurons of the hypothalamus after the introduction of a high-fat diet. The inhibition of hypothalamic fractalkine reduces diet-induced hypothalamic inflammation and the recruitment of bone marrow-derived monocytic cells to the hypothalamus; in addition, this inhibition reduces obesity and protects against diet-induced glucose intolerance. Thus, fractalkine is an important player in the early induction of diet-induced hypothalamic inflammation, and its inhibition impairs the induction of the obese and glucose intolerance phenotypes.

Evidences Of Endocytosis Via Caveolae Following Blood-brain Barrier Breakdown By Phoneutria Nigriventer Spider Venom.

Spider venoms contain neurotoxic peptides aimed at paralyzing prey or for defense against predators; that is why they represent valuable tools for studies in neuroscience field. The present study aimed at identifying the process of internalization that occurs during the increased trafficking of vesicles caused by Phoneutria nigriventer spider venom (PNV)-induced blood-brain barrier (BBB) breakdown. Herein, we found that caveolin-1α is up-regulated in the cerebellar capillaries and Purkinje neurons of PNV-administered P14 (neonate) and 8- to 10-week-old (adult) rats. The white matter and granular layers were regions where caveolin-1α showed major upregulation. The variable age played a role in this effect. Caveolin-1 is the central protein that controls caveolae formation. Caveolar-specialized cholesterol- and sphingolipid-rich membrane sub-domains are involved in endocytosis, transcytosis, mechano-sensing, synapse formation and stabilization, signal transduction, intercellular communication, apoptosis, and various signaling events, including those related to calcium handling. PNV is extremely rich in neurotoxic peptides that affect glutamate handling and interferes with ion channels physiology. We suggest that the PNV-induced BBB opening is associated with a high expression of caveolae frame-forming caveolin-1α, and therefore in the process of internalization and enhanced transcytosis. Caveolin-1α up-regulation in Purkinje neurons could be related to a way of neurons to preserve, restore, and enhance function following PNV-induced excitotoxicity. The findings disclose interesting perspectives for further molecular studies of the interaction between PNV and caveolar specialized membrane domains. It proves PNV to be excellent tool for studies of transcytosis, the most common form of BBB-enhanced permeability.

Albumin Is Synthesized In Epididymis And Aggregates In A High Molecular Mass Glycoprotein Complex Involved In Sperm-egg Fertilization.

The epididymis has an important role in the maturation of sperm for fertilization, but little is known about the epididymal molecules involved in sperm modifications during this process. We have previously described the expression pattern for an antigen in epididymal epithelial cells that reacts with the monoclonal antibody (mAb) TRA 54. Immunohistochemical and immunoblotting analyses suggest that the epitope of the epididymal antigen probably involves a sugar moiety that is released into the epididymal lumen in an androgen-dependent manner and subsequently binds to luminal sperm. Using column chromatography, SDS-PAGE with in situ digestion and mass spectrometry, we have identified the protein recognized by mAb TRA 54 in mouse epididymal epithelial cells. The ∼65 kDa protein is part of a high molecular mass complex (∼260 kDa) that is also present in the sperm acrosomal vesicle and is completely released after the acrosomal reaction. The amino acid sequence of the protein corresponded to that of albumin. Immunoprecipitates with anti-albumin antibody contained the antigen recognized by mAb TRA 54, indicating that the epididymal molecule recognized by mAb TRA 54 is albumin. RT-PCR detected albumin mRNA in the epididymis and fertilization assays in vitro showed that the glycoprotein complex containing albumin was involved in the ability of sperm to recognize and penetrate the egg zona pellucida. Together, these results indicate that epididymal-derived albumin participates in the formation of a high molecular mass glycoprotein complex that has an important role in egg fertilization.