Geochemistry and kinetic models od Cretaceous samples

The source rock potential of Cretaceous organic rich whole rock samples from deep sea drilling project (DSDP) wells offshore southwestern Africa was investigated using bulk and quantitative pyrolysis techniques. The sample material was taken from organic rich intervals of Aptian, Albian and Turonian aged core samples from DSDP site 364 offshore Angola, DSDP well 530A north of the Walvis Ridge offshore Namibia, and DSDP well 361 offshore South Africa. The analytical program included TOC, Rock-Eval, pyrolysis GC, bulk kinetics and micro-scale sealed vessel pyrolysis (MSSV) experiments. The results were used to determine differences in the source rock petroleum type organofacies, petroleum composition, gas/oil ratio (GOR) and pressure-volume-temperature (PVT) behavior of hydrocarbons generated from these black shales for petroleum system modeling purposes. The investigated Aptian and Albian organic rich shales proved to contain excellent quality marine kerogens. The highest source rock potential was identified in sapropelic shales in DSDP well 364, containing very homogeneous Type II and organic sulfur rich Type IIS kerogen. They generate P-N-A low wax oils and low GOR sulfur rich oils, whereas Type III kerogen rich silty sandstones of DSDP well 361 show a potential for gas/condensate generation. Bulk kinetic experiments on these samples indicate that the organic sulfur contents influence kerogen transformation rates, Type IIS kerogen being the least stable. South of the Walvis Ridge, the Turonian contains predominantly a Type III kerogen. North of the Walvis Ridge, the Turonian black shales contain Type II kerogen and have the potential to generate P-N-A low and high wax oils, the latter with a high GOR at high maturity. Our results provide the first compositional kinetic description of Cretaceous organic rich black shales, and demonstrate the excellent source rock potential, especially of the Aptian-aged source rock, that has been recognized in a number of the South Atlantic offshore basins.

Deepwater ports approach/exit control capabilities assessment : technology/service alternatives /

Contract no. DOT-CG-60, 351-A.

Production of renewable phenolic resins by thermochemical conversion of biomass: a review

This review covers the production and utilisation of liquids from the thermal processing of biomass and related materials to substitute for synthetic phenol and formaldehyde in phenol formaldehyde resins. These resins are primarily employed in the manufacture of wood panels such as plywood, MDF, particle-board and OSB. The most important thermal conversion methods for this purpose are fast pyrolysis and vacuum pyrolysis, pressure liquefaction and phenolysis. Many feedstocks have been tested for their suitability as sources of phenolics including hard and softwoods, bark and residual lignins. Resins have been prepared utilising either the whole liquid product, or a phenolics enriched fraction obtained after fractional condensation or further processing, such as solvent extraction. None of the phenolics production and fractionation techniques covered in this review are believed to allow substitution of 100% of the phenol content of the resin without impacting its effectiveness compared to commercial formulations based on petroleum derived phenol. This survey shows that considerable progress has been made towards reaching the goal of a price competitive renewable resin, but that further research is required to meet the twin challenges of low renewable resin cost and satisfactory quality requirements. Particular areas of concern are wood panel press times, variability of renewable resin properties, odour, lack of reactive sites compared to phenol and potential for increased emissions of volatile organic compounds.

Engines for combined heat and power

Spark-ignited (SI) gas engines are for the use of fuel gas only and are limited to the flammable range of the gas; this means the range of a concentration of a gas or vapor that will burn after ignition. Fuel gas like syngas from gasification or biogas must meet high quality and chemical purity standards for combustion in SI gas engines. Considerable effort has been devoted to fast pyrolysis over the years and some of the product oils have been tested in diesel or dual-fuel engines since 1993. For biogas conversion, usually dual-fuel engines are used, while for synthesis gas the use of gas engines is more common. The trials using wood derived pyrolysis oil from fast pyrolysis have not yet been a success story and these approaches have usually failed due to the high corrosivity of the pyrolysis oils.

Food-Web Complexity in Guaymas Basin Hydrothermal Vents and Cold Seeps

In the Guaymas Basin, the presence of cold seeps and hydrothermal vents in close proximity, similar sedimentary settings and comparable depths offers a unique opportunity to assess and compare the functioning of these deep-sea chemosynthetic ecosystems. The food webs of five seep and four vent assemblages were studied using stable carbon and nitrogen isotope analyses. Although the two ecosystems shared similar potential basal sources, their food webs differed: seeps relied predominantly on methanotrophy and thiotrophy via the Calvin-Benson-Bassham (CBB) cycle and vents on petroleum-derived organic matter and thiotrophy via the CBB and reductive tricarboxylic acid (rTCA) cycles. In contrast to symbiotic species, the heterotrophic fauna exhibited high trophic flexibility among assemblages, suggesting weak trophic links to the metabolic diversity of chemosynthetic primary producers. At both ecosystems, food webs did not appear to be organised through predator-prey links but rather through weak trophic relationships among co-occurring species. Examples of trophic or spatial niche differentiation highlighted the importance of species-sorting processes within chemosynthetic ecosystems. Variability in food web structure, addressed through Bayesian metrics, revealed consistent trends across ecosystems. Food-web complexity significantly decreased with increasing methane concentrations, a common proxy for the intensity of seep and vent fluid fluxes. Although high fluid-fluxes have the potential to enhance primary productivity, they generate environmental constraints that may limit microbial diversity, colonisation of consumers and the structuring role of competitive interactions, leading to an overall reduction of food-web complexity and an increase in trophic redundancy. Heterogeneity provided by foundation species was identified as an additional structuring factor. According to their biological activities, foundation species may have the potential to partly release the competitive pressure within communities of low fluid-flux habitats. Finally, ecosystem functioning in vents and seeps was highly similar despite environmental differences (e.g. physico-chemistry, dominant basal sources) suggesting that ecological niches are not specifically linked to the nature of fluids. This comparison of seep and vent functioning in the Guaymas basin thus provides further supports to the hypothesis of continuity among deep-sea chemosynthetic ecosystems.

New Catalysts for the Renewable Production of Monomers for Bioplastics

Terephthalic acid (PTA) is one of the monomers used for the synthesis of the polyester, polyethylene terephthalate (PET), that is used for the large-scale manufacture of synthetic fibers and plastic bottles. PTA is largely produced from the liquid-phase oxidation of petroleum-derived p-xylene (PX). However, there are now ongoing worldwide efforts exploring alternative routes for producing PTA from renewable, biomass resources.

In this thesis, I present a new route to PTA starting from the biomass-derived platform chemical, 5-hydroxymethylfurfural (HMF). This route utilizes new, selective Diels-Alder-dehydration reactions involving ethylene and is advantageous over the previously proposed Diels-Alder-dehydration route to PTA from HMF via 2,5-dimethylfuran (DMF) since the H₂ reduction of HMF to DMF is avoided. Specifically, oxidized derivatives of HMF are reacted as is, or after etherification-esterification with methanol, with ethylene over solid Lewis acid catalysts that do not contain strong Brønsted acids in order to synthesize intermediates of PTA and its equally important diester, dimethyl terephthalate (DMT). The partially oxidized HMF, 5-(hydroxymethyl)furoic acid (HMFA) is reacted with high pressure ethylene over a pure-silica molecular sieve catalyst containing framework tin (Sn-Beta) to produce the Diels-Alder-dehydration product, 4-(hydroxymethyl)benzoic acid (HMBA), with ~30% selectivity at ~20% yield. If HMFA is protected with methanol to form methyl 5-(methoxymethyl)furan-2-carboxylate (MMFC), MMFC can react with ethylene in the presence of a pure-silica molecular sieve containing framework zirconium (Zr-Beta) to produce methyl 4-(methoxymethyl)benzenecarboxylate (MMBC) with >70% selectivity at >20% yield. HMBA and MMBC can then be oxidized to produce PTA and DMT, respectively. When Lewis acid containing mesoporous silica (MCM-41) and amorphous silica, or Brønsted acid containing zeolites (Al-Beta), are used as catalysts, a significant decrease in selectivity/yield of the Diels-Alder-dehydration product is observed.

An investigation to elucidate the reaction network and side products in the conversion of MMFC to MMBC was performed, and the main side products are found to be methyl 4-formylcyclohexa-1,3-diene-1-carboxylate and the ethylene Diels-Alder adduct of this cyclohexadiene. These products presumably form by a different dehydration pathway of the MMFC/ethylene Diels-Alder adduct and should be included when determining the overall selectivity to PTA or DMT since, like MMBC, these compounds are precursors to PTA or DMT.

Fundamental physical and chemical information on the ethylene Diels-Alder-dehydration reactions catalyzed by the Lewis acid-containing molecular sieves was obtained. Madon-Boudart experiments using Zr-Beta as catalyst show that the reaction rates are limited by chemical kinetics only (physical transport limitations are not present), all the Zr⁴⁺ centers are incorporated into the framework of the molecular sieve, and the whole molecular sieve crystal is accessible for catalysis. Apparent activation energies using Zr-Beta are low, suggesting that the overall activation energy of the system may be determined by a collection of terms and is not the true activation energy of a single chemical step.

Análise de um queimador infravermelho funcionando com combustível híbrido : GLP/Bio-óleo

Biomass is considered the largest renewable energy source that can be used in an environmentally sustainable. From the pyrolysis of biomass is possible to obtain products with higher energy density and better use properties. The liquid resultant of this process is traditionally called bio-oil. The use of infrared burners in industrial applications has many advantages in terms of technical-operational, for example, uniformity in the heat supply in the form of radiation and convection, with a greater control of emissions due to the passage of exhaust gases through a macroporous ceramic bed. This paper presents a commercial infrared burner adapted with an ejector proposed able to burn a hybrid configuration of liquefied petroleum gas (LPG) and bio-oil diluted. The dilution of bio-oil with absolute ethanol aimed to decrease the viscosity of the fluid, and improving the stability and atomization. It was introduced a temperature controller with thermocouple modulating two stages (low heat / high heat), and solenoid valves for fuels supply. The infrared burner has been tested, being the diluted bio-oil atomized, and evaluated its performance by conducting energy balance. The method of thermodynamic analysis to estimate the load was used an aluminum plate located at the exit of combustion gases and the distribution of temperatures measured by thermocouples. The dilution reduced the viscosity of the bio-oil in 75.4% and increased by 11% the lower heating value (LHV) of the same, providing a stable combustion to the burner through the atomizing with compressed air and burns combined with LPG. Injecting the hybrid fuel there was increase in the heat transfer from the plate to the environment in 21.6% and gain useful benefit of 26.7%, due to the improved in the efficiency of the 1st Law of Thermodynamics of infrared burner

La relazione cinematografica tra Italia e Iran

Questa tesi illustra la presenza del cinema italiano in Iran e analizza come gli spettatori abbiano accettato il cinema straniero in concomitanza con le trasformazioni della società iraniana. L’indagine parte dagli aspetti economici derivati dal petrolio come motore di crescita e cambiamento della società iraniana. Elemento imprescindibile dai rapporti diplomatici con i paesi occidentali, la tesi ripercorre le tappe della nazionalizzazione petrolifera, analizza il ruolo giocato dall’Italia in questo contesto e la nascita del rapporto commerciale tra Italia e Iran. Lo studio prende poi in esame più nel dettaglio le relazioni italo-iraniane dal punto di vista cinematografico, e il successo dei film italiani in Iran. Pertanto, la tesi illustra le motivazioni della presenza cinematografica italiana in Iran e prende in esame l’influenza prodottasi attraverso le relazioni bilaterali. L’analisi attraversa le tappe del doppiaggio cinematografico in lingua persiana effettuato in Italia, il cinema popolare iraniano e il cinema intellettuale. Fermo restando una componente italiana nello studio, maggiore attenzione è dedicata al Paese d’arrivo, l’Iran, usando dati tratti da documenti storici, testi, giornali, risorse disponibili e interviste con persone informate in materia. Lo studio è concentrato su testi che approfondiscono la situazione economica e cinematografica iraniana all’epoca della monarchia di Mohammad Reza Pahlavi, coincidente con il secondo dopoguerra, durante il quale l’influenza cinematografica italiana si è fatta maggiormente sentire sul cinema iraniano. Obiettivo della tesi è definire le ragioni che hanno favorito lo sviluppo del rapporto cinematografico tra i due paesi, come il cinema italiano si sia manifestato nel cinema iraniano, e i presupposti che hanno comportato la crescita di quest’ultimo.

Bioremediation Potential Of Microorganisms Derived From Petroleum Reservoirs.

Bacterial strains and metagenomic clones, both obtained from petroleum reservoirs, were evaluated for petroleum degradation abilities either individually or in pools using seawater microcosms for 21 days. Gas Chromatography-Flame Ionization Detector (GC-FID) and Gas Chromatography-Mass Spectrometry (GC-MS) analyses were carried out to evaluate crude oil degradation. The results showed that metagenomic clones 1A and 2B were able to biodegrade n-alkanes (C14 to C33) and isoprenoids (phytane and pristane), with rates ranging from 31% to 47%, respectively. The bacteria Dietzia maris CBMAI 705 and Micrococcus sp. CBMAI 636 showed higher rates reaching 99% after 21 days. The metagenomic clone pool biodegraded these compounds at rates ranging from 11% to 45%. Regarding aromatic compound biodegradation, metagenomic clones 2B and 10A were able to biodegrade up to 94% of phenanthrene and methylphenanthrenes (3-MP, 2-MP, 9-MP and 1-MP) with rates ranging from 55% to 70% after 21 days, while the bacteria Dietzia maris CBMAI 705 and Micrococcus sp. CBMAI 636 were able to biodegrade 63% and up to 99% of phenanthrene, respectively, and methylphenanthrenes (3-MP, 2-MP, 9-MP and 1-MP) with rates ranging from 23% to 99% after 21 days. In this work, isolated strains as well as metagenomic clones were capable of degrading several petroleum compounds, revealing an innovative strategy and a great potential for further biotechnological and bioremediation applications.

Action mechanisms of petroleum hydrocarbons present in waters impacted by an oil spill on the genetic material of Allium cepa root cells

Chromosomal aberration (CA) assays have been widely used, not only to assess the genotoxic effects of chemical agents, but also to evaluate their action mechanisms on the genetic material of exposed organisms. This is of particular interest, since such analyses provide a better knowledge related to the action of these agents on DNA. Among test organisms, Allium cepa is an outstanding species due to its sensitivity and suitable chromosomal features, which are essential for studies on chromosomal damage or disturbances in cell cycle. The goal of the present study was to analyze the action mechanisms of chemical agents present in petroleum polluted waters. Therefore, CA assay was carried out in A. cepa meristematic cells exposed to the Guaeca river waters, located in the city of Sao Sebastiao, SP, Brazil, which had its waters impacted by an oil pipeline leak. Analyses of the aberration types showed clastogenic and aneugenic effects for the roots exposed to the polluted waters from Guaeca river, besides the induction of cell death. Probably all the observed effects were induced by the petroleum hydrocarbons derived from the oil leakage. (C) 2008 Elsevier B.V. All rights reserved.

Petroleum contamination impact on macrobenthic communities under the influence of an oil refinery: Integrating chemical and biological multivariate data

Petroleum contamination impact on macrobenthic communities in the northeast portion of Todos os Santos Bay was assessed combining in multivariate analyses, chemical parameters such as aliphatic and polycyclic aromatic hydrocarbon indices and concentration ratios with benthic ecological parameters. Sediment samples were taken in August 2000 with a 0.05 m(2) van Veen grab at 28 sampling locations. The predominance of n-alkanes with more than 24 carbons, together with CPI values close to one, and the fact that most of the stations showed UCM/resolved aliphatic hydrocarbons ratios (UCM:R) higher than two, indicated a high degree of anthropogenic contribution, the presence of terrestrial plant detritus, petroleum products and evidence of chronic oil pollution. The indices used to determine the origin of PAH indicated the occurrence of a petrogenic contribution. A pyrolytic contribution constituted mainly by fossil fuel combustion derived PAH was also observed. The results of the stepwise multiple regression analysis performed with chemical data and benthic ecological descriptors demonstrated that not only total PAH concentrations but also specific concentration ratios or indices such as >= C24:< C24, An/178 and Fl/Fl + Py, are determining the structure of benthic communities within the study area. According to the BIO-ENV results petroleum related variables seemed to have a main influence on macrofauna community structure. The PCA ordination performed with the chemical data resulted in the formation of three groups of stations. The decrease in macrofauna density, number of species and diversity from groups III to I seemed to be related to the occurrence of high aliphatic hydrocarbon and PAH concentrations associated with fine sediments. Our results showed that macrobenthic communities in the northeast portion of Todos os Santos Bay are subjected to the impact of chronic oil pollution as was reflected by the reduction in the number of species and diversity. These results emphasise the importance to combine in multivariate approaches not only total hydrocarbon concentrations but also indices, isomer pair ratios and specific compound concentrations with biological data to improve the assessment of anthropogenic impact on marine ecosystems. (c) 2008 Elsevier Ltd. All rights reserved.

USE OF BARU OIL (Dipteryx alata Vog.) TO PRODUCE BIODIESEL AND STUDY OF THE PHYSICAL AND CHEMICAL CHARACTERISTICS OF BIODIESEL/PETROLEUM DIESEL FUEL BLENDS

We describe production of methyl and ethyl esters derived from baru oil (Dipteryx alata Vog.). Water and alcohols are removed from the biodiesel obtained by simple distillation. We study the acidity, density, iodine number, viscosity, water content, peroxide number, external appearance, and saponification number of the oil, its methyl and ethyl esters (biodiesels) and their blends (B5, B10, B15, B20, and B30) with commercial diesel fuel.

The Laboratory Evaluation of Bio Oil Derived From Waste Resources as Extender for Asphalt Binder

A shortage of petroleum asphalt is creating opportunities for engineers to utilize alternative pavement materials. Three types of bio oils, original bio oil (OB), dewatered bio oil (DWB) and polymer-modified bio oil (PMB) were used to modify and partially replace petroleum asphalt in this research. The research investigated the procedure of producing bio oil, the rheological properties of asphalt binders modified and partially replaced by bio oil, and the mechanical performances of asphalt mixtures modified by bio oil. The analysis of variance (ANOVA) is conducted on the test results for the significance analysis. The main finding of the study includes: 1) the virgin bioasphalt is softer than the traditional asphalt binder PG 58-28 but stiffer after RTFO aging because bio oil ages much faster than the traditional asphalt binder during mixing and compaction; 2) the binder test showed that the addition of bio oil is expected to improve the rutting performance while reduce the fatigue and low temperature performance; 3) both the mass loss and the oxidation are important reasons for the bio oil aging during RTFO test; the mixture test showed that 1) most of the bio oil modified asphalt mixture had slightly higher rutting depth than the control asphalt mixture, but the difference is not statistically significant; 2) the dynamic modulus of some of the bio oil modified asphalt mixture were slightly lower than the control asphalt mixture, the E* modulus is also not statistically significant; 3) most of the bio oil modified asphalt mixture had higher fatigue lives than the control asphalt mixture; 4) the inconsistence of binder test results and mixture test results may be attributed to that the aging during the mixing and compaction was not as high as that in the RTFO aging simulation. 5) the implementation of Michigan wood bioasphalt is anticipated to reduce the emission but bring irritation on eyes and skins during the mixing and compaction.

Biodegradation of polyurethane derived from castor oil

The aim of this research was to study the biodegradation of a polymer derived from castor oil, which is a renewable, natural material that is a practical alternative for the replacement of traditional polyurethane foams. Due to its molecular structure, which contains polyester segments derived from vegetable oil, the polymeric surface is susceptible to microorganism attack. This study tested the biological degrading agent that was in contact with the microorganisms resulting from microbiological grease degrading agents, when foam was inoculated. Solid-media agar-plate tests were conducted for their potential to evaluate the biodegradation of polymeric particles by specific strains of microorganisms during 216 hours. The growth rate was defined. This technique provides a way of distinguishing the degradation abilities of microorganisms from the degradability of materials.

SOLID STATE STUDIES ON MOLECULAR INCLUSIONS OF LIPPIA SIDOIDES ESSENTIAL OIL OBTAINED BY SPRAY DRYING

Inclusion complexes of Lippia sidoides essential oil and beta-cyclodextrin were obtained by slurry method and its solid powdered form was prepared using spray drying. The influence of the spray drying, as well as the different essential oil:beta-cyclodextrin ratio on the characteristics of the final product was investigated. With regard to the total oil retention 1:10 mass/mass ratio as optimal was found between the essential oil and beta-cyclodextrin. Thermoanalytical techniques (TG, EGD, TG-MS) were used to support the formation of inclusion complex and to examine their physicochemical properties after accelerated storage conditions. It may be assumed that the thermal properties of the complexes were influenced not only by the different essential oil/beta-cyclodextrin ratio but also by the storage conditions. In the aspect of their thermal stabilities, complex prepared with 1:10 m/m ratio (essential oil: beta-cyclodextrin) was the most stable one.