Illinois energy production, 1960-1977 /

Prepared by the Research Division of the Dept. of Business and Economic Development under contract with the Illinois Institute of Natural Resources.

China oil production prospects.

"ER77-10030U."

Investigation of concentration of economic power. Hearings before the Temporary National Economic Committee, Congress of the United States, Seventy-fifth Congress, third session[--Seventy-sixth Congress, third session] pursuant to Public resolution no. 113 (Seventy-fifth Congress) authorizing and directing a select committee to make a full and complete study and investigation with respect to the concentration of economic power in, and financial control over, production of goods and services ...

1939.--pt.30. Technology and concentration of economic power. Apr.8-12, 15-19, 22-26, 1940.--31. Investments, profits, and rates of return for selected industries.

Petroleum System Analysis: Middle Magdalena Valley Basin, Colombia, South America

The purpose of this study is to create a petroleum system model and to assess whether or not the La Luna Formation has potential for unconventional exploration and production in the Middle Magdalena Valley Basin (MMVB), Colombia. Today, the Magdalena River valley is an intermontane valley located between the Central and Eastern Cordillera of Colombia. The underlying basin, however, represents a major regional sedimentary basin that received deposits from the Triassic through the Cenozoic. In recent years Colombia has been of great exploration interest because of its potentially vast hydrocarbon resources, existing petroleum infrastructure, and skilled workforce. Since the early 1900s when the MMVB began producing, it has led to discoveries of 1.9 billion barrels of oil (BBO) and 2.5 trillion cubic feet (Tcf) of gas (Willatt et al., 2012). Colombia is already the third largest producer of oil in South America, and there is good potential for additional unconventional exploration and production in the Cretaceous source rocks (Willatt et al., 2012). Garcia Gonzalez et al. (2009) estimate the potential remaining hydrocarbons in the La Luna Formation in the MMVB to be between 1.15 and 10.33 billion barrels of oil equivalent (BBOE; P90 and P10 respectively), with 2.02 BBOE cumulative production to date. Throughout the 1900s and early 2000s, Cenozoic continental and transitional clastic reservoirs were the primary exploration interest in the MMVB (Dickey, 1992). The Cretaceous source rocks, such as the La Luna Formation, are now the target for unconventional exploration and production. In the MMVB, the La Luna formation is characterized by relatively high total organic carbon (TOC) values, moderate maturity, and adequate thickness and depth (Veigal and Dzelalijal, 2014). The La Luna Formation is composed of Cenomanian-Santonian aged shales, marls, and limestones (Veigal and Dzelalijal, 2014). In addition to the in-situ hydrocarbons, the fractured limestones in the La Luna formation act as secondary reservoirs for light oil from other formations (Veigal and Dzelalijal, 2014). Thus the system can be considered more of a hybrid play, rather than a pure unconventional play. The Cretaceous source rocks of the MMVB exhibit excellent potential for unconventional exploration and production. Due to the complex structural nature of the MMVB, an understanding of the distribution of rocks and variations in rock qualities is essential for reducing risk in this play.

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.

Low severity Fischer-Tropsch synthesis for the production of synthetic hydrocarbon fuels

Currently, the main source for the production of liquid transportation fuels is petroleum, the continued use of which faces many challenges including depleting oil reserves, significant oil price rises, and environmental concerns over global warming which is widely believed to be due to fossil fuel derived CO2 emissions and other greenhouse gases. In this respect, lignocellulosic or plant biomass is a particularly interesting resource as it is the only renewable source of organic carbon that can be converted into liquid transportation fuels. The gasification of biomass produces syngas which can then be converted into synthetic liquid hydrocarbon fuels by means of the Fischer-Tropsch (FT) synthesis. This process has been widely considered as an attractive option for producing clean liquid hydrocarbon fuels from biomass that have been identified as promising alternatives to conventional fossil fuels like diesel and kerosene. The resulting product composition in FT synthesis is influenced by the type of catalyst and the reaction conditions that are used in the process. One of the issues facing this conversion process is the development of a technology that can be scaled down to match the scattered nature of biomass resources, including lower operating pressures, without compromising liquid composition. The primary aims of this work were to experimentally explore FT synthesis at low pressures for the purpose of process down-scaling and cost reduction, and to investigate the potential for obtaining an intermediate FT synthetic crude liquid product that can be integrated into existing refineries under the range of process conditions employed. Two different fixed-bed micro-reactors were used for FT synthesis; a 2cm3 reactor at the University of Rio de Janeiro (UFRJ) and a 20cm3 reactor at Aston University. The experimental work firstly involved the selection of a suitable catalyst from three that were available. Secondly, a parameter study was carried out on the 20cm3 reactor using the selected catalyst to investigate the influence of reactor temperature, reactor pressure, space velocity, the H2/CO molar ratio in the feed syngas and catalyst loading on the reaction performance measured as CO conversion, catalyst stability, product distribution, product yields and liquid hydrocarbon product composition. From this parameter study a set of preferred operating conditions was identified for low pressure FT synthesis. The three catalysts were characterized using BET, XRD, TPR and SEM. The catalyst selected was an unpromoted Co/Al2O3 catalyst. FT synthesis runs on the 20cm3 reactor at Aston were conducted for 48 hours. Permanent gases and light hydrocarbons (C1-C5) were analysed in an online GC-TCD/FID at hourly intervals. The liquid hydrocarbons collected were analyzed offline using GC-MS for determination of fuel composition. The parameter study showed that CO conversion and liquid hydrocarbon yields increase with increasing reactor pressure up to around 8 bar, above which the effect of pressure is small. The parameters that had the most significant influence on CO conversion, product selectivity and liquid hydrocarbon yields were reactor temperature and catalyst loading. The preferred reaction conditions identified for this research were: T = 230ºC, P = 10 bar, H2/CO = 2.0, WHSV = 2.2 h-1, and catalyst loading = 2.0g. Operation in the low range of pressures studied resulted in low CO conversions and liquid hydrocarbon yields, indicating that low pressure BTL-FT operation may not be industrially viable as the trade off in lower CO conversions and once-through liquid hydrocarbon product yields has to be carefully weighed against the potential cost savings resulting from process operation at lower pressures.

Nanoporous solid acid and base catalysts for sustainable biofuels production

Dwindling fossil fuel reserves, and growing concerns over CO2 emissions and associated climate change, are driving the quest for renewable feedstocks to provide alternative, sustainable fuel sources. Catalysis has a rich history of facilitating energy efficient, selective molecular transformations, and in a post-petroleum era will play a pivotal role in overcoming the scientific and engineering barriers to economically viable, and sustainable, biofuels derived from renewable resources. The production of second generation biofuels, derived from biomass sourced from inedible crop components, e.g. agricultural or forestry waste, or alternative non-food crops such as Switchgrass or Jatropha Curcas that require minimal cultivation, necessitate new heterogeneous catalysts and processes to transform these polar and viscous feedstocks [1]. Here we show how advances in the rational design of nanoporous solid acids and bases, and their utilisation in novel continuous reactors, can deliver superior performance in the energy-efficient esterification and transesterification of bio-oil components into biodiesel [2-4]. Notes: [1] K. Wilson, A.F. Lee, Cat. Sci. Tech. 2012 ,2, 884. [2] J. Dhainaut, J.-P. Dacquin, A. F. Lee, K. Wilson, Green Chem. 2010 , 12, 296. [3] C. Pirez, J.-M. Caderon, J.-P. Dacquin, A.F. Lee, K. Wilson, ACS Catal. 2012 , 2, 1607. [4] J.J. Woodford, J.-P. Dacquin, K. Wilson, A.F. Lee, Energy Environ. Sci. 2012 , 5, 6145.

Heterogeneous catalysts for biodiesel production

The combination of dwindling oil reserves and growing concerns over carbon dioxide emissions and associated climate change is driving the urgent development of clean, sustainable energy supplies. Biodiesel is non-toxic and biodegradable, with the potential for closed CO2 cycles and thus vastly reduced carbon footprints compared with petroleum fuels. However, current manufacturing routes employing soluble catalysts are very energy inefficient and produce copious amounts of contaminated water waste. This review highlights the significant progress made in recent years towards developing solid acid and base catalysts for biodiesel synthesis. Issues to be addressed in the future are also discussed including the introduction of non-edible oil feedstocks, as well as technical advances in catalyst and reactor design to ensure that biodiesel remains a key player in the renewable energy sector for the 21st century.

Catalysts in production of biodiesel:a review

Biodiesel is a renewable substitute fuel for petroleum diesel fuel which is made from nontoxic, biodegradable, renewable sources such as refined and used vegetable oils and animal fats. Biodiesel is produced by transesterification in which oil or fat is reacted with a monohydric alcohol in the presence of a catalyst. The process of transesterification is affected by the mode of reaction, molar ratio of alcohol to oil, type of alcohol, nature and amount of catalysts, reaction time, and temperature. Various studies have been carried out using different oils as the raw material and different alcohols (methanol, ethanol, butanol), as well as different catalysts, notably homogeneous ones such as sodium hydroxide, potassium hydroxide, sulfuric acid, and supercritical fluids or enzymes such as lipases. Recent research has focused on the application of heterogeneous catalysts to produce biodiesel, because of their environmental and economic advantages. This paper reviews the literature regarding both catalytic and noncatalytic production of biodiesel. Advantages and disadvantages of different methods and catalysts used are discussed. We also discuss the importance of developing a single catalyst for both esterification and transesterification reactions.

Natural Fibers for the Production of Green Composites

Development of green composite from natural fibers has gained increasing interests due to the environmental and sustainable benefits when compared with petroleum based non-degradable materials. However, a big challenge of green composites is the diversity of fiber sources, because of the large variation in the properties and characteristics of the lignocellulosic renewable resource. The lignocellulosic fibers/natural fibers used to reinforce green composites are reviewed in this chapter. A classification of fiber types and sources, the properties of various natural fibers, including structure, composition, physical and chemical properties are focused; followed by the impacts of natural fibers on composite properties, with identification of the main pathways from the natural fibers to the green composite. Furthermore, the main challenges and future trend of natural fibers are highlighted.

International capital and new frontiers of biofuel production in brazilian midwest

v. 18, n.1, jan./mar. 2016.

A bio-coke for anode production and the manufacturing method thereof

Dans l’industrie de l’aluminium, le coke de pétrole calciné est considéré comme étant le composant principal de l’anode. Une diminution dans la qualité du coke de pétrole a été observée suite à une augmentation de sa concentration en impuretés. Cela est très important pour les alumineries car ces impuretés, en plus d’avoir un effet réducteur sur la performance des anodes, contaminent le métal produit. Le coke de pétrole est aussi une source de carbone fossile et, durant sa consommation, lors du processus d’électrolyse, il y a production de CO2. Ce dernier est considéré comme un gaz à effet de serre et il est bien connu pour son rôle dans le réchauffement planétaire et aussi dans les changements climatiques. Le charbon de bois est disponible et est produit mondialement en grande quantité. Il pourrait être une alternative attrayante pour le coke de pétrole dans la fabrication des anodes de carbone utilisées dans les cuves d’électrolyse pour la production de l’aluminium. Toutefois, puisqu’il ne répond pas aux critères de fabrication des anodes, son utilisation représente donc un grand défi. En effet, ses principaux désavantages connus sont sa grande porosité, sa structure désordonnée et son haut taux de minéraux. De plus, sa densité et sa conductivité électrique ont été rapportées comme étant inférieures à celles du coke de pétrole. L’objectif de ce travail est d’explorer l’effet du traitement de chaleur sur les propriétés du charbon de bois et cela, dans le but de trouver celles qui s’approchent le plus des spécifications requises pour la production des anodes. L’évolution de la structure du charbon de bois calciné à haute température a été suivie à l’aide de différentes techniques. La réduction de son contenu en minéraux a été obtenue suite à des traitements avec de l’acide chlorhydrique utilisé à différentes concentrations. Finalement, différentes combinaisons de ces deux traitements, calcination et lixiviation, ont été essayées dans le but de trouver les meilleures conditions de traitement.

Ethanol production from brown seaweed using non-conventional yeasts

The use of macroalgae (seaweed) as a potential source of biofuels has attracted considerable worldwide interest. Since brown algae, especially the giant kelp, grow very rapidly and contain considerable amounts of polysaccharides, coupled with low lignin content, they represent attractive candidates for bioconversion to ethanol through yeast fermentation processes. In the current study, powdered dried seaweeds (Ascophylum nodosum and Laminaria digitata) were pre-treated with dilute sulphuric acid and hydrolysed with commercially available enzymes to liberate fermentable sugars. Higher sugar concentrations were obtained from L. digitata compared with A. nodosum with glucose and rhamnose being the predominant sugars, respectively, liberated from these seaweeds. Fermentation of the resultant seaweed sugars was performed using two non-conventional yeast strains: Scheffersomyces (Pichia) stipitis and Kluyveromyces marxianus based on their abilities to utilise a wide range of sugars. Although the yields of ethanol were quite low (at around 6 g/L), macroalgal ethanol production was slightly higher using K. marxianus compared with S. stipitis. The results obtained demonstrate the feasibility of obtaining ethanol from brown algae using relatively straightforward bioprocess technology, together with non-conventional yeasts. Conversion efficiency of these non-conventional yeasts could be maximised by operating the fermentation process based on the physiological requirements of the yeasts.

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.