Catalysing sustainable fuel and chemical synthesis

Concerns over the economics of proven fossil fuel reserves, in concert with government and public acceptance of the anthropogenic origin of rising CO2 emissions and associated climate change from such combustible carbon, are driving academic and commercial research into new sustainable routes to fuel and chemicals. The quest for such sustainable resources to meet the demands of a rapidly rising global population represents one of this century’s grand challenges. Here, we discuss catalytic solutions to the clean synthesis of biodiesel, the most readily implemented and low cost, alternative source of transportation fuels, and oxygenated organic molecules for the manufacture of fine and speciality chemicals to meet future societal demands.

Heterogeneously catalyzed lignin depolymerization

Biomass offers a unique resource for the sustainable production of bio-derived chemical and fuels as drop-in replacements for the current fossil fuel products. Lignin represents a major component of lignocellulosic biomass, but is particularly recalcitrant for valorization by existing chemical technologies due to its complex cross-linking polymeric network. Here, we highlight a range of catalytic approaches to lignin depolymerisation for the production of aromatic bio-oil and monomeric oxygenates.

Otimização do sistema de supervisão e controle de uma planta de tratamento de resíduos utilizando plasma

A major and growing problems faced by modern society is the high production of waste and related effects they produce, such as environmental degradation and pollution of various ecosystems, with direct effects on quality of life. The thermal treatment technologies have been widely used in the treatment of these wastes and thermal plasma is gaining importance in processing blanketing. This work is focused on developing an optimized system of supervision and control applied to a processing plant and petrochemical waste effluents using thermal plasma. The system is basically composed of a inductive plasma torch reactors washing system / exhaust gases and RF power used to generate plasma. The process of supervision and control of the plant is of paramount importance in the development of the ultimate goal. For this reason, various subsidies were created in the search for greater efficiency in the process, generating events, graphics / distribution and storage of data for each subsystem of the plant, process execution, control and 3D visualization of each subsystem of the plant between others. A communication platform between the virtual 3D plant architecture and a real control structure (hardware) was created. The goal is to use the concepts of mixed reality and develop strategies for different types of controls that allow manipulating 3D plant without restrictions and schedules, optimize the actual process. Studies have shown that one of the best ways to implement the control of generation inductively coupled plasma techniques is to use intelligent control, both for their efficiency in the results is low for its implementation, without requiring a specific model. The control strategy using Fuzzy Logic (Fuzzy-PI) was developed and implemented, and the results showed satisfactory condition on response time and viability

Tecnologia eletroquímica como tratamento alternativo de efluentes derivados da indústria têxtil e petroquímica

In this work, the treatment of wastewater from the textile industry, containing dyes as Yellow Novacron (YN), Red Remazol BR (RRB) and Blue Novacron CD (NB), and also, the treatment of wastewater from petrochemical industry (produced water) were investigated by anodic oxidation (OA) with platinum anodes supported on titanium (Ti/Pt) and boron-doped diamond (DDB). Definitely, one of the main parameters of this kind of treatment is the type of electrocatalytic material used, since the mechanisms and products of some anodic reactions depend on it. The OA of synthetic effluents containing with RRB, NB and YN were investigated in order to find the best conditions for the removal of color and organic content of the dye. According to the experimental results, the process of OA is suitable for decolorization of wastewaters containing these textile dyes due to electrocatalytic properties of DDB and Pt anodes. Removal of the organic load was more efficient at DDB, in all cases; where the dyes were degraded to aliphatic carboxylic acids at the end of the electrolysis. Energy requirements for the removal of color during OA of solutions of RRB, NB and YN depends mainly on the operating conditions, for example, RRB passes of 3.30 kWh m-3 at 20 mA cm-2 for 4.28 kWh m-3 at 60 mA cm-2 (pH = 1); 15.23 kWh m-3 at 20 mA cm-2 to 24.75 kWh m-3 at 60 mA cm-2 (pH 4.5); 10.80 kWh m-3 at 20 mA cm-2 to 31.5 kWh m-3 at 60 mA cm-2 (pH = 8) (estimated data for volume of treated effluent). On the other hand, in the study of OA of produced water effluent generated by petrochemical industry, galvanostatic electrolysis using DDB led to the complete removal of COD (98%), due to large amounts of hydroxyl radicals and peroxodisulphates generated from the oxidation of water and sulfates in solution, respectively. Thus, the rate of COD removal increases with increasing applied current density (15-60 mAcm-2 ). Moreover, at Pt electrode, approximately 50% removal of the organic load was achieved by applying from 15 to 30 mAcm-2 while 80% of COD removal was achieved for 60 mAcm-2 . Thus, the results obtained in the application of this technology were satisfactory depending on the electrocatalytic materials and operating conditions used for removal of organic load (petrochemical and textile effluents) as well as for the removal of color (in the case of textile effluents). Therefore, the applicability of electrochemical treatment can be considered as a new alternative like pretreatment or treatment of effluents derived from textiles and petrochemical industries.

Avaliação da biodegradação do dibenzotiofeno utilizando lodos ativados

During the oil refining process a huge discard volume of water occurs, which carries the contaminants from the process. A class of contaminant compounds resulting from the petrochemical industry are the Polyaromatic Hydrocarbons (PAH's). To evaluate the biodegradation of Dibenzothiophene in refinery water a synthetic wastewater was prepared to be treated using activated sludge. For this, a 2 3 Composite Design (plus 3 central points and six axial points) was carried out. The planning had as independent variables (factors) the initial concentration of DBT, pH and time of biodegradation. Biodegradation of DBT was assayed following the parameters COD, pH, temperature, SS, VSS, FVS, SVI. Concerned to the chromatographic conditions, a methodology was validated in order to verify the presence of DBT and its metabolite, 2-HBF, in the final wastewater treated by activated sludge system using a liquid - liquid extraction coupled to HPLC / UV analysis. The parameters used for validation were DL, QL, linearity, recovery and repeatability. As for optimization, the results indicated that the studied methodology can be used in monitoring the DBT degradation and 2- HBF by activated sludge, as they showed excellent linearity values, coefficients of variation, so as satisfactory recovery percentage. COD reduction efficiency tests showed an average percentage of 64.4%. The increasing trend for the results for the TSS and VSS tests showed that the activated sludge was well tailored. The best operating conditions for the reduction of COD were observed when operated with median concentrations of DBT, a higher time to biodegradation, and pH in both the acidic range as the basic one. The biodegradability of the DBT was confirmed by determining the presence of HBF-2. The highest concentrations of HBF-2 were obtained in extreme concentrations of DBT and pH, and higher biodegradation times.

Estudo de métodos de tratamento de efluentes (troca iônica e eletroquímico) separados e sequenciais para eliminação de derivados de petróleo

The produce of waste and the amount of the water produced coming from activities of petroleum production and extraction has been a biggest challenge for oil companies with respect to environmental compliance due to toxicity. The discard or the reuse this effluent containing organic compounds as BTEX (benzene, toluene, ethylbenzene and xylene) can cause serious environmental and human health problems. Thus, the objective this paper was study the performance of two process (separately and sequential) in one synthetic effluent for the benzene, toluene and xylene removal (volatile hydrocarbons presents in the produced water) through of electrochemical treatment using Ti/Pt electrode and exchange resin ionic used in the adsorption process. The synthetic solution of BTX was prepared with concentration of 22,8 mg L-1, 9,7 mg L-1 e 9,0 mg L-1, respectively, in Na2SO4 0,1 mol L-1. The experiments was developed in batch with 0.3 L of solution at 25ºC. The electrochemical oxidation process was accomplished with a Ti/Pt electrode with different current density (J = 10, 20 e 30 mA.cm-2). In the adsorption process, we used an ionic exchange resin (Purolite MB 478), using different amounts of mass (2,5, 5 and 10 g). To verify the process of technics in the sequential treatment, was fixed the current density at 10 mA cm-2 and the resin weight was 2.5 g. Analysis of UV-VIS spectrophotometry, chemical oxygen demand (COD) and gas chromatography with selective photoionization detector (PID) and flame ionization (FID), confirmed the high efficiency in the removal of organic compounds after treatment. It was found that the electrochemical process (separate and sequential) is more efficient than absorption, reaching values of COD removal exceeding 70%, confirmed by the study of the cyclic voltammetry and polarization curves. While the adsorption (separately), the COD removal did not exceed 25,8%, due to interactions resin. However, the sequential process (electrochemical oxidation and adsorption) proved to be a suitable alternative, efficient and cost-effectiveness for the treatment of effluents petrochemical.

Aplicação de tratamentos eletroquímicos integrados para remediação de solos e águas contaminadas com petróleo e pesticidas

Electrochemical technologies have been proposed as a promising alternative for the treatment of effluents and contaminated soils. Therefore, the objective of this work was to study the treatment of contaminated soils and wastewaters using electrochemical technologies. Thus, the study regarding the scale-up of the electrochemical system with continuous flow treatment of wastewater of the petrochemical industry was investigated using platinum electrodes supported on titanium (Ti / Pt), and boron-doped diamond (BDD). The results clearly showed that under the operating conditions studied and electrocatalytic materials employed, the better removal efficiency was achieved with BDD electrode reducing the chemical oxygen demand (COD) from 2746 mg L-1 to 200 mg L-1 in 5 h consuming 56.2 kWh m-3 . The decontamination of soils and effluents by petrochemical products was evaluated by studying the effects of electrokinetic remediation for removal of total petroleum hydrocarbons (HTP) from contaminated soil with diesel. The efficiency of this process was dependent on the electrolyte used Na2SO4 (96.46%), citric acid (81.36%) and NaOH (68.03%) for 15 days. Furthermore, the effluent after treatment of the soil was treated by electrochemical oxidation, achieving a good elimination of the organic polluting load dissolved. Depending on the physical behavior of wastewater contaminated with oil (emulsified state); atrazine emulsified effluents were investigated. The main characteristics of the effluent produced during the washing of contaminated soil were studied, being dependent on the surfactant dosage used; which determined its electrolytic treatment with BDD. The electrochemical oxidation of emulsified effluent of atrazine was efficient, but the key to the treatment is reducing the size of micelles.

Análise de confiabilidade de um moto-ventilador centrífugo: aplicação no sistema de pressurização de subestação industrial para garantia da segurança operacional na indústria petroquímica

The need of the oil industry to ensure the safety of the facilities, employees and the environment, not to mention the search for maximum efficiency of its facilities, makes it seeks to achieve a high level of excellence in all stages of its production processes in order to obtain the required quality of the final product. Know the reliability of equipment and what it stands for a system is of fundamental importance for ensuring the operational safety. The reliability analysis technique has been increasingly applied in the oil industry as fault prediction tool and undesirable events that can affect business continuity. It is an applied scientific methodology that involves knowledge in engineering and statistics to meet and or analyze the performance of components, equipment and systems in order to ensure that they perform their function without fail, for a period of time and under a specific condition. The results of reliability analyzes help in making decisions about the best maintenance strategy of petrochemical plants. Reliability analysis was applied on equipment (bike-centrifugal fan) between the period 2010-2014 at the Polo Petrobras Guamaré Industrial, situated in rural Guamaré municipality in the state of Rio Grande do Norte, where he collected data field, analyzed historical equipment and observing the behavior of faults and their impacts. The data were processed in commercial software reliability ReliaSoft BlockSim 9. The results were compared with a study conducted by the experts in the field in order to get the best maintenance strategy for the studied system. With the results obtained from the reliability analysis tools was possible to determine the availability of the centrifugal motor-fan and what will be its impact on the security of process units if it will fail. A new maintenance strategy was established to improve the reliability, availability, maintainability and decreased likelihood of Moto-Centrifugal Fan failures, it is a series of actions to promote the increased system reliability and consequent increase in cycle life of the asset. Thus, this strategy sets out preventive measures to reduce the probability of failure and mitigating aimed at minimizing the consequences.

Análise da biorremediação de compostos monoaromáticos em água através da pseudomonas aeruginosa

The monoaromatic compounds are toxic substances present in petroleum derivades and used broadly in the chemical and petrochemical industries. Those compounds are continuously released into the environment, contaminating the soil and water sources, leading to the possible unfeasibility of those hydrous resources due to their highly carcinogenic and mutagenic potentiality, since even in low concentrations, the BTEX may cause serious health issues. Therefore, it is extremely important to develop and search for new methodologies that assist and enable the treatment of BTEX-contaminated matrix. The bioremediation consists on the utilization of microbial groups capable of degrading hydrocarbons, promoting mineralization, or in other words, the permanent destruction of residues, eliminating the risks of future contaminations. This work investigated the biodegradation kinetics of water-soluble monoaromatic compounds (benzene, toluene and ethylbenzene), based on the evaluation of its consummation by the Pseudomonas aeruginosa bacteria, for concentrations varying from 40 to 200 mg/L. To do so, the performances of Monod kinetic model for microbial growth were evaluated and the material balance equations for a batch operation were discretized and numerically solved by the fourth order Runge-Kutta method. The kinetic parameters obtained using the method of least squares as statistical criteria were coherent when compared to those obtained from the literature. They also showed that, the microorganism has greater affinity for ethylbenzene. That way, it was possible to observe that Monod model can predict the experimental data for the individual biodegradation of the BTEX substrates and it can be applied to the optimization of the biodegradation processes of toxic compounds for different types of bioreactors and for different operational conditions.

Análise da biorremediação de compostos monoaromáticos em água através da pseudomonas aeruginosa

The monoaromatic compounds are toxic substances present in petroleum derivades and used broadly in the chemical and petrochemical industries. Those compounds are continuously released into the environment, contaminating the soil and water sources, leading to the possible unfeasibility of those hydrous resources due to their highly carcinogenic and mutagenic potentiality, since even in low concentrations, the BTEX may cause serious health issues. Therefore, it is extremely important to develop and search for new methodologies that assist and enable the treatment of BTEX-contaminated matrix. The bioremediation consists on the utilization of microbial groups capable of degrading hydrocarbons, promoting mineralization, or in other words, the permanent destruction of residues, eliminating the risks of future contaminations. This work investigated the biodegradation kinetics of water-soluble monoaromatic compounds (benzene, toluene and ethylbenzene), based on the evaluation of its consummation by the Pseudomonas aeruginosa bacteria, for concentrations varying from 40 to 200 mg/L. To do so, the performances of Monod kinetic model for microbial growth were evaluated and the material balance equations for a batch operation were discretized and numerically solved by the fourth order Runge-Kutta method. The kinetic parameters obtained using the method of least squares as statistical criteria were coherent when compared to those obtained from the literature. They also showed that, the microorganism has greater affinity for ethylbenzene. That way, it was possible to observe that Monod model can predict the experimental data for the individual biodegradation of the BTEX substrates and it can be applied to the optimization of the biodegradation processes of toxic compounds for different types of bioreactors and for different operational conditions.

Availability estimation and management for complex processing systems

“Availability” is the terminology used in asset intensive industries such as petrochemical and hydrocarbons processing to describe the readiness of equipment, systems or plants to perform their designed functions. It is a measure to suggest a facility’s capability of meeting targeted production in a safe working environment. Availability is also vital as it encompasses reliability and maintainability, allowing engineers to manage and operate facilities by focusing on one performance indicator. These benefits make availability a very demanding and highly desired area of interest and research for both industry and academia. In this dissertation, new models, approaches and algorithms have been explored to estimate and manage the availability of complex hydrocarbon processing systems. The risk of equipment failure and its effect on availability is vital in the hydrocarbon industry, and is also explored in this research. The importance of availability encouraged companies to invest in this domain by putting efforts and resources to develop novel techniques for system availability enhancement. Most of the work in this area is focused on individual equipment compared to facility or system level availability assessment and management. This research is focused on developing an new systematic methods to estimate system availability. The main focus areas in this research are to address availability estimation and management through physical asset management, risk-based availability estimation strategies, availability and safety using a failure assessment framework, and availability enhancement using early equipment fault detection and maintenance scheduling optimization.

Efeito da concentração de sólidos e de variáveis operacionais no desempenho de um hidrociclone concentrador

The hydrocycloning operation has a goal to separate solid-liquid suspensions and liquid-liquid emulsions through the centrifugal force action. Hydrocyclones are equipment with reduced size and used in both clarification and thickening. This device is used in many areas, like petrochemical and minerals process, and accumulate advantages like versatility and low cost of maintenance. However, the demand to improve the process and to reduce the costs has motivated several studies of equipment optimization. The filtering hydrocyclone is a non-conventional equipment developed at FEQUI/UFU with objective to improve the hydrocycloning separation efficiency. The purpose of this study is to evaluate the operating conditions of feed concentration and underflow diameter on the performance of a filtering geometry optimized to minimization of energy costs. The filtration effect was investigated through the comparison between the performance of the Optimized Filtering Hydrocyclone (HCOF) and the Optimized Concentrator Hydrocyclone (HCO). Because of the resemblance of hydrocyclones performance, the filtration did not represent significant effect on the performance of the HCOF. It was found that in this geometry the decrease of the variable underflow diameter was very favorable to thickening operation. The suspension concentration of quartzite at 1.0% of solids in volume was increased about 42 times when the 3 mm underflow diameter was used. The increase on the feed solid percentage was good for decreasing the energy spent, so that a minimum number of Euler of 730 was achieved at CVA = 10.0%v. However, a greater amount of solids in suspension leads to a lower efficiency of the equipment. Therefore, to minimize the underflow-to-throughput ratio and keep a high efficiency level, it is indicated to work with dilute suspension (CVA = 1.0%) and 3 mm underflow diameter (η = 67%). But if it is necessary to work with high feed concentration, the use of 5 mm underflow diameter provides a rise in the efficiency. The HCO hydrocyclone was compared to the traditional family of hydrocyclones Rietema and presented advantages like higher efficiency (34% higher in average) and lower energy costs (20% lower in average). Finally, the efficiency curves and project equation have been raised for the HCO hydrocyclone each with satisfactory adjust.

Tab. 2: Geochemical composition of metasomatites and parent rocks from the Polar Urals

Rare-metal alkali (quartz-feldspathic) metasomatites are considered in terms of their geologic position, structure, and composition. Their petrochemical and geochemical characteristics are given. In the Polar Urals, the metasomatites occur as lenticular and tube-like bodies in the fault zones of the Cambrian basement within the Kharbey block. Three types of the metasomatites, dated at ~300 Ma, have been recognised: quartz-bifeldspathic (kvalmites), quarzt-albitic, and albitites. They belong to the formation of quartz-feldspathic metasomatites of the fault zones.

Respuestas sindicales ante el desafío de la empresa-red: sector petroquímico y nuclear

El modelo de empresa-red constituye un desafío para los sistemas de relaciones laborales. Dicho modelo cuestiona el papel de las instituciones colectivas de trabajo, concebidas históricamente en el marco de una organización integrada verticalmente según el modelo fordista. En efecto, la empresa dispersa o el recurso a la subcontratación son contextos cada vez más habituales, en los cuales la organización del trabajo se encuentra disociada de la empresa en sentido jurídico y patrimonial, y donde se establecen relaciones de trabajo triangulares de facto entre empresa principal, empresa de servicios y trabajadores. La búsqueda de respuestas a esta problemática apunta a la reconstrucción de solidaridades entre los trabajadores, pasando por la acción de los representantes de los trabajadores. A partir de un estudio de casos llevado a cabo en dos industrias de flujo, la industria nuclear y la petroquímica, este artículo se propone analizar los efectos de la triangulación de la relación salarial a nivel de planta, y dos procesos experimentales de organización sindical y de negociación colectiva territorial que buscan dar respuesta a la problemática de la subcontratación. El artículo analiza los resultados y límites de dichas experiencias para reconstruir una “comunidad de trabajo” inclusiva de los trabajadores subcontratistas.

Coupled diusion and mechanics in battery electrodes

Thesis (Ph.D.)--University of Washington, 2016-08