Synthesis of activaded carbon materials from petroleum coke

Orientador: Antonio Carlos Luz LisboaDissertação (mestrado) - Universidade Estadual de Campinas, Faculdade de Engenharia QuimicaResumo: Materiais Carbonosos Ativados (MCA), tais como Carvões Ativados (CA) e Peneiras Moleculares de Carbono (PMC), são caracterizados por apresentar elevada área superficial específica e um grande volume de poros em sua matriz carbonosa, sendo sua principal propriedade a de adsorver moléculas tanto na fase líquida quanto na gasosa. O Brasil importa em sua totalidade peneiras moleculares produzidas a partir de precursores carbonosos, empregando-os nas mais diversas áreas de ciência e tecnologia e em vários segmentos industriais. O coque de petróleo é um resíduo com alto teor de carbono fixo e baixo teor de cinzas, e em decorrência de sua estrutura praticamente amorfa, é um material de pouco valor comercial, sendo considerado um resíduo problemático, tanto em termos ambientais quanto comerciais. Desta forma, a utilização de coque de petróleo para a produção de CAs e de PMCs torna-se atrativa para a utilização deste resíduo. O presente trabalho teve como objetivo estudar a síntese de carvões ativados através das ativações física e química de coque de petróleo proveniente da unidade de coqueamento retardado da REPLAN - PETROBRÁS, buscando avaliar as influências dos parâmetros de processo na qualidade dos CAs, tais como: concentração de agente ativante, tempo de ativação, temperatura de ativação e granulometria do coque de petróleo. A ativação física apresentou resultados insatisfatórios devido a baixa reatividade do coque de petróleo com o dióxido de carbono. Contudo, o coque de petróleo apresentou uma maior reatividade com hidróxido de potássio, permitindo desenvolver uma metodologia adequada para a ativação química do coque de petróleo com KOH, de modo a obter carvões ativados de elevada área superficial. Os resultados obtidos indicam a possibilidade de produção de carvões ativados de elevada área superficial, superiores a 2000 m2.g-1 a partir do coque de petróleoAbstract: Activated Carbon MateriaIs (ACM), such as Activated Carbons (AC) and Carbon Molecular Sieves (CMS), are characterized by a high specific surface area em high pore volume in their carbon matrix, being their principal property to adsorb molecules in liquid and gas phase. Brazil imports all its molecular sieves, using them in several areas of science and technology and industrial segments. Petroleum coke is a high carbon content residue with low ash content, and due to its amorphous structure have low comercial value, being considered an environmental and comercial problem. In this sense, the utilization of petroleum coke to produce AC and CMS becomes an atractive utilization of this residue. The objective of the present work was to study the synthesis of activated carbon by physical and chemical processes using as raw material the petroleum coke originated from the delayed coking unit from REPLAN PETROBRAS, evaluating the infiuence of process parameters, such as activating agent concentration, activation time, activation temperature and average particle size on the AC quality. The results of physical activation of petroleum coke was not satisfactory due to the low reactivity of the petroleum coke with the carbon dioxide. However, the petroleum coke presented higher reactivity with potassium hidroxide, given the possibility to develop an adequate methodology to chemically activate petroleum coke with KOH, in order to obtain activated carbon with high specific surface area. The results indicated the possibility to produce activated carbon materiaIs from petroleum coke with surface area higher than 2000 m2 .g-lMestradoEngenharia de ProcessosMestre em Engenharia Químic

Study of the dynamic of adsorption/desorption in activated carbon in storage tanks

Orientadores: Antonio Carlos Luz Lisbôa, Aparecido dos Reis CoutinhoTese (doutorado) - Universidade Estadual de Campinas, Faculdade de Engenharia QuímicaResumo: Gás natural (GN) é uma fonte de energia de origem fóssil, encontrado em formações rochosas subterrâneas ou associados em reservatórios de petróleo. O consumo anual de gás natural no Brasil em 2013 foi de 36,8 bilhões de metros cúbicos, equivalente a 1,1% do consumo mundial de 3,35 trilhões de metros cúbicos. Segundo o Ministério de Minas e Energia do Brasil, em 2013 o GN apresentou aproximadamente 12% da oferta interna de energia, com aumento em torno de 16% de 2012 para 2013. Porém o aumento nesta oferta enfrenta problemas devido aos elevados custos de transporte e armazenamento do GN, devido sua baixa densidade energética em condições de temperatura e pressão padrão, quando comparado com combustíveis líquidos derivados do petróleo. Os dois métodos convencionais de armazenamento e transporte de GN é a liquefação (GN Liquefeito ¿ GNL) e compressão (GN Comprimido ¿ GNC). O GN Adsorvido (GNA) é uma alternativa promissora aos métodos convencionais, pois em pressões moderadas, em torno de 4,0 MPa, um tanque com adsorvente possui capacidade de armazenamento superior a de um tanque vazio, devido à adsorção do gás natural nos microporos no adsorvente, que permite utilização de reservatórios mais leves e seguros. No presente trabalho foi realizado a produção de carvões ativados (CA) à partir de resíduos ou subprodutos de baixo valor agregado de setores industriais, com objetivo de avaliar a aplicabilidade destes CA em sistemas GNA, e de avaliar a influência de suas características na transferência de calor do leito adorvente. Coque de petróleo e biomassa foram ativadas física e/ou quimicamente, resultando em materiais adsorvente. Estes materiais foram caracterizados por meio de adsorção de nitrogênio gasoso a 77 K para identificar quais materiais e condições de produção são mais adequadas para o uso em sistemas GNA. Medidas de armazenamento de metano foram realizadas para avaliar a capacidade dos CA em função da pressão e temperatura. Os resultados de armazenamento foram analisados por meio de relações viriais, modelo de adsorção de Toth, potencial de adsorção e modelo de Dubinin-Stoeckli, permitindo obter parâmetros de adsorção, tais como, distribuição de poros e energias de adsorção. Modelo de transferência de calor em leito de armazenamento de gás natural foi desenvolvido considerando simultaneamente a transferência de calor e equilíbrio de adsorção. A resolução deste modelo permitiu avaliar parâmetros relativos aos efeitos da evolução térmica do leito e como esta afeta a operação de armazenamento. Perfis de temperatura no interior do leito de armazenamento em função da posição radial e tempo de armazenamento foram obtidos considerando diferentes cenários de troca térmica pela parede do tanqueAbstract: Natural gas (NG) is a energy source found in underground rock formations or associated with petroleum reservoirs. Brazil's annual natural gas consumption in 2013 was 36.8 billion cubic meters, equivalent to 1.1% of world consumption of 3.35 trillion cubic meters. According to the Ministry of Mines and Energy of Brazil, in 2013 the NG was approximately 12% of the domestic energy supply, an increase of around 16% from 2012 to 2013. However this offer is facing increasing problems due to high cost of transportation and storage, and because of its low energy density in standard conditions of temperature and pressure when compared to petroleum-derived liquid fuels. The two conventional methods of storage and transportation of natural gas is the liquefied natural gas (LNG) and compressed natural gas (CNG). The Adsorbed NG (ANG) is a promising alternative to conventional methods because at moderate pressures around 4.0 MPa, the adsorbent has a higher storage capacity than an empty storage tank, due to the adsorption of natural gas in the micropores of the adsorbent, which allows the use of lighter and safer tanks. In the present work production of activated carbon (AC) was made from waste or by-products of low cost from industries, in order to evaluate the applicability of these AC in ANG systems, and to evaluate the influence of their characteristics on the heat transfer of the asdorbent bed. Petroleum coke and biomass were activated physically and/or chemically. These materials were characterized by nitrogen gas adsorption at 77 K in order to identify wich materials and wich production conditions are better suited for use in ANG systems. Measurements of methane storage were carried out to evaluate the methane adsorption capacity of the AC as a function of pressure and temperature. The methane storage results were analyzed by adsorption virial relations, Toth adsorption model, potential adsorption model and Dubinin-Stoeckli model, allowing to obtain adsorption parameters such as pore distribution and adsorption energies. A heat transfer model in the adsorbent bed was developed considering heat transfer and adsorption equilibrium. The data obtained ny this model allow evaluate parameters related to the termal effects of the adsorbent bed and how this parameters affects the storage operation. Temperature profiles within the bed storage as function of the radial position and time of storage were obtained considering different scenarios by heat exchange through tank wallDoutoradoEngenharia de ProcessosDoutor em Engenharia Químic

Removal of cyanobacteria toxins from drinking water by adsorption on activated carbon fibers

Natural fibers from macadamia nut shell, dried coconut shell endocarp, unripe coconut mesocarp, sugarcane bagasse and pine wood residue were used to prepare activated carbon fibers (ACF) with potential application for removing microcystins. The ACF from pine wood and sugar cane bagasse were used to remove [D-Leucine¹]MCYST-LR from water. After 10 minutes of contact time, more than 98% of toxin was removed by the ACF. The microcystin adsorption monolayer, q m, in the ACF recovered 200 and 161 µg.mg-1, with the Langmuir adsorption constant, K L, of 2.33 and 1.23 L.mg-1. Adsorption of [D-Leucine¹]MCYST-LR in continuous process was studied for a fixed-bed ACF prepared from coconut shell and sugar cane bagasse and for two commercial activated carbon samples from treatment water plants of two Brazilian hemodialysis centers. Saturation of the beds occurred after 80 to 320 minutes, and the adsorption capacity for that toxin varied from 4.11 to 12.82 µg.mg-1

Effect of operating conditions on scrap tire pyrolysis

The ever growing focus on environmental issues has raised concerns about scrap tires, whose major component - vulcanized rubber - does not degrade easily. When burned, tires release toxic gases containing substantial amounts of sulfur and ammonia in addition to other pollutants. Dumped on empty city lots, tires are also a breeding ground for mosquitoes. Many proposals have been put forward to handle the disposal of scrap tires, but none of them have proved to offer a definitive solution. The study reported here investigated the production of fuel oil and activated carbon from the pyrolysis of scrap tires. The initial mass of rubber yielded approximately 46% of oil, 40% of activated carbon and 14% of gases. The resulting activated carbon displayed a specific surface area of 200 m².g-1

NEOTROPICAL ALIEN MAMMALS: a data set of occurrence and abundance of alien mammals in the Neotropics

Biological invasion is one of the main threats to native biodiversity. For a species to become invasive, it must be voluntarily or involuntarily introduced by humans into a nonnative habitat. Mammals were among first taxa to be introduced worldwide for game, meat, and labor, yet the number of species introduced in the Neotropics remains unknown. In this data set, we make available occurrence and abundance data on mammal species that (1) transposed a geographical barrier and (2) were voluntarily or involuntarily introduced by humans into the Neotropics. Our data set is composed of 73,738 historical and current georeferenced records on alien mammal species of which around 96% correspond to occurrence data on 77 species belonging to eight orders and 26 families. Data cover 26 continental countries in the Neotropics, ranging from Mexico and its frontier regions (southern Florida and coastal-central Florida in the southeast United States) to Argentina, Paraguay, Chile, and Uruguay, and the 13 countries of Caribbean islands. Our data set also includes neotropical species (e.g., Callithrix sp., Myocastor coypus, Nasua nasua) considered alien in particular areas of Neotropics. The most numerous species in terms of records are from Bos sp. (n = 37,782), Sus scrofa (n = 6,730), and Canis familiaris (n = 10,084); 17 species were represented by only one record (e.g., Syncerus caffer, Cervus timorensis, Cervus unicolor, Canis latrans). Primates have the highest number of species in the data set (n = 20 species), partly because of uncertainties regarding taxonomic identification of the genera Callithrix, which includes the species Callithrix aurita, Callithrix flaviceps, Callithrix geoffroyi, Callithrix jacchus, Callithrix kuhlii, Callithrix penicillata, and their hybrids. This unique data set will be a valuable source of information on invasion risk assessments, biodiversity redistribution and conservation-related research. There are no copyright restrictions. Please cite this data paper when using the data in publications. We also request that researchers and teachers inform us on how they are using the data