Used vulcanized rubber tires have caused serious trouble worldwide. Current disposal and recycling methods all have undesirable side effects, and they generally do not produce maximum benefits. A thermocatalytic process using aluminum chloride as the main catalyst was demonstrated previously from 1992 to 1995 in our laboratory to convert used rubber tire to branched and ringed hydrocarbons. Products fell in the range of C4 to C8. Little to no gaseous products or fuel oil hydrocarbons of lower value were present. This project extended the previous experiments to accumulate laboratory data, and provide fundamental understanding of the thermocatalytic decomposition reaction of the model compounds including styrene-butadiene copolymers (SBR), butyl, and natural rubber. The liquid product yields of SBR and natural rubber consistently represented 20 to 30% of the original feedstock by weight. Generally, approximately 1 to 3% of the feedstock was converted to naphtha, while the remainder was liquefied petroleum gas. The liquid yields for butyl rubber were significantly higher than for SBR and natural rubber, generally ranging from 30 to 40% of the feedstock. Experiments were conducted to separate the catalyst from the residue by evaporation. Temperatures between 400 °C and 500 °C range are required to drive off significant amounts of catalyst. Decomposition of the catalyst also occurred in the recovery process. Reports in the literature and our observations strongly suggest that the AlCl3 forms an organometallic complex with the decomposing hydrocarbons so that it becomes integrated into the residue. Catalyst mixtures also were tested. Both AlCl3/NaCl and AlCl3/KCl mixtures had very small AlCl3 partial pressures at temperatures as high as 250 °C, unlike pure AlCl3 and AlCl3/MgCl2 mixtures. With the AlCl3/NaCl mixtures, decomposition of the rubber was observed at temperatures as low as 150 °C, although the reaction rates were considerably slower at lower temperatures. The amount of naphtha produced by the reaction also increased markedly, as did the yields of aromatics and cyclic paraffin. Recommendations are made for future research to definitively determine the economic and technical feasibility of the proposed thermocatalytic depolymerization process.

Used vulcanized rubber tires have caused serious trouble worldwide. Current disposal and recycling methods all have undesirable side effects, and they generally do not produce maximum benefits. A thermocatalytic process using aluminum chloride as the main catalyst was demonstrated previously from 1992 to 1995 in our laboratory to convert used rubber tire to branched and ringed hydrocarbons. Products fell in the range of C4 to C8. Little to no gaseous products or fuel oil hydrocarbons of lower value were present. This project extended the previous experiments to accumulate laboratory data, and provide fundamental understanding of the thermocatalytic decomposition reaction of the model compounds including styrene-butadiene copolymers (SBR), butyl, and natural rubber. The liquid product yields of SBR and natural rubber consistently represented 20 to 30% of the original feedstock by weight. Generally, approximately 1 to 3% of the feedstock was converted to naphtha, while the remainder was liquefied petroleum gas. The liquid yields for butyl rubber were significantly higher than for SBR and natural rubber, generally ranging from 30 to 40% of the feedstock. Experiments were conducted to separate the catalyst from the residue by evaporation. Temperatures between 400 °C and 500 °C range are required to drive off significant amounts of catalyst. Decomposition of the catalyst also occurred in the recovery process. Reports in the literature and our observations strongly suggest that the AlCl3 forms an organometallic complex with the decomposing hydrocarbons so that it becomes integrated into the residue. Catalyst mixtures also were tested. Both AlCl3/NaCl and AlCl3/KCl mixtures had very small AlCl3 partial pressures at temperatures as high as 250 °C, unlike pure AlCl3 and AlCl3/MgCl2 mixtures. With the AlCl3/NaCl mixtures, decomposition of the rubber was observed at temperatures as low as 150 °C, although the reaction rates were considerably slower at lower temperatures. The amount of naphtha produced by the reaction also increased markedly, as did the yields of aromatics and cyclic paraffin. Recommendations are made for future research to definitively determine the economic and technical feasibility of the proposed thermocatalytic depolymerization process.

A thermal catalytic decomposition process has been developed to recycle used tire rubber. This process enables the recovery of useful products, such as hydrocarbons and carbon blacks. During the catalytic decomposition process, the tire rubber is decomposed into smaller hydrocarbons, which are collected in the process. The solid reaction residue, which normally consists of carbon black, catalysts, other inorganic rubber compound components, and organic carbonaceous deposits, was subjected to a series of treatments with the intention to recover the valuable carbon black and catalyst. The process economics depend strongly on the commercial value of the recovered carbon black and the ability to recover and recycle the catalysts used in the process. Some of the important properties of the recovered carbon black product have been characterized and compared with that of commercial-grade carbon blacks. The composition of the recovered carbon black was analyzed by TGA and EDX, the structure and morphology were studied through transmission electron microscopy (TEM), and the specific surface area was measured by BET nitrogen adsorption. The recovered products possess qualities at least comparable to (or even better than) that of the commercial-grade carbon black N660. Methods for increasing the market value of this recovered carbon black product are discussed. Anhydrous aluminum chloride (AlCl3) was used as the primary catalyst in the process. A catalyst recovery method based on the AlCl3 sublimation and recondensation was studied and found to be non-feasible. It is believed that the catalyst forms an organometallic complex with the decomposed hydrocarbons, such that it becomes chemically bonded to the residue material and hence not removable by evaporation. A scheme for the further study of the catalyst recovery is suggested.

A thermal catalytic decomposition process has been developed to recycle used tire rubber. This process enables the recovery of useful products, such as hydrocarbons and carbon blacks. During the catalytic decomposition process, the tire rubber is decomposed into smaller hydrocarbons, which are collected in the process. The solid reaction residue, which normally consists of carbon black, catalysts, other inorganic rubber compound components, and organic carbonaceous deposits, was subjected to a series of treatments with the intention to recover the valuable carbon black and catalyst. The process economics depend strongly on the commercial value of the recovered carbon black and the ability to recover and recycle the catalysts used in the process. Some of the important properties of the recovered carbon black product have been characterized and compared with that of commercial-grade carbon blacks. The composition of the recovered carbon black was analyzed by TGA and EDX, the structure and morphology were studied through transmission electron microscopy (TEM), and the specific surface area was measured by BET nitrogen adsorption. The recovered products possess qualities at least comparable to (or even better than) that of the commercial-grade carbon black N660. Methods for increasing the market value of this recovered carbon black product are discussed. Anhydrous aluminum chloride (AlCl3) was used as the primary catalyst in the process. A catalyst recovery method based on the AlCl3 sublimation and recondensation was studied and found to be non-feasible. It is believed that the catalyst forms an organometallic complex with the decomposed hydrocarbons, such that it becomes chemically bonded to the residue material and hence not removable by evaporation. A scheme for the further study of the catalyst recovery is suggested.

Made available in DSpace on 2014-12-17T14:08:49Z (GMT). No. of bitstreams: 1 AruzzaMMA_DISSERT.pdf: 1774693 bytes, checksum: a3fe2aad8bc5ee5d62f0d84e6a4733c6 (MD5) Previous issue date: 2011-07-01 / The use of biofuels remotes to the eighteenth century, when Rudolf Diesel made the first trials using peanut oil as fuel in a compression ignition engine. Based on these trials, there was the need for some chemical change to vegetable oil. Among these chemical transformations, we can mention the cracking and transesterification. This work aims at conducting a study using the thermocatalytic and thermal cracking of sunflower oil, using the Al-MCM-41 catalyst. The material type mesoporous Al-MCM-41 was synthesized and characterized by Hydrothermical methods of X-ray diffraction, scanning electron microscopy, nitrogen adsorption, absorption spectroscopy in the infrared and thermal gravimetric analysis (TG / DTG).The study was conducted on the thermogravimetric behavior of sunflower oil on the mesoporous catalyst cited. Activation energy, conversion, and oil degradation as a function of temperature were estimated based on the integral curves of thermogravimetric analysis and the kinetic method of Vyazovkin. The mesoporous material Al-MCM-41 showed one-dimensional hexagonal formation. The study of the kinetic behavior of sunflower oil with the catalyst showed a lower activation energy against the activation energy of pure sunflower oil. Two liquid fractions of sunflower oil were obtained, both in thermal and thermocatalytic pyrolisis. The first fraction obtained was called bio-oil and the second fraction obtained was called acid fraction. The acid fraction collected, in thermal and thermocatalytic pyrolisis, showed very high level of acidity, which is why it was called acid fraction. The first fraction was collected bio-called because it presented results in the range similar to petroleum diesel / O uso dos biocombust?veis remota ao s?culo XVIII, quando Rudolf Diesel realizou os primeiros ensaios utilizando o ?leo de amendoim como combust?vel em um motor de igni??o por compress?o. Com base nesses ensaios, constatou-se a necessidade de realizar algumas transforma??es qu?micas ao ?leo vegetal. Dentre essas transforma??es qu?micas, pode-se citar a transesterifica??o e o craqueamento. Este trabalho tem como objetivo, realizar um estudo utilizando-se o craqueamento t?rmico e termocatal?tico do ?leo de girassol, utilizando o Al-MCM-41 como catalisador. O material mesoporoso tipo Al-MCM-41 foi sintetizado hidrotermicamente e caracterizado pelos m?todos de difra??o de raios-X, microscopia eletr?nica de varredura, adsor??o de nitrog?nio, espectroscopia de absor??o na regi?o do infravermelho e an?lise termogravim?trica (TG/DTG). Ainda foi realizado o estudo do comportamento termogravim?trico do ?leo de girassol sobre o catalisador mesoporoso citado. Com base nas curvas integrais das an?lises termogravim?tricas e o m?todo cin?tico de Vyazovkin, foram estimados a energia de ativa??o, a convers?o e a degrada??o do ?leo em fun??o da temperatura. O material mesoporoso Al-MCM-41 apresentou forma??o hexagonal unidimensional. O estudo do comportamento cin?tico do ?leo de girassol com o catalisador mostrou uma menor energia de ativa??o frente ? energia de ativa??o do ?leo de girassol puro. Na pir?lise t?rmica e termocatal?tica do ?leo de girassol foram obtidas duas fra??es l?quidas. A primeira fra??o obtida foi denominada de bio?leo e a segunda fra??o obtida foi denominada de fra??o ?cida. A fra??o ?cida coletada tanto na pir?lise t?rmica como na termocatal?tica apresentou ?ndice de acidez muito elevado, raz?o pela qual foi denominada fra??o ?cida. A primeira fra??o coletada foi denominada de bio?leo porque apresentou resultados na faixa semelhante ao diesel de petr?leo

Made available in DSpace on 2014-12-17T15:42:09Z (GMT). No. of bitstreams: 1 AnaCRM_TESE.pdf: 3734770 bytes, checksum: 59720290841ee6807d60b116e21f2090 (MD5) Previous issue date: 2010-12-06 / Coordena??o de Aperfei?oamento de Pessoal de N?vel Superior / Microporous materials zeolite type Beta and mesoporous type MCM-41 and AlMCM-41 were synthesized hydrothermally and characterized by methods of X-ray diffraction, Fourier transform infrared, scanning electron microscopy, surface acidity, nitrogen adsorption, thermal analysis TG / DTG. Also we performed a kinetic study of sunflower oil on micro and mesoporous catalysts. The microporous material zeolite beta showed a lower crystallinity due to the existence of smaller crystals and a larger number of structural defects. As for the mesoporous materials MCM-41 and AlMCM-41 samples showed formation of hexagonal one-dimensional structure. The study of kinetic behavior of sunflower oil with zeolite beta catalysts, AlMCM-41 and MCM-41 showed a lower activation energy in front of the energy of pure sunflower oil, mainly zeolite beta. In the thermal cracking and thermocatalytic of sunflower oil were obtained two liquid fractions containing an aqueous phase and another organic - organic liquid fraction (FLO). The FLO first collected in both the thermal cracking as the thermocatalytic, showed very high level of acidity, performed characterizations of physicochemical properties of the second fraction in accordance with the specifications of the ANP. The second FLO thermocatalytic collected in cracking of sunflower oil presented results in the range of diesel oil, introducing himself as a promising alternative for use as biofuel liquid similar to diesel, either instead or mixed with it / Os materiais microporosos tipo ze?lita beta e mesoporosos tipo MCM-41 e AlMCM-41 foram sintetizados hidrotermicamente e caracterizados pelos m?todos de difra??o de raios X, infravermelho por transformada de Fourier, microscopia eletr?nica de varredura, acidez superficial, adsor??o de nitrog?nio, an?lise t?rmica via TG/DTG. Ainda foi realizado um estudo do comportamento cin?tico termogravim?trico do ?leo de girassol sobre os catalisadores micro e mesoporosos citados. Usando curvas integrais da TG e o m?todo cin?tico de Vyazovkin, foram estimados a energia de ativa??o, as taxas de convers?o e o tempo degrada??o do ?leo em fun??o da temperatura. O material microporoso ze?lita beta apresentou menor cristalinidade, devido ? exist?ncia de cristais menores e um maior n?mero de defeitos estruturais. Quanto aos materiais mesoporosos MCM-41 e AlMCM-41 apresentaram amostras com forma??o da estrutura hexagonal unidimensional. O estudo do comportamento cin?tico do ?leo de girassol com os catalisadores ze?lita beta, AlMCM-41 e MCM-41, mostrou uma menor energia de ativa??o frente a energia do ?leo de girassol puro, principalmente a ze?lita beta. No craqueamento t?rmico e termocatal?tico do ?leo de girassol foram obtidas duas fra??es l?quidas contendo uma fase aquosa e outra org?nica fra??o l?quida org?nica (FLO). A primeira FLO coletada, tanto no craqueamento t?rmico quanto no termocatal?tico, apresentou ?ndice de acidez muito elevado, sendo assim foi realizada as caracteriza??es das propriedades f?sico-qu?micas da segunda fra??o de acordo com as especifica??es da ANP. As segundas FLOs coletadas no craqueamento termocatal?tico do ?leo de girassol apresentaram resultados na faixa adequada ao diesel de petr?leo, apresentando-se como uma alternativa promissora para utiliza??o como biocombust?vel l?quido similar ao diesel, seja em substitui??o, ou misturado a este

nÃo hà / O CO2 lanÃado na atmosfera pela atividade antropogÃnica à considerado o maior agente causador da mudanÃa climÃtica. No mundo todo, as usinas termoelÃtricas sÃo as maiores fontes estacionÃrias de emissÃes de CO2. Segundo algumas previsÃes, atà 2100, os efeitos climÃticos podem se tornar irreversÃveis com consequÃncias desastrosas para todos os ecossistemas do planeta. Assim, à essencial a pesquisa de formas de fixaÃÃo do CO2 atravÃs da captura e armazenamento ou por processos naturais de reciclagem de carbono. A integraÃÃo entre processos emissores de CO2 e processos que utilizam o CO2 como matÃria-prima pode ser implementada dentro do princÃpio da Ecologia Industrial. Segundo esse conceito, o resÃduo de uma indÃstria à usado como matÃria-prima de outra, de modo que o impacto ambiental do sistema ampliado seja reduzido ao mÃnimo. O objetivo do presente trabalho foi o de realizar uma avaliaÃÃo tÃcnico-econÃmica do potencial de rotas tecnolÃgicas para reciclagem das emissÃes de CO2 em termoelÃtricas a gÃs natural pelo uso de microalgas. Para essa finalidade foram selecionadas duas rotas de reciclagem de CO2, analisadas cada uma, em dois cenÃrios alternativos (R1C1, R1C2, R2C1 e R2C2). A primeira rota està inserida no contexto da geraÃÃo de energia ou produtos quÃmicos pela tecnologia NGCC, enquanto que a segunda rota visa a produÃÃo do biohidrogÃnio. A avaliaÃÃo foi levada a efeito atravÃs da simulaÃÃo computacional utilizando o simulador de plantas quÃmicas AspenHysys. Na rota 1, o cenÃrio 1 estudou a utilizaÃÃo direta do gÃs natural para a produÃÃo do gÃs de sÃntese pelo processo de reforma a vapor. O cenÃrio 2 analisou a contribuiÃÃo da biomassa algal, atravÃs do processo de gaseificaÃÃo, para a geraÃÃo de gÃs de sÃntese, a ser utilizado para aumentar a eficiÃncia de geraÃÃo de energia. Os resultados obtidos com a rota R1C1 revelaram uma avaliaÃÃo tÃcnica positiva, com rendimentos em torno de 80%, mas o aspecto ambiental desfavorÃvel, associada a uma pequena geraÃÃo adicional de energia (3,8%). A rota R2C1 apresentou rendimentos de processo insatisfatÃrios (em torno de 64%) e uma avaliaÃÃo ambiental desfavorÃvel. A rota R2C2 apresentou rendimentos satisfatÃrios (em torno de 76%), nenhuma emissÃo de CO2 alÃm da geraÃÃo de um subproduto de grande interesse comercial, o carbono. A avaliaÃÃo econÃmica preliminar realizada para essa rota foi feita levando-se em conta trÃs diferentes cenÃrios: reciclagem ou nÃo dos efluentes do reator UASB para o cultivo de microalgas (dois primeiros cenÃrios) e acrÃscimo de crÃditos de carbono à receita proveniente da venda dos produtos (terceiro cenÃrio). Os dois primeiros cenÃrios mostraram-se economicamente desfavorÃveis, porÃm o terceiro cenÃrio demonstrou a possibilidade de viabilidade econÃmica do processo, com um tempo de retorno do capital investido em torno de cinco anos. Pode-se concluir do trabalho realizado que a produÃÃo de biohidrogÃnio a partir de fontes renovÃveis, segundo a rota R2C2 proposta, pode ser viabilizada pela utilizaÃÃo das microalgas como mecanismo de biofixaÃÃo das emissÃes de CO2 de termoelÃtricas. Finalmente pode-se constatar que o Nordeste brasileiro dispÃe de condiÃÃes climÃticas adequadas para a implantaÃÃo desse tipo de tecnologia. / CO2 emissions released into the atmosphere by anthropogenic activity are considered the largest causative agent of climate change. Worldwide, power plants are the largest stationary sources of CO2 emissions. According to some forecasts, by 2100, the climatic effects can become irreversible with disastrous consequences for all ecosystems on the planet. Thus, it is essential to research ways of fixing CO2 by capture and storage through natural carbon recycling processes. The integration of CO2 emitting processes and processes using CO2 as a feedstock can be implemented within the principle of Industrial Ecology. According to this concept, the residue of an industry is used as raw material to another unit, so that the environmental impact of the expanded system is minimized. The aim of this study was to conduct a technical and economic evaluation of the potential for technological pathways for recycling CO2 in natural gas fired power plants by microalgae fixation. For this purpose, two routes of CO2 were analyzed each one in two different scenarios (R1C1 , R1C2 , R2C1 and R2C2). The first route is related to the context of power generation by NGCC technology or chemical production, while the second route aims at the production of bio-hydrogen. The evaluation was carried out by computer simulation using the chemical plants simulator AspenHysys. Route R1C1, studied the direct use of natural gas for the production of synthesis gas by steam reforming process. Route R1C2 analyzed the contribution of algal biomass through gasification process for generating synthesis gas to be used to increase the efficiency of power generation. The results obtained with the route R1C1 showed a positive technical evaluation, with yields around 80 %, but the unfavorable environmental aspect associated and a small additional power generation (3.8 %). The route presented R2C1 showed unsatisfactory yields (around 64 %) and an unfavorable environmental assessment . The route R2C2 showed satisfactory yields ( around 76 %), no CO2 emissions as well as generating a byproduct of great commercial interest, carbon. The prelimiar economic evaluation performed for this route was made taking into account three different scenarios: no recycling of UASB reactor effluents for the microalgae cultivation and the addition of carbon credits to revenue from the sale of products. The first two scenarios were shown to be economically unfavorable, but the third scenario showed the possibility of economic viability of the process, with a time of return to capital invested in around five years. It can be concluded that the process of biohydrogen production from renewable sources, according to the proposed route R2C2, by the use of microalgae as a mechanism biofixaÃÃo CO2 emissions from gas-fired power plants may be technically and economically possible. Finally it can be seen that the Brazilian Northeast has suitable climatic conditions for the deployment of such technology.