Petroleum coke-derived activated carbons were prepared and used for the adsorptive removal of a single-ring naphthenic acid (NA) from synthetic oil sands tailings pond water (TPW). The overall adsorption process was found to be intra-particle diffusion-controlled. The Weber-Morris intra-particle diffusion rate constants decreased from 7.43 to 1.23 mg/g min0.5 after activated carbon was post-oxidized with oxygen, suggesting a hindering effect of oxygen surface groups. The Freundlich model fit of the equilibrium adsorption isotherms and the small negative ΔHo pointed to a physisorption-dominated process and the importance of specific surface area. It was estimated that about 2.7 g/L of basic CO2-activated carbon is needed to reduce NA concentration from 120 mg/L to 2.5 mg/L (~98% removal) in synthetic TPW. However, equilibrium adsorption capacity was found to vary significantly after oxygen or nitrogen groups were introduced onto the surface. Therefore, there is a potential for enhanced adsorption by chemical functionalization of carbon.

Petroleum coke-derived activated carbons were prepared and used for the adsorptive removal of a single-ring naphthenic acid (NA) from synthetic oil sands tailings pond water (TPW). The overall adsorption process was found to be intra-particle diffusion-controlled. The Weber-Morris intra-particle diffusion rate constants decreased from 7.43 to 1.23 mg/g min0.5 after activated carbon was post-oxidized with oxygen, suggesting a hindering effect of oxygen surface groups. The Freundlich model fit of the equilibrium adsorption isotherms and the small negative ΔHo pointed to a physisorption-dominated process and the importance of specific surface area. It was estimated that about 2.7 g/L of basic CO2-activated carbon is needed to reduce NA concentration from 120 mg/L to 2.5 mg/L (~98% removal) in synthetic TPW. However, equilibrium adsorption capacity was found to vary significantly after oxygen or nitrogen groups were introduced onto the surface. Therefore, there is a potential for enhanced adsorption by chemical functionalization of carbon.

This work investigates the interactions of carbonaceous materials (metallurgical coke, natural graphite and HDPE/coke blends) with three EAF slags [FeO: 24% to 32%]. Experiments were conducted using the sessile drop technique (1500??C-1600??C) with off-gases (CO, CO2) measured using an IR analyzer; the wetting behaviour was determined from contact angle measurements. Estimation of slag foaming behaviour was determined from the droplet volume changes calculated using specialized software. At 1550??C, all slags were non-wetting with coke due to increased surface tension due to sulphur. At 1550??C, slag 1 was initially non-wetting on natural graphite due to gas entrapment in the slag droplet; the wetting improved after that. Other slags showed comparatively better wetting. At 1600??C, all slags were non-wetting with coke. Slags showed a shift from non-wetting to wetting behaviour with natural graphite. Slag/coke reactions produced high off-gases levels causing extensive FeO reduction; gas entrapment in the slag was poor (small volume droplets). Slag/natural graphite interactions revealed both slow gas generation rates and FeO reduction, and excellent gas entrapment (higher droplet volumes) with minor changes in slag properties due to low ash levels. The iron oxide reduction rates were determined to be 1.54x10-5 and 4.2x10-6 mol.cm-2/sec (Slag 1, 1550??C) for metallurgical coke and natural graphite respectively. Slag interactions with coke/HDPE blends showed increasing off-gas levels with increasing HDPE levels. Blend#3 produced the highest off-gas levels, extensive FeO reduction and displayed significantly higher slag foaming and better wetting compared to coke. Our line on trends compared well for slag/carbon interactions and resulted in deceased specific energy consumption and carbon usage and increased productivity. These findings have enhanced the possibility of utilizing polymeric wastes in blends with coke in EAF steelmaking for slag/carbon interactions.

Thèse (M.Sc.)--Université Laval, 2008. / Bibliogr.: f. 50-52. Publié aussi en version électronique dans la Collection Mémoires et thèses électroniques.

In blast furnace ironmaking one major challenge is to control and measure the alkalis circulating and accumulating in the blast furnace (BF). Alkali enter the BF with the primary raw material and will form a cycle where it is first reduced to metal at the lower parts forming gas. Alkali then follows the gas flow up where it oxidizes and solidies as the oxide form has a higher melting and volatilization temperature. Condensation then occurs on burden material and in their pores and by that it is following the burden downwards. The circular nature of the reactions leads to a build-up of alkali in the form of potassium in the BF that is hard to control or measure. Condensation of alkali compounds can also occur on the BF walls functioning like a glue to which particles attach, forming scaffolds that can rapidly increase and disturb the burden descent. The increased alkali catalyzes gasication of coke with CO2 that increasescoke consumption and leads to disintegration of coke. A common method today to control alkali is by varying the basicity in the BF. As lower basicity increases the amount alkali removed through slag while at the same time reducing the amount of sulfur that can be removed with the slag. This project was divided into two parts. The first part was a continuation of a previous study performed at Swerea MEFOS. Where to control the effect of alkali on coke gasication a method was tested using coke ash modication to inhibit the catalyzing properties of alkali bound on coke. The method has previously shown that alkalis are bound in the desired form but the added amount was not sufficient for inhibition of all picked-up alkalis. In this study, additional trials with higher additions of kaolin was performed. 2 wt% kaolin was added to the coal blend for producing coke that was then added to LKAB's experimental blast furnace (EBF) as basket samples in the end of a campaign. The excavated samples were analyzed using XRF, XRD, SEM-EDS and TGA to find if the alkali was bound in aluminum silicates in the coke ash, if the addition was sufficient for binding all alkalis and if the catalytic effect in coke gasication had been achieved. The second part was a novel approach with a statistical process analysis using SIMCA to connect top gas composition of SSAB Oxelösund's BF No. 4 to alkali content using process data. The approach investigated the correlation between NH3(g) and HCN(g) in the top gas to alkali content. Expanding on the possibility to measure alkali content quickly for the operators using top gas measurements. Top gas composition was measured using a mass spectrometer (MS) and where complimented with process and tap data provided by SSAB. Data was analyzed using the multivariate analysis tool SIMCA 15 to find possible correlations. Results from the first part showed that the alkali that was found was present as alkali aluminum silicates independent of kaolin addition after the EBF. As temperature along gas composition was the main factors behind alkali uptake in coke. Main differences in alkali uptake and development of coke properties in the BF was linked to the temperature and gas composition profile during tests campaigns compared. Results from TGA showed that the reaction rate of coke with CO2 increases with increasing K2O and that start of reaction was lower with increasing alkali. The results from the second approach did not find a correlation between HCN(g) and K2O in slag. Positive correlation could be seen between HCN(g) and increased SiO2 in slag and that H2O(g) would affect HCN(g) negatively.

A reutilização de resíduos e sua destinação são desafios seguidamente enfrentados na indústria. Por ser extensa e empregar uma grande variedade de processos, matérias-primas e insumos, a cadeia do aço se beneficia por ter ampla flexibilidade e diversas possibilidades de reintrodução de compostos em sua rota de fabricação. Resíduos carbonosos, por exemplo, podem ser parcialmente usados em misturas de carvões no processo de coqueificação dependendo do tamanho e da composição química. Este trabalho, teve como objetivo, avaliar a influência da adição de moinha de carvão vegetal em uma mistura de carvões para a produção de coques em forno piloto de coqueificação e determinar os teores máximos de incorporação suportados pela mistura, avaliando parâmetros de qualidade do coque. Para isso, a moinha de carvão vegetal de eucalipto foi introduzida em duas frações granulométricas distintas, uma composta por partículas mais grosseiras (fração G) e outra composta por partículas mais finas (fração F), e caracterizado juntamente com a mistura utilizada. Posteriormente, os coques produzidos em forno piloto também foram caracterizados através de diversas análises: imediata, elementar, área superficial, porosidade, textura óptica, reatividade em termobalança, CRI/CSR e DI150/15. Os resultados atingidos mostraram que inserção da fração G de moinha comprometeu menos os parâmetros de qualidade dos coques com carvão vegetal. Teores de até 3% de moinha foram suportados para essa distribuição de tamanho de partícula enquanto que para a fração F, somente 1%. Outro fator observado foi que os coques produzidos com adição de moinha de carvão vegetal não tiveram queda significativa no teor de enxofre, a exceção da amostra contendo 10% de carvão vegetal na fração G. Em todas as amostras com moinha de carvão vegetal também foi possível notar o aumento da área superficial em relação ao coque de referência. Os testes termogravimétricos dinâmicos também trouxeram informações relevantes a respeito das temperaturas e taxas aparentes de reações dos coques feitos com moinha de carvão vegetal. / The reuse of waste materials and its destination are challenges continuously faced for industry. For being far-flung and apply a huge variety of process, raw materials and inputs, the steel supply chain benefits from having a high flexibility and many possibilities of reintroducing compounds in its manufacturing route. For example, carbonaceous materials can be used partially in coal blends for cokemaking process depending on particle size and chemical composition. The current work aimed to evaluate the influence of adding fine charcoal to a coal blend for coke production in a pilot oven and to determine the maximum content tolerated for the blend, assessing coke quality parameters. For this, a eucalyptus charcoal residue was introduced in two different size distributions, one composed of coarser particles (fraction G) and another of finer (fraction F), and characterized together with the coal blend used. Afterwards, the cokes produced in pilot oven were also characterized through several analyzes: proximate, ultimate, surface area, porosity, optical texture, reactivity on thermobalance, CRI/CSR e DI150/15. The results achieved showed that the insertion of charcoal on fraction G compromised less the quality parameters of cokes with charcoal. Contents up to 3% of charcoal were tolerated for this particle size distribution while for fraction F, only 1%. Another point noticed was that the coke produced with charcoal addition had no significant drop on sulfur content, with the exception of the coke sample with 10% of charcoal and fraction G. In all samples with charcoal it was also possible to see an increase on surface area in relation to the reference coke. The dynamic thermogravimetric tests also provided relevant information regarding to the temperatures and apparent reaction rates of cokes made with charcoal.

A reutilização de resíduos e sua destinação são desafios seguidamente enfrentados na indústria. Por ser extensa e empregar uma grande variedade de processos, matérias-primas e insumos, a cadeia do aço se beneficia por ter ampla flexibilidade e diversas possibilidades de reintrodução de compostos em sua rota de fabricação. Resíduos carbonosos, por exemplo, podem ser parcialmente usados em misturas de carvões no processo de coqueificação dependendo do tamanho e da composição química. Este trabalho, teve como objetivo, avaliar a influência da adição de moinha de carvão vegetal em uma mistura de carvões para a produção de coques em forno piloto de coqueificação e determinar os teores máximos de incorporação suportados pela mistura, avaliando parâmetros de qualidade do coque. Para isso, a moinha de carvão vegetal de eucalipto foi introduzida em duas frações granulométricas distintas, uma composta por partículas mais grosseiras (fração G) e outra composta por partículas mais finas (fração F), e caracterizado juntamente com a mistura utilizada. Posteriormente, os coques produzidos em forno piloto também foram caracterizados através de diversas análises: imediata, elementar, área superficial, porosidade, textura óptica, reatividade em termobalança, CRI/CSR e DI150/15. Os resultados atingidos mostraram que inserção da fração G de moinha comprometeu menos os parâmetros de qualidade dos coques com carvão vegetal. Teores de até 3% de moinha foram suportados para essa distribuição de tamanho de partícula enquanto que para a fração F, somente 1%. Outro fator observado foi que os coques produzidos com adição de moinha de carvão vegetal não tiveram queda significativa no teor de enxofre, a exceção da amostra contendo 10% de carvão vegetal na fração G. Em todas as amostras com moinha de carvão vegetal também foi possível notar o aumento da área superficial em relação ao coque de referência. Os testes termogravimétricos dinâmicos também trouxeram informações relevantes a respeito das temperaturas e taxas aparentes de reações dos coques feitos com moinha de carvão vegetal. / The reuse of waste materials and its destination are challenges continuously faced for industry. For being far-flung and apply a huge variety of process, raw materials and inputs, the steel supply chain benefits from having a high flexibility and many possibilities of reintroducing compounds in its manufacturing route. For example, carbonaceous materials can be used partially in coal blends for cokemaking process depending on particle size and chemical composition. The current work aimed to evaluate the influence of adding fine charcoal to a coal blend for coke production in a pilot oven and to determine the maximum content tolerated for the blend, assessing coke quality parameters. For this, a eucalyptus charcoal residue was introduced in two different size distributions, one composed of coarser particles (fraction G) and another of finer (fraction F), and characterized together with the coal blend used. Afterwards, the cokes produced in pilot oven were also characterized through several analyzes: proximate, ultimate, surface area, porosity, optical texture, reactivity on thermobalance, CRI/CSR e DI150/15. The results achieved showed that the insertion of charcoal on fraction G compromised less the quality parameters of cokes with charcoal. Contents up to 3% of charcoal were tolerated for this particle size distribution while for fraction F, only 1%. Another point noticed was that the coke produced with charcoal addition had no significant drop on sulfur content, with the exception of the coke sample with 10% of charcoal and fraction G. In all samples with charcoal it was also possible to see an increase on surface area in relation to the reference coke. The dynamic thermogravimetric tests also provided relevant information regarding to the temperatures and apparent reaction rates of cokes made with charcoal.

CoordenaÃÃo de AperfeÃoamento de Pessoal de NÃvel Superior / Dry reforming of methane reaction was conducted in the presence of titanate nanotubes (TNTs) modified with Co, Ni and Pt. TNTs were synthesized by hydrothermal treatment and than these solids were either submitted to ion exchange for Ni and Co using hexahydrate nitrate solutions, or they were submitted to wet impregnation with H2Ptl6.6H2O (1% w/w of Pt) solution. The solids were characterized before and after the dry reforming of methane by elemental chemical analysis (CHN), X-ray diffraction (XRD), Raman spectroscopy, nitrogen adsorption-desorption isotherms, thermoprogrammed reduction (TPR), CO2 thermoprogrammed desorption (CO2-TPD), transmission electronic microscopy (TEM), scanning electronic microscopy (SEM-EDS) and X-ray photoelectron spectroscopy (XPS). Raman and XRD results showed the presence of Na2Ti3O7 phase to all sodic nanotubes, while that the nanotubes modified displayed peaks and vibrational modes relative to CoTi3O7, NiTi3O7 and PtOx/Na2Ti3O7 phases. TEM images exhibited tubular morphology composed by multi-walls, as observed by XRD and Raman. SEM-EDS results showed the nanotubes composition with M/Ti ratio lower than the theoretical (value of 0,33), due to the presence of structural water. The XPS results confirmed the presence of M(OH)2 phase (M=Co, Ni or Pt) present on nanotubes surface. TPR patterns suggested the formation of M0/MTiO3 (M = Co, Ni and Pt) after the reduction of the nanotubes at 650 ÂC. The nitrogen adsorption-desorption isotherms of sodic and modified TNTs showed isotherms type IV with an essentially mesoporous structure. CO2-TPD patterns suggested the presence of weak and moderate basic sites in all catalysts, indicating phase transformation due to the decomposition, in situ, of as-prepared nanotubes. The catalyst NiTNT exhibited the highest CO2 and methane conversion at 600 ÂC, with about 43 and 25%, respectively, and H2/CO ratio equal 1, without deactivation over time. PtTNT was lesser susceptible to coking, although sintering remarkably decreased the performance of this solid. On the other hand, PtTNT and CoTNT showed formation of coke over the PtOx/PtTiO3 and Co0/CoTiO3 active phase, respectively, so that the latter solid deactivated during the dry reforming of methane. / A reaÃÃo da reforma seca do metano foi conduzida na presenÃa de nanotubos de titanatos (TNTs) modificados com Co, Ni e Pt. Os TNTs foram sintetizados via tratamento hidrotÃrmico e, posteriormente, foram submetidos à troca iÃnica por Ni e Co, utilizando soluÃÃes de nitrato hexahidratado, ou foram submetidos à impregnaÃÃo via-Ãmida com soluÃÃo de H2PtCl6.6H2O (1% m/m de Pt). Os catalisadores foram caracterizados antes e apÃs reaÃÃo de reforma seca do metano por anÃlise quÃmica (CHN), difraÃÃo de raios-X (DRX), espectroscopia Raman, isotermas de adsorÃÃo-dessorÃÃo de nitrogÃnio, reduÃÃo termoprogramada (TPR), dessorÃÃo termoprogramada de CO2 (TPD-CO2), microscopia eletrÃnica de transmissÃo (TEM), microscopia eletrÃnica de varredura (MEV-EDS) e espectroscopia fotoeletrÃnica de raios-X (XPS). Os resultados de Raman e DRX evidenciaram a presenÃa da fase Na2Ti3O7 para os nanotubos sÃdicos, enquanto que para os nanotubos modificados foram identificados picos e modos vibracionais referentes Ãs fases CoTi3O7, NiTi3O7 e PtOx/Na2Ti3O7. As imagens de TEM exibiram morfologia tubular composta por multiparedes, corroborando com os resultados de DRX e Raman. Os resultados de MEV-EDS mostraram a composiÃÃo dos nanotubos com razÃo M/Ti menor que o teÃrico (0,33), devido à presenÃa de Ãgua estrutural. Os resultados de XPS confirmaram a existÃncia da fase M(OH)2 (M=Co, Ni ou Pt) presentes na superfÃcie dos nanotubos. As curvas de TPR sugeriram a formaÃÃo da fase M0/MTiO3 (M = Co, Ni e Pt), apÃs a reduÃÃo dos nanotubos a 650 ÂC. As isotermas de adsorÃÃo-dessorÃÃo de nitrogÃnio dos TNTs sÃdicos e modificados apresentaram isotermas do tipo IV com estrutura essencialmente formada por mesoporos. Os perfis de TPD-CO2 sugeriram a presenÃa de sÃtios bÃsicos fracos e moderados em todos os catalisadores, indicando mudanÃa de fase devido à decomposiÃÃo in situ dos nanotubos como sintetizados. O catalisador NiTNT apresentou os melhores resultados de conversÃo de CO2 e metano a 600 ÂC, com aproximadamente 43 e 25%, respectivamente, e razÃo H2/CO igual a 0,5, sem desativaÃÃo ao longo do tempo. PtTNT foi menos susceptÃvel à formaÃÃo de coque, embora o fenÃmeno de sinterizaÃÃo tenha desfavorecido o desempenho do sÃlido. Por outro lado, os sÃlidos PtTNT e CoTNT apresentaram formaÃÃo de coque sobre as fases ativas PtOx/PtTiO3 e Co0/CoTiO3, respectivamente, de modo que este Ãltimo sÃlido desativou durante a reaÃÃo da reforma seca do metano.

Submitted by Irene Nascimento (irene.kessia@ufpe.br) on 2017-04-12T16:58:50Z No. of bitstreams: 2 license_rdf: 1232 bytes, checksum: 66e71c371cc565284e70f40736c94386 (MD5) Dissertação_Ulysses.pdf: 2292611 bytes, checksum: 94f0d93357c24023b30a73414786b32e (MD5) / Made available in DSpace on 2017-04-12T16:58:50Z (GMT). No. of bitstreams: 2 license_rdf: 1232 bytes, checksum: 66e71c371cc565284e70f40736c94386 (MD5) Dissertação_Ulysses.pdf: 2292611 bytes, checksum: 94f0d93357c24023b30a73414786b32e (MD5) Previous issue date: 2016-01-29 / CAPES / O processo de obtenção do gesso beta, que consiste na desidratação do minério da gipsita a uma temperatura entre 125 °C e 160°C, é realizado em fornos rotativos através de queima direta ou indireta. Os principais combustíveis utilizados neste processo no Polo Gesseiro do Araripe são a lenha, o coque de petróleo, o óleo BPF e gás natural. Esta dissertação estuda a modelagem matemática de um sistema de calcinação com aquecimento indireto utilizando dois combustíveis sólidos diferentes: a lenha e o coque de petróleo. A modelagem é feita por meio do Método dos Volumes Finitos em um modelo bidimensional de coordenadas cilíndricas. Através da simulação numérica é possível prever o perfil de temperatura em uma seção transversal do forno, tal como suas taxas de aquecimento. São observadas as influências de parâmetros como vazão mássica do combustível, percentual de excesso de ar na combustão e teor de umidade da lenha. Também é realizada uma comparação entre os processos utilizando a lenha e o coque com relação ao custo e à emissão de dióxido de enxofre (SO2). / The process of obtaining the beta plaster, which consists of dehydration of the gypsum ore under a temperature between 100°C and 160 °C, is performed in rotary kilns through direct or indirect burn. The main fuels utilized in this process at Araripe Gypsum District are firewood, petroleum coke, heavy fuel oil and natural gas. This dissertation studies the mathematical modeling of a calcination system with indirect heating using two different solid fuels: firewood and petroleum coke. The modeling is made by using the Finite Volume Method in a two-dimensional model of cylindrical coordinates. Through the simulation is possible to predict the temperature behavior in a cross section of the kiln, as well as its heating rates. It was analyzed the influence of parameter such as mass flow rate, percent excess combustion air and moisture content of the firewood. A comparison between the processes using firewood and coke is also conducted, concerning the cost and the sulfur dioxide (SO2) emission.

Orientador: Vladimir Antonio Paulon / Dissertação (mestrado) - Universidade Estadual de Campinas, Faculdade de Engenharia Civil, Arquitetura e Urbanismo / Made available in DSpace on 2018-08-05T19:59:19Z (GMT). No. of bitstreams: 1 Massucato_CarlosJose_M.pdf: 776667 bytes, checksum: f202112f226f07e627ccbebfb07f5bed (MD5) Previous issue date: 2005 / Resumo: Este estudo teve como objetivo principal avaliar propriedades oriundas da adição de escória de alto-forno à carvão vegetal, do concreto no estado fresco e endurecido, produzido com cimentos que já utilizam em sua composição a escória de alto-forno. Com a determinação da quantidade de escória de alto-forno pelo método de dissolução seletiva, foi possível adicionar escória de alto-forno no concreto até os limites estabelecidos na especificação do cimento de alto-forno (CPIII) pela NBR 5735 (ABNT, 1991) e conhecer o efeito na resistência mecânica, módulo de elasticidade, abatimento, incorporação de ar, tempo de pega e exsudação, em traços de concreto sem adição e com adição de escória de alto-forno à carvão vegetal e à coque. As indústrias de cimento utilizam, em sua maioria, escórias provenientes dos altos-fornos à coque. Entretanto, o tratamento adequado nas escórias de alto-forno à carvão vegetal pode ampliar o consumo deste produto como adição mineral diretamente nas centrais de concreto, com a vantagem de ser uma fonte renovável de energia e eliminar este resíduo que se acumula nas usinas siderúrgicas. O estudo comprovou que, a utilização da escória de alto-forno à carvão vegetal como adição, não provoca alterações nas propriedades do concreto no estado fresco, em comparação com a escória de alto-forno à coque. A resistência à compressão com adição da escória de alto-forno à carvão vegetal aumentou em até 5% em idades superiores a 60 dias em comparação com o concreto sem adição de escória / Abstract: This study had the main purpose to evaluate properties of fresh and hardened concrete in with slag addition of blast furnace from charcoal in concrete produced with cements that already use in its composition the blast furnace slag. With the determination of the amount of slag of blast furnace by the selective method of dissolution, it was possible to add slag of blast furnace in concrete up to the limits established by NBR 5735 (ABNT, 1991) and to know the effect in concrete resistance, modulus of elasticity, slump test, air entrained concrete, setting of the cement and bleeding, in the mix proportions of concrete with and without slag addition of blast furnace from charcoal and coke. The cement industries use in its majority slag from coke deriving from blast furnace. However, the suitable treatment in slag of blast furnace from charcoal can extend the consumption of this product as mineral addition directly in the concrete plant, with the advantage of being a renewable source of energy and to eliminate this residue that accumulates in the siderurgical plants. The study proved that the use of the slag of blast furnace from charcoal as addition in concrete presented the same properties of fresh concrete compared with the slag of blast furnace with coke. The compressive strength increased in 5% at superior ages at 60th day in comparison without slag addition / Mestrado / Edificações / Mestre em Engenharia Civil