Petroleum coke (petcoke) has been burned at kraft pulp mills to partially substitute for natural gas and fuel oil used in lime kilns. Due to the high vanadium and sulfur contents in petcoke, there had been concerns over the impact of burning petcoke on kiln and chemical recovery operations. Laboratory studies were performed to examine the fate of vanadium and sulfur in lime kilns and chemical recovery cycle. The results suggest that most of the vanadium in petcoke quickly forms calcium vanadates with lime in the kiln, mostly 3CaO•V2O5. In the causticizers, calcium vanadates react with Na2CO3 in green liquor to form sodium vanadate (NaVO3). Due to its high solubility, NaVO3 dissolves in the liquor circulating around the chemical recovery system. V becomes enriched in the liquor, leading to vanadium build-up in the system. The S in petcoke would stay in the reburned lime, lower the lime availability, increase SO2 emissions from the kiln stack, alter the S balance, increase the liquor sulphidity, and potentially contribute to ring formation in the kiln.

Petroleum coke (petcoke) has been burned at kraft pulp mills to partially substitute for natural gas and fuel oil used in lime kilns. Due to the high vanadium and sulfur contents in petcoke, there had been concerns over the impact of burning petcoke on kiln and chemical recovery operations. Laboratory studies were performed to examine the fate of vanadium and sulfur in lime kilns and chemical recovery cycle. The results suggest that most of the vanadium in petcoke quickly forms calcium vanadates with lime in the kiln, mostly 3CaO•V2O5. In the causticizers, calcium vanadates react with Na2CO3 in green liquor to form sodium vanadate (NaVO3). Due to its high solubility, NaVO3 dissolves in the liquor circulating around the chemical recovery system. V becomes enriched in the liquor, leading to vanadium build-up in the system. The S in petcoke would stay in the reburned lime, lower the lime availability, increase SO2 emissions from the kiln stack, alter the S balance, increase the liquor sulphidity, and potentially contribute to ring formation in the kiln.

No description available.

Oil sands companies produce substantial quantities of tailings known to contain high concentrations of dissolved organic by-products. The use of petroleum coke was proposed as a potential adsorbent for organic contaminant removal from tailings pond water. Physical activation was used to create a greater surface area and porosity within the delayed and fluid coke. Increased temperature (900oC), steam rate (0.5 mL/min), and activated time (6 h) led to high iodine numbers of 670 and 620 mg/g for activated delayed and fluid cokes, respectively. For both best activated cokes, the micropore to mesopore ratio was approximately 50:50. When 5 g/L of activated delayed and fluid cokes were added to the tailings water, 91% of the dissolved organic carbon and 92% of the naphthenic acids were removed. Such analyses indicate that an oil sands waste by-product can be used to treat tailings pond water to remove toxic and corrosive organic contaminants. / Geoenvironmental Engineering

Neste trabalho foi desenvolvido um procedimento analítico empregando o processo de multicomutação para determinação de íons cloreto com detecção fotométrica para aplicação em amostras de coque de petróleo. O procedimento foi baseado no método espectrofotométrico descrito no Standard Methods, onde a reação entre tiocianato de mercúrio (II) e cloreto leva ao deslocamento dos íons tiocianato e à formação de um complexo de coloração vermelha com o Fe (III), que foi monitorado em 455 nm. Foram construídos dois módulos de análise empregando válvulas solenóide de três vias no primeiro e válvulas de estrangulamento no outro. Com os parâmetros analíticos otimizados para o primeiro módulo, obteve-se uma curva analítica linear para o intervalo de 0,25 a 4,0 mg L-1 de cloreto (R= 0,997), com um limite de detecção de 0,12 mg L-1 (3xbranco/inclinação); RSD de 1,7% (n=15) e uma freqüência de amostragem de 50 det h-1. O segundo módulo de análise foi proposto a fim de eliminar a etapa de acidificação das soluções de referência e amostras. Esta etapa era efetuada off line para liberar as bolhas formadas na reação. A curva analítica obtida para este módulo foi linear para o intervalo de 0,25 a 6,0 mg L-1 de cloreto (R= 0,999), com um limite de detecção de 0,04 mg L-1 (3xbranco/inclinação); RSD de 0,8% (n=15) e uma frequência de amostragem de 50 det h-1. O módulo foi aplicado em amostras de coque de petróleo e também no material de referência certificado. / In this work was developed an analytical procedure employing multicommutation for the photometric determination of chloride in petroleum coke. The procedure was based on the photometric method described on Stand Method, where the reaction between mercury(II) thyocyanate and chloride causes the displacement of the thyocyanate ions, which reacted with iron(III) forming a compound that monitored at 472 nm. Two analysis modules were designed employing three-way and pinch solenoid valves. After the optimizing of the analytical parameters related to analysis module that employed three-way solenoid valves, the analytical curve presented a linear response in the concentration range of 0.25 to 4.0 mg L-1 (R = 0.997). A detection limit of 0.12 mg L-1 chloride, a relative standard deviation of 1.7 % (n = 15) and a sampling frequency of 50 determination per hour were also achieved. The second analysis module was designed to avoid acidification step of sample and reference solutions that was carried out off line to prevent bubbled delivering. The analytical curve presented a linear response within the concentration range of 0.25 up to 6.0 mg L-1 chloride (R=0.999). Detection limit of 0.04 mg L-1, standard deviation of 0.8 % (n=15), and sampling frequency of 50 determination per hours were of achieved. The proposed system was used for the determination of chloride in petroleum coke and also in certified material.

The aims of this research project were to identify and classify the binder-filler interfaces formed in carbon electrodes and to determine the effects of the interfacial quality on important electrode properties. The effects of raw materials and some fabrication process variables on interfacial characteristics and quality of laboratory produced test electrodes were also studied, and the development of binder-filler interfaces during the carbonisation process followed. Electrode quality was assessed by measurement of density, electrical resistivity and tensile strength. Pore structural data were also obtained by using a computerised image analysis system allied to an optical microscope. Interface quality data were obtained by examining etched surfaces in a scanning electron microscope and classifying the binder-filler interface observed into one of five categories. The category depending on the extent of contact between the binder and filler. Accordingly, test electrodes were produced from combinations of four filler carbons, comprising three grades of calcined petroleum coke and an electro-calcined anthracite, and four coal-tar binder pitches which varied in the type and quantity of insoluble matter content. Examination of these test electrodes showed that the nature of the filler carbon used had a dominant influence on the quality of the interface formed, as assessed by this technique. A combination of one filler carbon and one binder pitch was used to study the effects of some fabrication process variables. These were pitch content and, mixing time and temperature. Of these process variables, pitch content and mixing temperature were found to have the major effects on the binder-filler interface and electrode quality. Investigation of the development of the binder-filler interfaces during the carbonisation process showed three distinct zones of interface development and transformation. These zones were associated with three temperature dependent mechanisms; thermal stress relaxation between 200-350 degrees C, volatile gas evolution from coal-tar pitch decompositionb etween3 50-600 degrees C and stresses induced by thermal contraction of the binder phase between 600-1000 degrees C.

Neste trabalho foi desenvolvido um procedimento analítico empregando o processo de multicomutação para determinação de íons cloreto com detecção fotométrica para aplicação em amostras de coque de petróleo. O procedimento foi baseado no método espectrofotométrico descrito no Standard Methods, onde a reação entre tiocianato de mercúrio (II) e cloreto leva ao deslocamento dos íons tiocianato e à formação de um complexo de coloração vermelha com o Fe (III), que foi monitorado em 455 nm. Foram construídos dois módulos de análise empregando válvulas solenóide de três vias no primeiro e válvulas de estrangulamento no outro. Com os parâmetros analíticos otimizados para o primeiro módulo, obteve-se uma curva analítica linear para o intervalo de 0,25 a 4,0 mg L-1 de cloreto (R= 0,997), com um limite de detecção de 0,12 mg L-1 (3xbranco/inclinação); RSD de 1,7% (n=15) e uma freqüência de amostragem de 50 det h-1. O segundo módulo de análise foi proposto a fim de eliminar a etapa de acidificação das soluções de referência e amostras. Esta etapa era efetuada off line para liberar as bolhas formadas na reação. A curva analítica obtida para este módulo foi linear para o intervalo de 0,25 a 6,0 mg L-1 de cloreto (R= 0,999), com um limite de detecção de 0,04 mg L-1 (3xbranco/inclinação); RSD de 0,8% (n=15) e uma frequência de amostragem de 50 det h-1. O módulo foi aplicado em amostras de coque de petróleo e também no material de referência certificado. / In this work was developed an analytical procedure employing multicommutation for the photometric determination of chloride in petroleum coke. The procedure was based on the photometric method described on Stand Method, where the reaction between mercury(II) thyocyanate and chloride causes the displacement of the thyocyanate ions, which reacted with iron(III) forming a compound that monitored at 472 nm. Two analysis modules were designed employing three-way and pinch solenoid valves. After the optimizing of the analytical parameters related to analysis module that employed three-way solenoid valves, the analytical curve presented a linear response in the concentration range of 0.25 to 4.0 mg L-1 (R = 0.997). A detection limit of 0.12 mg L-1 chloride, a relative standard deviation of 1.7 % (n = 15) and a sampling frequency of 50 determination per hour were also achieved. The second analysis module was designed to avoid acidification step of sample and reference solutions that was carried out off line to prevent bubbled delivering. The analytical curve presented a linear response within the concentration range of 0.25 up to 6.0 mg L-1 chloride (R=0.999). Detection limit of 0.04 mg L-1, standard deviation of 0.8 % (n=15), and sampling frequency of 50 determination per hours were of achieved. The proposed system was used for the determination of chloride in petroleum coke and also in certified material.

Clean and efficient electricity can be generated using an Integrated Gasification Combined Cycle (IGCC). Although IGCC is typically used with coal, it can also be used to gasify other carbonaceous species like biomass and petroleum coke. It is important to understand the pyrolysis and gasification of these species in order to design commercial gasifiers and also to determine optimal conditions for operation. High heating-rate (100,000 K/s) pyrolysis experiments were performed with biomass (sawdust) in BYU's atmospheric flat-flame burner reactor at conditions ranging from 1163 to 1433 K with particle residence times ranging from 23 to 102 ms. Volatile yields and mass release of the sawdust were measured. The measured pyrolysis yields of sawdust are believed to be similar to those that would occur in an industrial entrained-flow gasifier since biomass pyrolysis yields depend heavily on heating rate and temperature. Sawdust pyrolysis was modeled using the Chemical Percolation Devolatilization model assuming that biomass pyrolysis occurs as a weighted average of its individual components (cellulose, hemicellulose, and lignin). Thermal cracking of tar into light gas was included using a first-order kinetic model. The pyrolysis and CO2 gasification of petroleum coke was studied in a pressurized flat-flame burner up to 15 atm for conditions where the peak temperature ranged from 1402 to 2139 K. The measured CO2 gasification kinetics are believed to be representative of those from an entrained-flow gasifier since they were measured in similar conditions of elevated pressure and high heating rates (100,000 K/s). This is in contrast to the gasification experiments commonly seen in the literature that have been carried out at atmospheric pressure and slow particle heating rates. The apparent first-order Arrhenius kinetic parameters for the CO2 gasification of petroleum coke were determined. From the experiments in this work, the ASTM volatiles value of petroleum coke appeared to be a good approximation of the mass release experienced during pyrolysis in all experiments performed from 1 to 15 atm. The reactivity of pet coke by CO2 gasification exhibited strong pressure dependence.

The inorganic chemistries of coal and petroleum differ because of their disparate geologic environments of formation, the physical state of the fuels, and the type and quantity of minerals and organic compounds in the fuels. Commercial coals typically contain 2 to 25% ash (average ~ 10%) while petroleums contain 0.003 to 0.07% ash (average ~ 0.01 %). Globally averaged, coal ash is dominated by Si, Fe, Ca, AI, and S, whereas petroleum ash contains significant quantities of V, Ni, S, Fe, Ca, Na, K, Mg, Si and AI. This larger number of important elements causes petroleum combustion slags to have more complex phase assemblages. The high vanadium contents of petroleum-based combustion feedstocks yield numerous crystalline V -oxides with stoichiometric amounts of Ca, Fe, Mg, AI, Ni andlor Na in the resulting slags. Slightly lower nickel contents yield abundant NiFe and Ni sulfides. The dominance of metals over silicon results in the formation of crystalline silicates following metal saturation of immiscible Si-rich glasses. High gasification temperatures (1200 - 1500°C) promote the development of equilibrial assemblages. Chemical variations between individual feedstock cokes coupled with nonuniform operational conditions result in three principal categories of petroleum coke slag; 1) sulfide dominant, 2) silica dominant, and 3) oxide dominant. Sulfide dominant slags are not necessarily derived from feedstocks with high sulfur contents, instead they appear to derive from feedstocks rich in chalcophile elements, predominantly Fe and Ni, by attracting sulfur otherwise lost by volatilization. Slagging additives can change the chemical categorization of resulting slags through phase modifications and the formation of new phases; this in tum can strongly alter the physical behavior of the slags. Compositionally diverse spinel oxides are the most common crystalline slag phase because of their wide thermal and compositional stability ranges, refractory nature, and rapid growth kinetics. Spinel compositions are strongly influenced by the inorganic chemistry of the feedstock, the composition of host phases, and the composition of additives. Coke slag spinels are generally enriched in AI, Fe, V, Mg, and Ni, and often contain Cr that is derived from reaction with refractory material. / Ph. D.

Slags are crystalline to vitreous by-product materials generated in many high temperature industrial processes. This study presents a general technique for the identification of the phases present in petroleum coke gasification slags. documents the phase assemblages and textures, and finally determines the dissolution of vanadium from these slags as part of the considerations of potential resource reclamation. The general identification procedure utilizes (1) recognition of separate phases using optical microscopy and scanning electron microscopy; (2) electron probe microanalysis (EPM) of chemical compositions of individual phases; (3) statistical analysis of the EPM data to eliminate spurious data; (4) estimation of valence states of transition metals using thermodynamic and computational methods; (5) derivation of chemical formulae for the phases using computational methods and chemistry of ionic substitutions; (6) verification of phase identity using X-ray diffraction analysis. More than twenty phases were determined in petroleum coke slags including oxides, silicates. vanadates, sulfate. sulfides and alloys. The reduced slags are rich in V₂>0₃ with silicates and minor amounts of sulfides and native metals whereas the oxidized slags are composed of V₂>0₄, nickel aluminum spinels. various vanadates and glass. Textural analysis provided information on the crystallization process, reaction with gasifier refractory lining materials, sulfide exsolution processes, glass devitrification. and the development of chemical zonation in some spinels. This information offers some perspectives on the potential of resource reclamation. Resource reclamation for petroleum coke slags is best assessed with a knowledge of phases, phase assemblages, textures and dissolution behavior of the material. The dissolution of vanadium. the most significant element. was examined using long term dissolution experiments. These demonstrate that vanadium concentrations are pH dependent ranging from 1500 ppm to 5000 ppm with a minimum concentration near pH 6. Vanadium dissolution rates range from L28xlO⁴ mol m² sec⁻¹ to 3.08xlO^-6 mol m² sec⁻¹. In view of the strategic nature of vanadium and the fact that the concentration of vanadium in slags is almost two orders of magnitude higher than the current mining grades, petroleum coke slags offer significant potential to serve as resources for vanadium. / Ph. D.