Viscosity Reduction and Upgrading of Athabasca Oilsands Bitumen by Natural Zeolite Cracking (original) (raw)
Related papers
Natural zeolite bitumen cracking and upgrading
Microporous and Mesoporous Materials, 2007
The oilsands of North America may well represent the world's largest available petroleum reserves. We investigated the interaction of a number of catalysts with unprocessed oilsands in sealed reactors at 400°C. The viscosity of bitumen is much higher than conventional crude oil, requiring dilution with solvents to pipeline it from the production fields. Its levels of sulfur, nitrogen and metals (especially nickel and vanadium) are also much higher than conventional crude. The catalytic and adsorptive properties of the modified mineral zeolite chabazite were found to reduce viscosity dramatically and remove much of the metals, nitrogen and sulfur at 400°C. Simple, economical, disposable, in-field bitumen upgrading materials, such as modified natural zeolites, could improve bitumen production by lowering or eliminating the need for expensive solvents during pipelining and improving the quality of the product shipped from the field.
Natural zeolites for oilsands bitumen cracking: Structure and acidity
Microporous and Mesoporous Materials, 2011
a b s t r a c t Clay minerals are well known for their ability to breakdown heavy oils by catalytic cracking, but not much is known of the potential of natural zeolites for oilsands bitumen cracking. Our previous work shows that natural zeolites can effectively crack oilsands bitumen into lighter, less viscous products, while producing fewer residues than analogous thermal cracking reactions. In this follow up study we have investigated the potential of both ion-exchanged and untreated forms of natural zeolites as solid acid agents for petroleum cracking. We compared the acid properties of various treated and untreated natural zeolites (particularly chabazites and clinoptiolites from different deposits) with the commercial petroleum cracking catalyst, zeolite Y. Energy dispersive X-ray analysis, inductively coupled Argon plasma-atomic emission spectrometry, acid-base titration using Hammett indicators and temperature programmed desorption of ammonia revealed that natural zeolites, both treated and untreated, have higher or comparable strength and density of acid sites compared to commercial zeolite Y. We propose that higher acid strength and site density, combined with a favorable morphology and a high fraction of accessible surface area contribute to the unique cracking ability of these extraordinary minerals.
Fuel, 2012
Inexpensive natural zeolites such as chabazites and clinoptilolites, found in abundance in multiple global deposits, can offer an effective, economical and environmentally friendly alternative to current methods of oilsands bitumen upgrading. This study shows that water added ($3 wt.% of feed) natural zeolite catalysts, can effectively convert up to 8181% of the residue within oilsands bitumen in a stirred batch system under relatively low severity conditions. The reactions produce very high total liquid yields (up to 8196%), significant amounts of which are residue-free (up to $71%). The resulting liquids have lower viscosity, boiling point distribution and average molecular weight than the bitumen from both raw samples and uncatalyzed oilsands treated thermally under the same conditions. These reactions, particularly when conducted under low severity conditions, produce little gas and result in minimal coking. In addition, the, natural zeolite-processed bitumen is less aromatic than thermally processed bitumen and contains much lower concentrations of heteroatoms (nitrogen, sulfur) and heavy metals (vanadium) compared to raw and untreated bitumen. Based on our results, we envision an alternative, more effective and environmentally friendly, low temperature, integrated extraction and upgrading process for oilsands bitumen that uses water-enhanced natural zeolites, requires fewer steps and improves pipeline transportation.
2014 On the Role of Water in Natural-Zeolite-Catalyzed Cracking of Athabasca Oilsands Bitumen
Water addition to natural-zeolite-catalyzed reactions significantly improves cracking of oilsands bitumen compared to analogous reactions in the absence of water. We report that the addition of 3% water to the catalyzed cracking reactions results in samples with lower viscosities and average molecular weights, less residue, olefin, and coke formation, and higher C 2 + gas production compared to analogous reactions in the absence of water. Our study suggests that untreated natural zeolites undergo self-acidification by hydrolysis reactions in the presence of water. Fourier transform infrared spectroscopy and solid-state NMR analyses detected the presence of acid −OH groups on the raw untreated chabazite and clinoptilolite surfaces that are capable of supplying protons to initiate carbocation reactions. Stable isotopic mass spectrophotometric analyses on bitumen on D 2 O-doped catalytic reactions confirm up to ∼56% hydrogen incorporation from added water to the liquid products. Aromaticity and proton and deuterium distribution of products by liquid NMR indicate the occurrence of a number of catalytic reactions, including aromatization, rearrangement and substitution in the aliphatic chains, β-scission, dehydrogenation, and increased hydrogen enrichment at βand γ-positions. On the basis of our findings, we postulate that water addition to natural zeolites generates catalytic reactions that involve carbocation on acid sites. Studies with model compounds such as cumene and hexadecane also demonstrated significant cracking activity with water addition.
On the Role of Water in Natural-Zeolite-Catalyzed Cracking of Athabasca Oilsands Bitumen
Energy & Fuels, 2014
Water addition to natural-zeolite-catalyzed reactions significantly improves cracking of oilsands bitumen compared to analogous reactions in the absence of water. We report that the addition of 3% water to the catalyzed cracking reactions results in samples with lower viscosities and average molecular weights, less residue, olefin, and coke formation, and higher C 2 + gas production compared to analogous reactions in the absence of water. Our study suggests that untreated natural zeolites undergo self-acidification by hydrolysis reactions in the presence of water. Fourier transform infrared spectroscopy and solid-state NMR analyses detected the presence of acid −OH groups on the raw untreated chabazite and clinoptilolite surfaces that are capable of supplying protons to initiate carbocation reactions. Stable isotopic mass spectrophotometric analyses on bitumen on D 2 O-doped catalytic reactions confirm up to ∼56% hydrogen incorporation from added water to the liquid products. Aromaticity and proton and deuterium distribution of products by liquid NMR indicate the occurrence of a number of catalytic reactions, including aromatization, rearrangement and substitution in the aliphatic chains, β-scission, dehydrogenation, and increased hydrogen enrichment at βand γ-positions. On the basis of our findings, we postulate that water addition to natural zeolites generates catalytic reactions that involve carbocation on acid sites. Studies with model compounds such as cumene and hexadecane also demonstrated significant cracking activity with water addition.
Partial Upgrading of Athabasca Bitumen Using Thermal Cracking
Catalysts
The current industry practice is to mix bitumen with a diluent in order to reduce its viscosity before it can be pumped to refineries and upgraders. The recovery of the diluent and its recycling to the producers, on the other hand, pose major environmental and economic concerns. Hence, onsite partial upgrading of the extracted bitumen to pipeline specifications presents an attractive alternative. In this work, thermal cracking of Athabasca bitumen was carried out in an autoclave at 400 °C, 420 °C and 440 °C in presence and absence of drill cuttings catalyst. At 400 °C, despite no coke formation, the reduction in viscosity was insufficient, whereas at 440 °C, the coke yield was significant, ~20 wt.%. A balance between yield and viscosity was found at 420 °C, with 88 ± 5 wt.% liquid, ~5 wt.% coke and a liquid viscosity and °API gravity of 60 ± 20 cSt and 23 ± 3, respectively. Additionally, the sulfur content and the Conradson carbon residue were reduced by 25% and 10%, respectively. T...
Thermal cracking of naTural biTumen in presence of acTivaTing addiTives
2019
The paper presents the results of thermal cracking of natural bitumens of the Beke and Munaily Mola oil sand deposits (Kazakhstan). The data obtained show that the high-molecular components of the bitumen of the Munaily Mola deposit are more easily cracked than those of the Beke deposit. The cracking of natural Beke bitumen in a medium of water vapor, acetonitrile and isopropanol is studied at different temperatures and pressures. The effect of the heterogeneous additive – nano-sized copper (II) oxide on the cracking efficiency of natural bitumen components is identified. The total yield of gas and coke is 3.2 %, while the distillate fractions is 40.8 mass % in case of cracking of the Beke natural bitumen in a flow reactor.
Handbook on Theory and Practice on Bitumen Recovery from Athabasca Oil Sands
2011
History has shown how oil sands development has progressed by building on existing technology platforms. As such, this handbook is a consolidation of the current technological foundation. It is intended to be a living document that is updated and augmented over time with ongoing technological and operational advancements. It is meant to engage the minds of professors, students, researchers, engineers, and technical operating staff. It will provide them with the technology foundation that will serve as the springboard for the future enhancements required for the sustainable development of our vast oil sands resource. It is their bright ideas and innovations that will be so vitally important if we, as Canadians, are to realize the huge socio-economic potential of this strategic global resource. The lead authors and the many others who have contributed to this handbook deserve our gratitude. It is a monumental undertaking that will have immediate application and impact. Dr. Eric P. Newell, O.C., AOE, FCAE, P.Eng Canada's crude bitumen resource is present mainly in the northeastern part of the province of Alberta, within three core oil sands areas (OSAs): Athabasca Wabiskaw-McMurray, Cold Lake Clearwater, and Peace River Bluesky-Gething (Figure .1). Together, these three OSAs occupy an area of approximately 142 000 km 2 (Energy Resources Conservation Board [ERCB] 2009, p. 2-4). The Athabasca Wabiskaw-McMurray OSA, known commonly as the Athabasca oil sands, is the largest of the three oil sands areas in Alberta. Other crude bitumen reserves are present within the Devonian and Mississippian carbonate deposits that unconformably underlie the Athabasca and Peace River unconsolidated sands. The deposits at Peace River, referred to as carbonate bitumen deposits, have not been commercially produced. Within the three OSAs, there are 15 separate oil sands deposits across different geological zones . Figure .2 shows the locations of bitumen-in-clastic sands and bitumen-in-carbonate rocks that form the main deposits in Alberta. Collectively, Alberta's oil sands contain one of the largest known hydrocarbon deposits in the world. With initial established reserves estimated at 28.092 10 9 m 3 (176.7 billion bbl), 4 the province was ranked second in the world in terms of oil reserves, after Saudi Arabia (Radler 2003). Conversion to barrels is rounded off in agreement to cited references. One cubic metre is equivalent to 6.29 barrels. A barrel is 42 US gallons. Cold Lake W a b is k a w -M c M u r ra y D e p o s it Fort McMurray At ha ba sc a Pe ac e Ri ve r B lu e s k y -G e t h in g D e p o s it C le a rw a te r D e p o s it
Experimental Investigation of Bitumen Recovery from Fractured Carbonates Using Hot-Solvents
SPE Annual Technical Conference and Exhibition, 2012
With the decrease in conventional oil and gas reserves throughout the world and an ever-increasing demand for fossil-fuel-based energy and resulting high oil prices, focus has been shifting to unconventional and heavy oil and bitumen. Grosmont carbonates in northern Alberta have been estimated to contain at least 300 billion bbl of heavy oil or bitumen. However, recovering this oil is extremely difficult because of the complexity associated with carbonate reservoirs in general (e.g., the Grosmont unit is known to possess a triple-porosity system of matrix, fractures, and vugs, on the basis of core studies). The second problem is the fluid itself, which is highly viscous bitumen that is immobile at reservoir conditions. To extract this bitumen from heterogeneous carbonate rock, both heat and dilution using solvents may be needed. This paper reports the results and analysis of hot-solvent experiments conducted on original Grosmont carbonate cores. Three experiments were conducted using propane and one using butane as solvent. After heating the entire system containing the core sample, solvent gas was injected. The rock was allowed to soak in the hot solvent for a long time. The experimental temperature and pressure were decided on the basis of the results of our earlier work that suggested they be slightly above the saturation line of the particular solvent. An attempt was made to keep the conditions close to the saturation conditions of the solvent being used to maximize the dilution and, hence, the recovery. The oil produced was analyzed for viscosity and asphaltene content. The results in terms of recovery, the degree of dilution, and upgrading achieved suggested that butane was a better solvent for this bitumen. Finally, the optimum conditions for operation of the hot-solvent process were verified for Grosmont carbonates. Problem Statement Bitumen recovery from complex carbonate structures is a challenging task. Although experimental studies are limited, it is a general consensus that heavy-oil or bitumen recovery from carbonates by steam injection (Babadagli and Al-Bemani 2007) or cold-solvent injection (Edmunds et al. 2009) is not highly promising, even for simple (single-matrix) systems. Alternative ideas should be tested at the laboratory scale first to promote further field-scale applications. The hot-solvent process is a combination of thermal and miscible processes for heavy-oil and bitumen recovery and involves the injection of a hydrocarbon solvent into a preheated reservoir. It is