Partial Upgrading of Bitumen by Thermal Conversion at 150–300 °C

Jaramillo, Lina M. Yañez; Klerk, Arno de

doi:10.1021/acs.energyfuels.7b04145

Cited by 20 publications

(19 citation statements)

References 39 publications

(63 reference statements)

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“…Indirect evidence of this was experimentally found. − The extent of conversion and viscosity reduction observed at lower operating temperatures exceeded that predicted on the basis of using high-temperature kinetics, e.g., eq . However, to what extent these experimental observations could be attributed to the higher than predicted free radical concentration (section ) and to what extent this is due to the increased contribution of transfer reactions is undetermined.…”

Section: Impact Of the Temperature On The Description Of Thermal Conv...mentioning

confidence: 86%

Thermal Conversion Modeling of Visbreaking at Temperatures below 400 °C

Klerk

2020

Energy Fuels

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This paper is in honor of Michael (Mike) T. Klein, and his contributions to the modeling of thermal conversion are highlighted within the context of this study. The question that was posed is whether thermal conversion models developed for conventional visbreaking (430–490 °C) are adequate for the description of visbreaking at lower temperatures? This topic is relevant to partial upgrading of bitumen by visbreaking at temperatures of <400 °C. Insights from thermal conversion performed at 100–430 °C were employed to revisit the description of the free radical chemistry and how temperature affected the relative importance of thermal reactions. With a decreasing temperature, the increasing contribution of reactions, such as molecule-induced homolysis and the presence of “persistent” free radical species in the feed, results in a higher free radical concentration than is predicted by initiation through thermally induced homolytic bond dissociation. With a decreasing temperature, transfer reactions are also increasing in relative importance. This affects propagation and termination reactions. One of the important consequences of the increased contribution of transfer reactions at lower temperatures is that the apparent activation energy of cracking is reduced. The threshold temperature below which conventional visbreaking models no longer provide an adequate description of conversion is 380–400 °C. Drawing on the differences that must be captured to model low-temperature thermal conversion, it was shown that the development work by Mike Klein provided a solid basis for such modeling. Of particular importance is the ability to incorporate reactive intermediates that include radical isomers and to model transfer reactions. Quantitative structure–reactivity relationships captured the essence of the chemistry that must be reflected to model low-temperature thermal conversion.

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Section: Impact Of the Temperature On The Description Of Thermal Conv...mentioning

confidence: 86%

Thermal Conversion Modeling of Visbreaking at Temperatures below 400 °C

Klerk

2020

Energy Fuels

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“…The decrease in the viscosity of bitumen treated alone at 250 °C was also observed in the work by Yañez Jaramillo and de Klerk in the investigation of viscosity changes in Cold Lake bitumen upon thermal conversion between 150 and 300 °C. In their work, the viscosity of bitumen measured at 40 °C decreased from 88 to 4.4 Pa·s upon thermal treatment at 250 °C for 2 h, and it was noted that the change in viscosity with reaction time was not a monotonous decrease.…”

Section: Discussionmentioning

confidence: 99%

“…A temperature of 250 °C was chosen for this study, because it is a temperature that is low enough to be achieved using steam heating (instead of a furnace) but at which the bitumen can still undergo some conversion. 14,15 2. EXPERIMENTAL SECTION 2.1.…”

Section: Introductionmentioning

confidence: 99%

“…This was done by performing reactions using industrially obtained bitumen froth and measuring the properties of bitumen before and after reaction. A temperature of 250 °C was chosen for this study, because it is a temperature that is low enough to be achieved using steam heating (instead of a furnace) but at which the bitumen can still undergo some conversion. , …”

Section: Introductionmentioning

confidence: 99%

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Hydrothermal Treatment of Bitumen Froth: Impact of Mineral Solids and Water on Bitumen Properties

Turuga

Klerk

2021

Energy Fuels

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Hydrothermal treatment, i.e., thermal treatment of bitumen in the presence of water and solids, as a potential approach for combined froth treatment and upgrading was investigated in this work. Reactions were performed in batch reactors at 250 °C with the bitumen, water, and solid phases separated from industrially obtained bitumen froth, and the impact of the presence or absence of water and/or solids on the bitumen conversion was studied. Statistical analysis of bitumen properties revealed that the hydrothermal treatment of the bitumen froth at 250 °C did not lead to upgrading of the bitumen. Treatment at the conditions used in this study was beneficial only when the bitumen was converted on its own. Water and/or mineral solids contributed to an increase in viscosity, which was accompanied by an increase in free radical content. These observations were tentatively explained based on the generation of free radicals by redox reactions and heavier product formation promoted by free radical addition reactions. While the treatment did not significantly impact the density of bitumen, changes in the H/C ratio, n-heptane insoluble content, and metal content of bitumen were noted. The total acid number (TAN) of bitumen increased in the presence of water and mineral solids. Base-catalyzed hydrolysis of esters and anhydrides in bitumen might be responsible for the increase in TAN, and the solids and water appeared to promote these reactions.

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“…A methane upgrading unit at relatively mild conditions of 400 • C and 3 MPa for successful partial upgrading of bitumen in an autoclave was proposed [22][23][24]. Moreover, a low temperature viscosity reduction scheme to achieve upgrading in situ during production has been attempted to some success [25]. A hydro-conversion process was applied to achieve high sulfur and residue conversion in a fixed-bed reactor configuration [26].…”

Section: Introductionmentioning

confidence: 99%

Partial Upgrading of Athabasca Bitumen Using Thermal Cracking

Kaminski

Husein

2019

Catalysts

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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. The catalytic thermal cracking at 420 °C further improved the quality of the liquid product to 40 ± 6 cSt and 25 ± 2 °API gravity, however at slightly lower liquid yield of 86 ± 6 wt.%. Both catalytic and non-catalytic cracking provide a stable liquid product, which by far exceeds pipeline standards. Although small relative to the energy required for upgrading in general, the pumping energy requirement for the partially upgraded bitumen was 3 times lower than that for diluted bitumen. Lastly, a 5-lump, 6-reaction, kinetic model developed earlier by our group successfully predicted the conversion of the bitumen to the different cuts.

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Partial Upgrading of Bitumen by Thermal Conversion at 150–300 °C

Cited by 20 publications

References 39 publications

Thermal Conversion Modeling of Visbreaking at Temperatures below 400 °C

Thermal Conversion Modeling of Visbreaking at Temperatures below 400 °C

Hydrothermal Treatment of Bitumen Froth: Impact of Mineral Solids and Water on Bitumen Properties

Partial Upgrading of Athabasca Bitumen Using Thermal Cracking

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