Kinetic Models for Upgrading Athabasca Bitumen Using Unsupported NiWMo Catalysts at Low Severity Conditions

Galarraga, C.; Scott, Carlos E.; Loria, Herbert; Pereira‐Almao, Pedro

doi:10.1021/ie201202b

Cited by 48 publications

(40 citation statements)

References 30 publications

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“…Suppression of coke formation due to hydrogen addition is widely thought of as a capping of free radical coke precursors formed when carbon-to-carbon bonds split leading to lower molecular weight compounds than the original THAI feed oil molecules. 44,45 A significant effect of hydrogen in this study was its ability to suppress the formation of coke compared to nitrogen as the flowing gas atmosphere (Figures 9a,b and 10), and as is commonly practiced in the refining industry the phenomenon is known to increase the yield of distillates and its quality. 46 Table 3S shows the composition of the produced gases when hydrogen was injected as the reaction atmosphere.…”

Section: Resultsmentioning

confidence: 81%

Optimization of the CAPRI Process for Heavy Oil Upgrading: Effect of Hydrogen and Guard Bed

Hart

Shah

Leeke

et al. 2013

Ind. Eng. Chem. Res.

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Toe-to-heel air injection (THAI) and its catalytic version CAPRI are relatively new technologies for the recovery and upgrade of heavy oil and bitumen. The technologies combine horizontal production well, in situ combustion, and catalytic cracking to convert heavy feedstock into light oil down-hole. The deposition of asphaltenes, coke, and metals can drastically deactivate the catalyst in the CAPRI process. A fixed bed microreactor was used to experimentally simulate the conditions in the catalyst zone of the oil well of CAPRI. In this study, oil upgrading and catalyst deactivation in the CAPRI process were investigated in the temperature range of 350−425°C, pressure of 20 barg and residence time of 9.2 min. Additionally, a guard bed consisting of activated carbon particles prior to the active catalyst in a microreactor and/or the addition of hydrogen to the gas feed were used to minimize coke formation and catalyst deactivation through respectively removing and hydrocracking the coke precursors. It was found that depending on the upgrading temperature, the viscosity of the produced oil reduced significantly by 42−82% and (American Petroleum Institute) API gravity increased by ∼2 to 7°API relative to the feedstock of 0.49 Pa·s and 13°API, respectively. Conversely, the use of hydrogen further increased the API gravity by 2°API and the viscosity by 5.3%. Notably, the coke content of the catalyst reduced from 57.3 wt % in nitrogen to 34.8 wt % in hydrogen atmosphere. The use of a guard bed increased the API gravity of the produced oil by a further 2°and reduced the viscosity by an average of 8.5% further than achieved with the active HDS catalyst CoMo/alumina.

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Section: Resultsmentioning

confidence: 81%

Optimization of the CAPRI Process for Heavy Oil Upgrading: Effect of Hydrogen and Guard Bed

Hart

Shah

Leeke

et al. 2013

Ind. Eng. Chem. Res.

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“…Moreover nano-sized catalysts have a high surface to volume ratio, low intraparticle mass transfer resistance and thus may be more resistant to deactivation than pelleted catalysts [9,11]. Ultrafine (micron) scale particles may also offer some of these advantages whilst being cheaper to produce, not requiring specialist preparation and easier to handle, for example not being absorbed easily through the skin.…”

Section: Introductionmentioning

confidence: 99%

Effect of cyclohexane as hydrogen-donor in ultradispersed catalytic upgrading of heavy oil

Hart

Lewis

White

et al. 2015

Fuel Processing Technology

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The incorporation of catalysts to enhance downhole upgrading in the Toe-to-Heel Air Injection (THAI) process is limited by deactivation due to coking arising from the cracking of heavy oil. This study aims to reduce the catalyst deactivation problems that can occur with upgrading of heavy oils. Ultradispersed catalyst particles could potentially replace pelleted catalysts which may be difficult to regenerate once deactivated during the THAI operation. The dispersed particles could potentially be applied once through, down-hole for in situ upgrading of heavy oil. The catalyst studied was finely crushed pelleted Ni-Mo/Al 2 O 3 catalyst (2.4 μm). The product distribution of liquid, coke and gas may be influenced by the presence of a suitable hydrogen source which promotes hydroconversion reactions rather than simple cracking. In order to improve liquid yield whilst suppressing coke formation, the effect of cyclohexane as hydrogen-donor solvent was studied in a stirred batch reactor (100 mL) at temperature 425°C, initial pressure 17.5 bar, agitation 500 rpm, and a short reaction time of 10 min. The use of cyclohexane was evaluated against that of hydrogen gas. The reaction under hydrogen atmosphere significantly reduced coke yield by 41.3% compared with a nitrogen environment under the same conditions. Also, the coke decreased by 6.2-45.4% as the cyclohexane:oil ratio increased from 0.01 to 0.08 (g·g −1 ) relative to 4.67 wt.% of coke observed without added cyclohexane in ultradispersed catalytic upgrading under nitrogen environment. As the cyclohexane:oil ratio increases, the produced oil API gravity and middle distillate fractions (200-343°C) increase whilst the viscosity decreases. An estimated 0.073 CH:oil ratio was found to suppress coke formation in a similar manner to upgrading under hydrogen atmosphere at the same conditions.

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“…[4,5,6,9,10] Another type of asphalt binder's modifier may be organometallic catalysts. Their operation depends mainly on the stiffening of the bitumen as a result of oxidative polymerization [1,2,3,7,11,12]. The obtained effects depend on the type of organometallic salt used and the course of the oxidation reaction [1,2,7,11].…”

Section: Introductionmentioning

confidence: 99%

Asphalt concretes with metal-organic frameworks for highways and expressway road surfaces

Mieczkowski

Jurczak

Budziński

2018

TO - PK

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The aim of performed research and analysis is the evaluation of the influence of metal-organic catalyst (MOC) on the properties of asphalt concretes designed for KR5-7 traffic load. The anhydrous iron (III) chloride was added as a metal-organic catalyst in the amount of 2,5% of asphalt mass. The study determined the properties of asphalt concrete with modified binder (70/100+2,5% FeCl3) and referential asphalt concrete with typical binder 35/50. The test included determination of water and freeze-thaw resistance (ITSR) and resistance to permanent deformation. Additional basic tests were performed to compare the properties of modifies, the 70/100 and 35/50 asphalt. The research was performed for three binder conditions: before aging, short-term aging in accordance with RTFOT and PAV long-term aging. The test results allowed to determine the IP penetration index. Additionally, for 35/50 asphalt and modified binder the dynamic viscosity was determined before and after aging in accordance with RTFOT. The addition of metal-organic catalyst increased the resistance of the asphalt concrete to permanent deformation without changing its water and freeze-thaw resistance. In case of the 70/100 asphalt the addition of MOC improved the hardness (especially after short- and long-term aging) and influenced the rheology.

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Kinetic Models for Upgrading Athabasca Bitumen Using Unsupported NiWMo Catalysts at Low Severity Conditions

Cited by 48 publications

References 30 publications

Optimization of the CAPRI Process for Heavy Oil Upgrading: Effect of Hydrogen and Guard Bed

Optimization of the CAPRI Process for Heavy Oil Upgrading: Effect of Hydrogen and Guard Bed

Effect of cyclohexane as hydrogen-donor in ultradispersed catalytic upgrading of heavy oil

Asphalt concretes with metal-organic frameworks for highways and expressway road surfaces

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