Comparison of the effects of dispersed noble metal (Pd) biomass supported catalysts with typical hydrogenation (Pd/C, Pd/Al2O3) and hydrotreatment catalysts (CoMo/Al2O3) for in-situ heavy oil upgrading with Toe-to-Heel Air Injection (THAI)

Hart, Abarasi; Omajali, Jacob B.; Murray, Angela J.; Macaskie, Lynne E.; Gréaves, M.; Wood, Joseph

doi:10.1016/j.fuel.2016.04.064

Cited by 28 publications

(27 citation statements)

References 40 publications

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“…The coke contents of the recovered catalyst after experiment with nitrogen (20 bar) and hydrogen (20 to 40 bar) as determined using TGA are presented in Figure 4. It has been reported that the burn-off beyond 600 • C represents coke [44]. The thermogram (TG), that is weight loss with temperature and its differential (DTG) curves show that the coke formation under nitrogen environment is higher (35.4 wt %) compared to hydrogen (27.2 wt %).…”

Section: Upgraded Oil Asphaltene and Spent Catalyst Coke Contentsmentioning

confidence: 99%

In Situ Catalytic Upgrading of Heavy Crude with CAPRI: Influence of Hydrogen on Catalyst Pore Plugging and Deactivation due to Coke

Hart

Wood

2018

Energies

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Heavy crude oil is known to have low hydrogen-to-carbon ratios compared to light oil. This is due to the significant content of carbon-rich species such as resins and asphaltenes; hence their upgrading is commonly through carbon-rejection. However, carbon-rejection promotes rapid fouling of catalyst and pore plugging, yielding low upgraded oil and consequently low fuel distillate fractions when distilled. The roles of hydrogen-addition on in situ catalytic upgrading were investigated at pre-established conditions (425 • C, LHSV 11.8 h −1 , and 20-40 bars) using a simulated fixed-bed reactor that mimics the annular sheath of catalyst (CAPRI) surrounding the horizontal producer well of the Toe-to-Heel Air Injection (THAI) process. It was found that with H-addition, the upgraded oil American Petroleum Institute (API) gravity increased to about 5 • compared to 3 • obtained with N 2 above 13 • (THAI feed oil). The fuel distillate fractions increased to 62% (N 2 , 20 bar), 65% (H 2 , 20 bar), and 71.8% (H 2 , 30 bar) relative to 40.6% (THAI feed oil); while the coke contents of the catalyst after experiments were 35.3 wt % (N 2), and 27.2 wt % (H 2). It was also found that catalyst pore plugging and deactivation due to coke was significantly lower under hydrogen than with nitrogen; hence the catalyst is less susceptible to coke fouling when the upgrading reaction is carried out under hydrogen. The coke fouling further decreases with increasing hydrogen pressure while the API gravity of the upgraded oil marginally increases by 0.3 • for every 10 bar increase in pressure from 20 to 40 bar.

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Section: Upgraded Oil Asphaltene and Spent Catalyst Coke Contentsmentioning

confidence: 99%

In Situ Catalytic Upgrading of Heavy Crude with CAPRI: Influence of Hydrogen on Catalyst Pore Plugging and Deactivation due to Coke

Hart

Wood

2018

Energies

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“…However, Pd or Pt cannot withstand the sulphur content in heavy oil. Hence, transition metals such as Ni, Co and Mo supported on alumina and/or silica are commonly used in catalytic upgrading of heavy oil and were used in this study [24,25]. In this study, a laboratory-scale inductive heated reactor to be combined with THAI-CAPRI process for heavy oil recovery and in situ upgrading was developed.…”

Section: Introductionmentioning

confidence: 99%

Inductive Heating Assisted-Catalytic Dehydrogenation of Tetralin as a Hydrogen Source for Downhole Catalytic Upgrading of Heavy Oil

et al. 2019

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The Toe-to-Heel Air Injection (THAI) combined with a catalytic add-on (CAPRI, CATalytic upgrading PRocess In-situ) have been a subject of investigation since 2002. The major challenges have been catalyst deactivation due to coke deposition and low temperatures (~ 300 °C) of the mobilised hot oil flowing over the catalyst packing around the horizontal well. Tetralin has been used to suppress coke formation and also improve upgraded oil quality due to its hydrogen-donor capability. Herein, inductive heating (IH) incorporated to the horizontal production well is investigated as one means to resolve the temperature shortfall. The effect of reaction temperature on tetralin dehydrogenation and hydrogen evolution over NiMo/ Al 2 O 3 catalyst at 250-350 °C, catalyst-to-steel ball ratio (70% v/v), 18 bar and 0.75 h −1 was investigated. As temperature increased from 250 to 350 °C, tetralin conversion increased from 40 to 88% while liberated hydrogen increased from 0.36 to 0.88 mol based on 0.61 mol of tetralin used. The evolved hydrogen in situ hydrogenated unreacted tetralin to trans and cis-decalins with the selectivity of cis-decalin slightly more at 250 °C while at 300-350 °C trans-decalin showed superior selectivity. With IH the catalyst bed temperature was closer to the desired temperature (300 °C) with a mean of 299.2 °C while conventional heating is 294.3 °C. This thermal advantage and the nonthermal effect from electromagnetic field under IH improved catalytic activity and reaction rate, though coke formation increased.

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“…<0.5 wt.%). Despite this, the authors of a previous study utilising the same native oil and reactor conditions as used here, assumed that although sulfur is present in potentially inhibitory concentrations, it may be present in non-available forms due to its association with other metals present in the native feed oil [34]. Although the extent of sulphur deactivation was not evaluated in this study, the data suggest that the Pd-BnM catalyst performed comparably with typically refinery catalysts (table 1).…”

Section: Catalytic Upgrading Of Oil By Palladised Biogenic Magnetitementioning

confidence: 78%

“…The amount of coke in the deposit was determined from the temperature-weight loss curve. Previous analyses under the same experimental conditions have established the temperatures at which residual oil (25 to 410 °C), resins and asphaltenes (410 to 620 °C) and coke (>620 °C ) are burnt-off [32][33][34]. Upon heating, it is possible that the remaining catalyst may undergo modification, e.g.…”

Section: Analysis Of Oilmentioning

confidence: 99%

Upgrading of heavy oil by dispersed biogenic magnetite catalysts

Brown

Hart

Coker

et al. 2016

Fuel

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In situ catalytic upgrading of heavy oil offers significant cost savings and overcomes logistical challenges associated with the high viscosity, low API gravity and high molecular weight fractions of unconventional hydrocarbon resources. The THAI-CAPRI process (toe-to-heel air injection-catalytic upgrading process in situ) offers one such route to upgrading through the use of high surface area transition metal cracking catalysts surrounding the production well. Here, we describe the catalytic upgrading of heavy oil in a stirred batch reactor by a biogenic nanoscale magnetite (BnM; Fe 3 O 4). A 97.8% decrease in viscosity relative to the feed oil was achieved and coking was lower compared to thermal cracking alone (6.9 wt% versus 10.2 wt%). The activity of this catalyst was further enhanced by a simple one-step addition of surface associated Pd to achieve loadings of 4.3, 7.1 and 9.5 wt% Pd. This led to significant decreases in viscosity of up to 99.4% for BnM loaded with 9.5 wt% Pd. An increment of 7.8° in API gravity with respect to the feed oil was achieved for 9.5 wt% Pd-BnM, compared with thermal cracking alone (5.3°). Whilst this level of upgrading was comparable to commercially available and previously tested catalysts, significant decreases in the coke content (3 wt% for 9.5 wt% Pd-BnM versus 10 wt% for thermal cracking) and associated increases in liquid content (~90 wt% for 9.5 wt% Pd-BnM versus ~79 wt% for thermal cracking) demonstrate the potential for the use of Pd-augmented biogenic magnetite as a catalyst in the THAI CAPRI process.

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Comparison of the effects of dispersed noble metal (Pd) biomass supported catalysts with typical hydrogenation (Pd/C, Pd/Al2O3) and hydrotreatment catalysts (CoMo/Al2O3) for in-situ heavy oil upgrading with Toe-to-Heel Air Injection (THAI)

Cited by 28 publications

References 40 publications

In Situ Catalytic Upgrading of Heavy Crude with CAPRI: Influence of Hydrogen on Catalyst Pore Plugging and Deactivation due to Coke

In Situ Catalytic Upgrading of Heavy Crude with CAPRI: Influence of Hydrogen on Catalyst Pore Plugging and Deactivation due to Coke

Inductive Heating Assisted-Catalytic Dehydrogenation of Tetralin as a Hydrogen Source for Downhole Catalytic Upgrading of Heavy Oil

Upgrading of heavy oil by dispersed biogenic magnetite catalysts

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