In Situ Upgrading of Athabasca Bitumen Using Multimetallic Ultradispersed Nanocatalysts in an Oil Sands Packed-Bed Column: Part 2. Solid Analysis and Gaseous Product Distribution

Abstract

Thermal cracking of Athabasca bitumen was carried out in an oilsand packed-bed column, in the presence and absence of in situ prepared trimetallic nanocatalysts at a pressure of 3.5 MPa, residence time of 36 h, and temperatures of 320 and 340°C. In this part of the study, the effects of reaction severity (time and temperature) as well as the presence of nanocatalysts in packed media on solid and gaseous products were investigated. Results showed that the presence of trimetallic nanocatalysts enhanced the hydrogenation reactions and, consequently, led to significant reduction of coke formation (51.3%) and CO 2 emission reduction. Further, the analysis of the gaseous products and deposited solids confirmed the previous findings reported in part 1 (10.1021/ef401716h) of this study. The accumulative volume of coke precursor gases, such as ethylene and propylene, increased with the reaction severity. However, reaction severity has no significant effect on the atomic metallic ratios (metal/total metal) of the employed trimetallic nanocatalysts, which clearly demonstrates the stability of injected ultradispersed (UD) nanocatalysts (metal/total metal: Mo, 0.6267; Ni, 0.1808; and W, 0.1924) in the porous media at high pressure and temperature. Nonetheless, aggregation of nanocatalysts inside the porous media was observed and graphically demonstrated by environmental scanning electron microscopy (ESEM) images. Overall, the presence of trimetallic nanocatalysts in porous media not just enhanced bitumen upgrading but also improved the produced liquid quality and reduced the coke content as well as CO 2 emission by 50%.

Adsorption-desorption of n–C7 asphaltenes over micro- and nanoparticles of silica and its impact on wettability alteration

“…Hence, as proven by the studies above, once asphaltene compounds are adsorbed on the reservoir rock surface, wettability is altered to an oil-wet state until an effective treatment for asphaltene desorption is applied. Recently, nanoparticles have shown high potential for in-situ applications in the areas of inhibition of different types of formation damage (Franco, Nassar, Ruiz, Pereira-Almao, & Cortés, 2013c;Hashemi et al, 2015;Kazemzadeh, Malayeri, Riazi, & Parsaei, 2015a;Nassar, Betancur, Acevedo, Franco, & Cortés, 2015a;Shayan and Mirzayi, 2015;Zabala et al, 2014), enhanced oil recovery (Ehtesabi, Ahadian, & Taghikhani, 2014;Giraldo, Benjumea, Lopera, Cortés, & Ruiz, 2013a;Hashemi, Nassar, & Almao, 2014a;Hashemi, Nassar, & Pereira-Almao, 2012;Hashemi, Nassar, & Pereira Almao, 2013a;Hosseinpour, Mortazavi, Bahramian, Khodatars, & Khodadadi, 2014;Karimi et al, 2012;Kazemzadeh et al, 2015b) and heavy and extra-heavy oil upgrading (Franco et al, 2013b;Franco et al, 2014;Franco et al, 2015;Hamedi Shokrlu and Babadagli, 2013;Hosseinpour, Khodadadi, Bahramian, & Mortazavi, 2013;Hashemi, Nassar, & Pereira Almao, 2013b;Hashemi, Nassar, & Pereira Almao, 2014b;Mora, Franco, & Cortés, 2013;Nassar et al, 2015b;Nassar et al, 2012). Regarding the asphaltene-related problems, nanoparticles can restore wettability from an oil-wet state to a waterwet state (Giraldo et al, 2013a;Karimi et al, 2012).…”

“…Also, regarding asphaltene precipitation/deposition, nanoparticles can selectively adsorb asphaltenes from large asphaltene aggregate systems, leading to the reduction of the mean asphaltene aggregate size, which subsequently decreases the probability of asphaltene precipitation and deposition (Nassar et al, 2015a;Zabala et al, 2014). In thermal processes, such as insitu combustion, once asphaltenes are adsorbed on the nanoparticle surface, aquathermolysis or thermolysis, a catalytic cracking of the asphaltene molecule, can occur, leading to the formation of new and lighter compounds that would promote the in-situ upgrading of heavy and extra-heavy oils (Franco et al, 2013b;Franco et al, 2014;Franco et al, 2015;Hamedi Shokrlu and Babadagli, 2013;Hashemi et al, 2013b;Hashemi et al, 2014b;Mora et al, 2013;Nassar et al, 2015b;Nassar et al, 2012;Nassar et al, 2011a). However, the re-use of nanoparticles and the changes in their intrinsic properties after asphaltene adsorption are not yet fully understood.…”

Heavy Crude Oil Recovery Enhancement and In-Situ Upgrading During Steam Injection Using Ni-Co-Mo Dispersed Catalyst

“…This shows that the in-situ generated catalytic particles are of submicron scale as expected. The metals are Mo, Ni and Co. Submicron catalytic metals are reported to have these kind of morphology especially when generated insitu in an organic media (C. E. Gallaraga, 2011;Hashemi, et al, 2014;Thomson, 2008).…”

“…It can be seen different percentages of metal catalyst particles were recorded on the basis of selected spectrum. These differences are attributed to the different transport behavior of the metals in oil sand porous media (Hashemi, Nassar, & Pereira-Almao, 2012;Hashemi, et al, 2014).…”

“…Therefore, it is expected that, when steam injection processes and in-situ catalytic upgrading are carried out simultaneously, not just the capital cost will be significantly reduced but the whole process on the environmental impact will decrease as well (Hashemi, Nassar, & Pereira Almao, 2014;.…”