In Situ Upgrading of Athabasca Bitumen Using Multimetallic Ultradispersed Nanocatalysts in an Oil Sands Packed-Bed Column: Part 1. Produced Liquid Quality Enhancement

Abstract

Conventional crude oil production is declining, while the consumption of petroleum-based fuels is increasing. Therefore, bitumen and heavy oil exploitation is steadily growing. However, in the present context, heavy oil and bitumen exploitation processes are high-energy and water-intensive and, consequently, have significant environmental footprints because of the production of gaseous emissions, such as CO 2 , and generating huge amounts of produced water. In situ catalytic conversion or upgrading is a promising cost-effective and environmentally friendly technology that aims at reducing the environmental footprints of oil sand exploitation and producing of high-quality oil that meets pipeline and refinery specifications. In this study, in situ prepared Ni−W−Mo ultradisperse nanocatalysts within a vacuum gas oil matrix were used for Athabasca bitumen upgrading in a packed-bed flow reactor at a high pressure and temperature. Experiments were performed at a pressure of 3.5 MPa, temperatures from 320 to 340 °C, and a hydrogen flow rate of 1 cm 3 /min. The produced liquid was analyzed on the basis of residue conversion, microcarbon residue (MCR) content, sulfur and nitrogen contents, American Petroleum Institute (API) gravity, and viscosity. Results showed that nanocatalysts enhanced the quality of Athabasca bitumen by increasing the API gravity and decreasing the viscosity and MCR, sulfur, and nitrogen contents. Nanocatalysts effectively favored the hydrogenation reactions and inhibited the massive formation of coke that usually occurs via olefin polymerization and heavy free radical condensation during the classical thermal cracking process of heavy oils.

Application of Nanoparticles in Enhanced Oil Recovery: A Critical Review of Recent Progress

“…For instance, Nassar et al [96] was the first to propose in-situ upgrading of heavy oil by adding nanocatalysts in combination with SAGD ( Figure 15). Then, in order to investigate the effect of reaction severity and nanocatalysts on solid and gaseous products, Hashemi et al [97] studied for the first time in situ upgrading of Athabasca bitumen using Ni-W-Mo nanocatalysts in a continuous flow mode. The results showed that nanocatalysts bettered the quality of Athabasca bitumen by improving the bitumen properties such as decreasing the density, viscosity and microcarbon residue.…”

Influence of Asphaltene Aggregation on the Adsorption and Catalytic Behavior of Nanoparticles

“…[5][6][7][8][9][10][11][12][13][14][15][16][17][18][19][20][21] Because of their special and unique properties, nanoparticles are able to improve the mobility of oil under reservoir conditions and may be used as adsorbents/catalysts for 3 enhancing the upgrading and recovery of heavy oil. 5,11,13,14,22,23 The small size of the nanoparticles (between 1 and 100 nm) allows these particles unimpeded transport and a good dispersion ability through porous media, without risk of blocking the pores. 13 Further, the high ratio of the surface area/volume of the nanoparticles as well as their surface functionality makes them good adsorbents for heavy polar hydrocarbons in crude oils, such as asphaltenes.…”

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.…”