Tetralin and Decalin H-Donor Effect on Catalytic Upgrading of Heavy Oil Inductively Heated with Steel Balls

Abstract

The Toe-to-Heel Air Injection (THAI) combined with catalytic upgrading process in situ (CAPRI) has demonstrated it can simultaneously extract and upgrade heavy oil in situ. This paper reports the investigation of augmenting temperature deficit and suppressing coke formation in the CAPRI section through the incorporation of induction heating and H-donor solvents. An induction-heated catalytic reactor was designed and developed, heated with steel balls in a mixed bed of NiMo/Al2O3 catalyst (66% v/v) to 425 °C temperature, 15 bar pressure and 0.75 h−1 LHSV (Liquid Hourly Space Velocity). The catalyst surface area, pore volume and pore size distribution were determined by using nitrogen adsorption–desorption, while the location of coke deposits within the microstructure of the pelleted spent catalyst was analyzed with X-ray nano-Computed Tomography (X-ray nano-CT). Findings showed that induction heating improved the catalyst performance, resulting in a 2.2° American Petroleum Institute (API) gravity increase of the upgraded oil over that achieved with the conventional heating method. The increment in API gravity and viscosity reduction in the upgraded oils with nitrogen gas only, N2 and H-donor solvents, and hydrogen gas environments can be summarized as follows: decalin > H2 gas >= tetralin > N2 gas. Meanwhile, the improvement in naphtha fraction, middle distillate fractions and suppression of coke formation are as follows: decalin > H2 gas > tetralin > N2 gas. The X-ray nano-CT of the spent catalyst revealed that the pellet suffers deactivation due to coke deposit at the external surface and pore-mouth blockage, signifying underutilization of the catalyst interior surface area.

Hydrogenation and Dehydrogenation of Tetralin and Naphthalene to Explore Heavy Oil Upgrading Using NiMo/Al2O3 and CoMo/Al2O3 Catalysts Heated with Steel Balls via Induction

“…The physisorption analysis reveals type IV isotherm and mesoporous structure characteristics for both catalysts. This is affirmed by their pore sizes between 2 and 50 nm [20]. The X-ray diffraction (XRD) pattern of the NiMo/Al2O3 and CoMo/Al2O3 catalysts is shown in Figure 1.…”

“…Therefore, hydrogen gas addition will promote the desorption of hydrogenated radicals from the catalyst surface while halting free radical's addition reactions to improve fuel distillate fractions, hence reducing pore plugging and suppressing coke formation [10]. Since the catalyst surface is hotter with steel balls inductive heated catalyst bed than conventional heated via furnace ( Figure 6), it suggests that under hydrogen-rich environment, the desorption of hydrogenated molecule would be enhanced as well [20].…”

Optimization of reaction temperature and Ni–W–Mo catalyst soaking time in oil upgrading: application to kinetic modeling of in-situ upgrading

“…These materials, which are named catalysts 11 , not only decrease oil viscosity followed by increasing the mobility ratio of oil in porous media, but also increase heavy oil quality. The quality of heavy oil depends on the amount of heavy fraction of oil (based on boiling point distribution such as residue and vacuum gas oil (VGO)) and light fractions (such as distillate and naphtha) 12 , 13 .…”

Batch Reactor Study for Partial Upgrading of a Heavy Oil with a Novel Solid Hydrogen Transfer Agent

“…The main findings are: Hydrogen donors enhanced hydrogen transfer to coal during coal liquefaction. − Hydrogen transferred from cyclic olefins, such as 1,4,5,8,9,10-hexahydroanthracene and 1,4,5,8-tetrahydronaphthalene (isotetralin), to coal Paraffins and single-ring naphthenic compounds were not active as hydrogen donors, and condensed-ring naphthenic compounds such as decalin showed some activity, whereas mixed naphthenic–aromatic condensed-ring compounds such as 1,2,3,4-tetrahydronaphthalene (tetralin) showed good hydrogen transfer capacity. − Polar hydrogen donors such as tetrahydroquinoline (THQ) and indoline are good hydrogen donor solvents in the upgrading of petroleum residues by thermal processing Crude oil residue can be thermally converted to more valuable products by using tetralin, which donates hydrogen to the cracked residue .…”

“…Paraffins and single-ring naphthenic compounds were not active as hydrogen donors, and condensed-ring naphthenic compounds such as decalin showed some activity, whereas mixed naphthenic–aromatic condensed-ring compounds such as 1,2,3,4-tetrahydronaphthalene (tetralin) showed good hydrogen transfer capacity. − …”