Use of Nickel Oxide Catalysts (Bunsenites) for In-Situ Hydrothermal Upgrading Process of Heavy Oil.

In this study, Nickel oxide-based catalysts (NixOx) were synthesized and used for the in-situ upgrading process of heavy crude oil (viscosity 2157 mPa·s, and API gravity of 14.1° at 25 °C) in aquathermolysis conditions for viscosity reduction and heavy oil recovery. All characterizations of the obtained nanoparticles catalysts (NixOx) were performed through Scanning Electron Microscopy (SEM), Transmission Electron Microscopy (TEM), Atomic Force Microscopy (AFM), X-Ray and Diffraction (XRD), and ASAP 2400 analyzer from Micromeritics (USA), methods. Experiments of catalytic and non-catalytic upgrading processes were carried out in a discontinuous reactor at a temperature of 300 °C and 72 bars for 24 h and 2% of catalyst ratio to the total weight of heavy crude oil. XRD analysis revealed that the use of nanoparticles of NiO significantly participated in the upgrading processes (by desulfurization) where different activated form catalysts were observed, such as α-NiS, ß-NiS, Ni3S4, Ni9S8, and NiO. The results of viscosity analysis, elemental analysis, and 13C NMR analysis revealed that the viscosity of heavy crude oil decreased from 2157 to 800 mPa·s, heteroatoms removal from heavy oil ranged from S-4.28% to 3.32% and N-0.40% to 0.37%, and total content of fractions (ΣC8-C25) increased from 59.56% to a maximum of 72.21%, with catalyst-3 thank to isomerization of normal and cyclo-alkanes and dealkylation of lateral chains of aromatics structures, respectively. Moreover, the obtained nanoparticles showed good selectivity, promoting in-situ hydrogenation-dehydrogenation reactions, and hydrogen redistribution over carbons (H/C) is improved, ranging from 1.48 to a maximum of 1.77 in sample catalyst-3. On the other hand, the use of nanoparticle catalysts have also impacted the hydrogen production, where the H2/CO provided from the water gas shift reaction has increased. Nickel oxide catalysts have the potential for in-situ hydrothermal upgrading of heavy crude oil because of their great potential to catalyze the aquathermolysis reactions in the presence of steam.

Experimental study of non-oxidized and oxidized bitumen obtained from heavy oil.

Heavy oil and vacuum residue were used to obtain road bitumen BND 50/70 using two different methods of steam distillation at 323-362 °C and by oxidation, a method using packed column at temperature of 211-220 °C. The obtained residues using two methods steam distillation and oxidation are known as non-oxidized bitumen and oxidized bitumen, respectively. The products were evaluated using different standards including GOST 33133-2014, GOST 22245-90, and ASTM D5. The results showed that the yield of oxidized bitumen reached a maximal rate of 89.59% wt., while that of non-oxidized bitumen is 55% wt. The softening point of oxidized bitumen is 49-57 °C compared to non-oxidized bitumen (46-49 °C). Remarkably, the previous softening point and penetrability of 47-71 points of oxidized bitumen are consistent with norms to BND 50/70 bitumen, according standard. The non-oxidized bitumen has a relatively low softening point and a higher penetration value of 71-275, which refers to BND 200/300 bitumen. Comparatively, the use of a packed column is beneficial than the steam distillation, due to high capability of the nozzles to strengthens contact between feedstock and compressed air in the reaction zone and decreases the reaction time to 4.15 h.

Deep Insights into Heavy Oil Upgrading Using Supercritical Water by a Comprehensive Analysis of GC, GC-MS, NMR, and SEM-EDX with the Aid of EPR as a Complementary Technical Analysis.

Upgrading of heavy oil in supercritical water (SCW) was analyzed by a comprehensive analysis of GC, GC-MS, NMR, and SEM-EDX with the aid of electron paramagnetic resonance (EPR) as a complementary technical analysis. The significant changes in the physical properties and chemical compositions reveal the effectiveness of heavy oil upgrading by SCW. Especially, changes of intensities of conventional EPR signals from free radicals (FRs) and paramagnetic vanadyl complexes (VO2+) with SCW treatment were noticed, and they were explained, respectively, to understand sulfur removal mechanism (by FR intensity and environment destruction) and metal removal mechanism (by VO2+ complexes' transformation). For the first time, it was shown that electronic relaxation times extracted from the pulsed EPR measurements can serve as sensitive parameters of SCW treatment. The results confirm that EPR can be used as a complementary tool for analyzing heavy oil upgrading in SCW, even for the online monitoring of oilfield upgrading.