Alonso Jiménez Padilla Pedro, Djimasbe Richard, Zairov Rustem, Yuan Chengdong, Al-Muntaser Ameen A, Stepanov Alexey, Nizameeva Guliya, Dovzhenko Alexey, Suwaid Muneer A, Varfolomeev Mikhail A, Zinnatullin Almaz L
Department of Petroleum Engineering, Kazan Federal University, 420008 Kazan, Russia.
Department of Physical Chemistry, Kazan Federal University, 420008 Kazan, Russia.
Nanomaterials (Basel). 2023 Apr 12;13(8):1351. doi: 10.3390/nano13081351.
In this study, Nickel oxide-based catalysts (NiO) 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 (NiO) 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, β-NiS, NiS, NiS, and NiO. The results of viscosity analysis, elemental analysis, and C 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 (ΣC-C) 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 H/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.
在本研究中,合成了基于氧化镍的催化剂(NiO),并将其用于重质原油(25℃下粘度为2157 mPa·s,API重度为14.1°)在水热裂解条件下的原位提质过程,以降低粘度并回收重油。通过扫描电子显微镜(SEM)、透射电子显微镜(TEM)、原子力显微镜(AFM)、X射线衍射(XRD)以及美国麦克默瑞提克公司的ASAP 2400分析仪等方法对所得纳米颗粒催化剂(NiO)进行了所有表征。在间歇式反应器中,于300℃和72巴的条件下进行了24小时的催化和非催化提质过程实验,催化剂用量占重质原油总重量的2%。XRD分析表明,使用NiO纳米颗粒显著参与了提质过程(通过脱硫),观察到了不同的活化形式催化剂,如α-NiS、β-NiS、NiS、NiS和NiO。粘度分析、元素分析和碳核磁共振分析结果表明,重质原油的粘度从2157 mPa·s降至800 mPa·s,重油中杂原子的去除率范围为:硫从4.28%降至3.32%,氮从0.40%降至0.37%,馏分总含量(ΣC-C)从59.56%增加至最高72.21%,这分别得益于正构烷烃和环烷烃的异构化以及芳烃结构侧链的脱烷基化,对于催化剂-3而言。此外,所得纳米颗粒表现出良好的选择性,促进了原位加氢-脱氢反应,并且碳上的氢再分布(H/C)得到改善,在样品催化剂-3中从1.48增加至最高1.77。另一方面,使用纳米颗粒催化剂也影响了氢气的产生,水煤气变换反应提供的H/CO增加。氧化镍催化剂因其在蒸汽存在下催化水热裂解反应的巨大潜力,具有用于重质原油原位水热提质的潜力。