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使用新型氧化石墨烯-铜锌铁氧体纳米复合材料作为催化剂,通过催化水热裂解优化重质原油的原位升级。

Optimizing in-situ upgrading of heavy crude oil via catalytic aquathermolysis using a novel graphene oxide-copper zinc ferrite nanocomposite as a catalyst.

作者信息

Soliman Ahmed Ashraf, Aboul-Fetouh Mostafa E, Gomaa Sayed, Aboul-Fotouh Tarek M, Attia Attia Mahmoud

机构信息

Mining and Petroleum Engineering Department, Faculty of Engineering, Al-Azhar University, Nasr City, Cairo, 11884, Egypt.

Petroleum Engineering and Gas Technology Department, Faculty of Energy and Environmental Engineering, British University in Egypt (BUE), El Sherouk City, Cairo, Egypt.

出版信息

Sci Rep. 2024 Oct 28;14(1):25845. doi: 10.1038/s41598-024-73953-0.

Abstract

Unconventional resources, such as heavy oil, are increasingly being explored and exploited due to the declining availability of conventional petroleum resources. Heavy crude oil poses challenges in production, transportation, and refining, due to its high viscosity, low API gravity, and elevated sulfur and metal content. Improving the quality of heavy oil can be achieved through the application of steam injection, which lowers the oil's viscosity and enhances its flow. However, steam injection alone falls short of meeting the growing demand for higher-quality petroleum products. Catalytic upgrading is therefore being investigated as a viable solution to improve heavy oil quality. This study experimentally investigates the application of two novel catalysts, namely copper-substituted zinc ferrite (ZCFO) synthesized via the sol-gel combustion method and a graphene oxide-based nanocomposite (GO-ZCFO) with different ratios, for catalyzing aquathermolysis reactions in the steam injection process, with the aim of enhancing the in-situ upgrading of heavy oil. These catalysts underwent characterization using X-ray powder diffraction (XRD), Fourier Transform Infrared Spectroscopy (FTIR), and Transmission Electron Microscopy (TEM). Their catalytic performance was assessed utilizing a high-pressure/high-temperature reactor (300 ml), with a comprehensive analysis of the changes in the physical and chemical properties of the heavy oil before and after upgrading. This analysis included measurements of sulfur content, SARA fractions, viscosity, API gravity, and Gas Chromatography (GC) of saturated hydrocarbons and evolved gases. All upgrading experiments, including both catalytic and non-catalytic aquathermolysis processes, were conducted under a reaction time of 6 h, a reaction temperature of 320 °C, and high pressure (86-112 bar). The results indicated that the introduction of the proposed catalysts as additives into the upgrading system resulted in a significant reduction in sulfur content. This, in turn, led to a decrease in resin and asphaltene content, an increase in the content of saturated hydrocarbon, particularly low-molecular-weight alkanes, and ultimately, a reduction in viscosity along with higher API gravity of the crude oil. GO-ZCFO with a weight ratio (50:50) exhibited the best catalytic performance. The heavy crude oil, upgraded with this 50:50 ratio, exhibited significant enhancements, including a 29.26% reduction in sulfur content, a 21.27% decrease in resin content, a 37.60% decrease in asphaltene content, a 46.92% increase in saturated hydrocarbon content, a 66.48% reduction in viscosity, and a 25.49% increase in API gravity. In comparison, the oil upgraded through non-catalytic aquathermolysis showed only marginal improvements, with slight reductions in sulfur content by 5.41%, resin content by 3.60%, asphaltene content by 11.36%, viscosity by 17.89%, and inconsiderable increases in saturated hydrocarbon content by 9.9% and API gravity by 3.02%. The GO-ZCFO, with its high catalytic activity, stands as a promising catalyst that contributes to improving the in-situ upgrading and thermal conversion of heavy crude oil.

摘要

由于常规石油资源的可采性不断下降,诸如重油等非常规资源正越来越多地被勘探和开发。重质原油因其高粘度、低API重度以及较高的硫和金属含量,在生产、运输和精炼方面都面临挑战。通过注蒸汽可以提高重油质量,因为注蒸汽能降低油的粘度并增强其流动性。然而,仅靠注蒸汽无法满足对更高质量石油产品日益增长的需求。因此,催化提质作为一种提高重油质量的可行解决方案正在被研究。本研究通过实验研究了两种新型催化剂在蒸汽注入过程中催化水热裂解反应的应用,这两种催化剂分别是通过溶胶 - 凝胶燃烧法合成的铜取代铁酸锌(ZCFO)以及不同比例的氧化石墨烯基纳米复合材料(GO - ZCFO),目的是加强重油的原位提质。这些催化剂通过X射线粉末衍射(XRD)、傅里叶变换红外光谱(FTIR)和透射电子显微镜(TEM)进行表征。利用高压/高温反应器(300毫升)评估它们的催化性能,并对提质前后重油的物理和化学性质变化进行全面分析。这种分析包括硫含量、SARA组分、粘度、API重度的测量以及饱和烃和逸出气体的气相色谱(GC)分析。所有提质实验,包括催化和非催化水热裂解过程,均在反应时间为6小时、反应温度为320℃和高压(86 - 112巴)的条件下进行。结果表明,将所提出的催化剂作为添加剂引入提质系统可显著降低硫含量。这进而导致树脂和沥青质含量降低,饱和烃含量增加,特别是低分子量烷烃,最终原油粘度降低且API重度升高。重量比为(50:50)的GO - ZCFO表现出最佳催化性能。用这种50:50比例提质的重质原油表现出显著改善,包括硫含量降低29.26%、树脂含量降低21.27%、沥青质含量降低37.60%、饱和烃含量增加46.92%、粘度降低66.48%以及API重度增加25.49%。相比之下,通过非催化水热裂解提质的油仅略有改善,硫含量略有降低5.41%、树脂含量降低3.60%、沥青质含量降低11.36%、粘度降低17.89%,饱和烃含量增加9.9%且API重度增加3.02%,增幅不大。具有高催化活性的GO - ZCFO是一种有前景的催化剂,有助于改善重质原油的原位提质和热转化。

https://cdn.ncbi.nlm.nih.gov/pmc/blobs/61e7/11519547/687acded57a5/41598_2024_73953_Fig1_HTML.jpg

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