Babaei Elahe, Bazyari Amin, Shojaei Behzad, Thompson Levi T
Catalysis and Nanomaterials Research Laboratory, School of Chemical, Petroleum, and Gas Engineering, Iran University of Science and Technology, P.O. Box 16765-163, Tehran, Iran.
Department of Chemical and Biomolecular Engineering, University of Delaware, Newark, DE, 19717, USA.
Sci Rep. 2025 Apr 13;15(1):12729. doi: 10.1038/s41598-025-95667-7.
Asphaltenes, complex molecules in crude oil, cause significant challenges in oil production and refining due to their tendency to form agglomerates and precipitate. This study investigates the effectiveness of preparation method of metal oxide-based adsorbents (NiO and FeO) in removing asphaltenes. Nanostructured NiO and FeO xerogels and aerogels were produced through the Pechini-type and epoxide-derived sol - gel methods and employed for the adsorption of Ap1, a specific asphaltene extracted from Iranian crude oil. The nanomaterials were characterized by XRD, N adsorption-desorption, FE-SEM, EDS, and FT-IR. The influence of synthesis parameters, including citric acid to metal precursor molar ratio, type of adsorbent, textural characteristics, adsorption temperature, sol-gel protocols, calcination temperatures, and drying conditions, on the adsorbent performance was systematically studied. The NiO(X-300) xerogel synthesized by the epoxide-derived sol - gel with calcination at 300 °C exhibited the highest asphaltene adsorption capacity (q = 558 mg/g) among all xerogels tested. This capacity was 102% and 87% higher than those achieved on optimized reference NiO(P-600) (q = 276 mg/g) and FeO(P-600) (q = 298 mg/g) adsorbents prepared by the Pechini-type method, respectively. The textural properties of both NiO and FeO materials were improved upon supercritical CO drying of the epoxide-derived gels, leading to the nanostructured NiO(A-300) (q = 699 mg/g) aerogel with significantly higher (~ 135%) asphaltene adsorption capacity than FeO(P-600). For the best aerogels, NiO(A-300) and FeO(A-450), the adsorption isotherms and the kinetic data were best fitted by the Jovanovic and the Elovich models, respectively. Ap1 exhibited rapid adsorption onto NiO(A-300) and NiO(X-300), achieving equilibrium within 20 min. The adsorption process was demonstrably spontaneous and exothermic.
沥青质是原油中的复杂分子，由于其易于形成团聚体和沉淀，给石油生产和精炼带来了重大挑战。本研究考察了金属氧化物基吸附剂（NiO和FeO）的制备方法对去除沥青质的有效性。通过佩琴尼型和环氧化物衍生的溶胶-凝胶法制备了纳米结构的NiO和FeO干凝胶和气凝胶，并用于吸附从伊朗原油中提取的一种特定沥青质Ap1。通过XRD、N吸附-脱附、FE-SEM、EDS和FT-IR对纳米材料进行了表征。系统研究了合成参数，包括柠檬酸与金属前驱体的摩尔比、吸附剂类型、织构特性、吸附温度、溶胶-凝胶方案、煅烧温度和干燥条件对吸附剂性能的影响。通过环氧化物衍生的溶胶-凝胶法在300℃煅烧合成的NiO(X-300)干凝胶在所有测试的干凝胶中表现出最高的沥青质吸附容量最高（q = 558 mg/g）。该容量分别比通过佩琴尼型方法制备的优化参考NiO(P-600)（q = 276 mg/g）和FeO(P-600)（q = 298 mg/g）吸附剂高102%和87%。环氧化物衍生凝胶的超临界CO2干燥改善了NiO和FeO材料的织构性能，得到了纳米结构的NiO(A-300)（q = 699 mg/g）气凝胶，其沥青质吸附容量比FeO(P-600)高约135%。对于最佳气凝胶NiO(A-300)和FeO(A-450)，吸附等温线和动力学数据分别最符合约万诺维奇模型和埃洛维奇模型。Ap1在NiO(A-300)和NiO(X-300)上表现出快速吸附，在20分钟内达到平衡。吸附过程明显是自发的且放热的。
