Sulphur retention and in-situ preparation of metal sulphide catalysts during activation of petroleum coke

Ye Xiao; Vicente Montes; Josephine M Hill

doi:10.1016/j.chemosphere.2022.136340

Sulphur retention and in-situ preparation of metal sulphide catalysts during activation of petroleum coke

Chemosphere. 2022 Dec;308(Pt 2):136340. doi: 10.1016/j.chemosphere.2022.136340. Epub 2022 Sep 7.

Authors

Ye Xiao¹, Vicente Montes², Josephine M Hill³

Affiliations

¹ Department of Chemical and Petroleum Engineering, Schulich School of Engineering, University of Calgary, 2500 University Drive NW, Calgary, Alberta, T2N 1N4, Canada; School of Environmental Science and Engineering, Sun Yat-Sen University, Guangzhou, 510006, China. Electronic address: xiaoy299@mail.sysu.edu.cn.
² Department of Chemical and Petroleum Engineering, Schulich School of Engineering, University of Calgary, 2500 University Drive NW, Calgary, Alberta, T2N 1N4, Canada; Department of Chemical Engineering and Physis Chemistry, University Institute of Research in Water, Climate Change and Sustainability (IACYS), University of Extremadura, Badajoz, Spain. Electronic address: vmontes@unex.es.
³ Department of Chemical and Petroleum Engineering, Schulich School of Engineering, University of Calgary, 2500 University Drive NW, Calgary, Alberta, T2N 1N4, Canada. Electronic address: jhill@ucalgary.ca.

PMID: 36087736
DOI: 10.1016/j.chemosphere.2022.136340

Abstract

Petroleum coke (petcoke) containing sulphur has limited direct applications, but stockpiling the material creates an environmental issue. Although chemical activation can be used to valorise the petcoke to activated carbon, sulphur is released creating alternative environmental problems. In this study, a new activation method for high sulphur content (∼6.5 wt%) petcoke was developed to retain sulphur and prepare transition metal sulphide catalysts simultaneously. Petcoke was mixed with tungsten and nickel precursors and then activated by KOH at 600 °C in the presence of steam. After washing, the activated petcoke had a sulphur content of 5.1 wt%, which was much higher than that in the absence of steam during activation (0.4 wt%). Sulphur was also retained (>4 wt% of sulphur) when other transition metals including molybdenum and cobalt were used. Characterization by XRD, XPS, and SEM-EDS suggested that sulphur was retained on the activated petcoke in the form of metal sulphides. Further thermodynamic analysis of the system revealed that in the presence of steam an H₂S/H₂ mixture was generated, and this mixture promoted the formation of the metal sulphide species when metal precursors were introduced. The prepared metal sulphide catalysts were active for several reactions including the photoreduction of CO₂. Overall, this study provided an effective method to prepare metal sulphide catalysts from sulphur containing carbonaceous waste.

Keywords: Activation; Metal sulphide catalyst; Petroleum coke; Sulphur; Thermodynamic analysis.