Conversion of petroleum coke into valuable products using oxy-cracking technique

• Published in: Fuel (Guildford) 2018-03, Vol.215, p.865-878
• Main Authors: Manasrah, Abdallah D., Nassar, Nashaat N., Ortega, Lante Carbognani
• Format: Article
• Language: English
• Subjects: Carbonyls; Catalytic cracking; Coke; Coking; Conversion; Cracking; Decomposition reactions; Demineralization; Demineralizing; Gasification; Intermediates; Kinetics; Metals; NMR; Nuclear magnetic resonance; Operating temperature; Oxidation; Oxy-cracking; Petroleum; Petroleum coke; Petroleum residues; Phenolic compounds; Phenols; Pressure; Reaction kinetics; Reaction time; Refineries; Selectivity; Solubility; Temperature effects; Vacuum; X ray photoelectron spectroscopy
• ISSN: 0016-2361; 1873-7153
• DOI: 10.1016/j.fuel.2017.11.103

[Display omitted] •Oxy-cracking process is conducted as an alternative approach to petcoke utilization.•The process was optimized for high conversion, selectively and small amount of CO2.•The petcoke oxidation undergoes in parallel consecutive reactions.•The oxy-cracked petcoke was found to be carboxylic and phenolic acids and their salt.•The oxy-cracking technique could be employed for petcoke demineralization. The global production of residual feedstock has reached 150 million metric tons per annum and is expected to increase in the future due to the progressively increasing heavier nature of the crudes. Petroleum coke (petcoke), one of these residues, is a solid-rich carbon typically produced during the upgrading of heavy oil and delay coking of vacuum residue in the refinery. Finding an alternative technique to treat this massive amount of petcoke is highly needed as the conventional processes like gasification and combustion have limitations in terms of efficiency and environmental friendliness. In this study, an oxy-cracking technique, which is a combination of cracking and oxidation reactions, is conducted as an alternative approach for petcoke utilization. The reaction is conducted in a Parr reactor where petcoke particles are solubilized in an aqueous alkaline medium and partially oxidized under mild operating temperature and pressure. Several operating conditions on petcoke oxy-cracking were investigated, such as temperature, oxygen pressure, reaction time, particle size and mixing rate to optimize the solubility and selectivity of oxy-cracked products. The results showed that the temperature and the residence time are the two major important parameters that affect the reaction conversion and selectivity. This enabled us to propose a reaction pathway based on the radical mechanism to describe the kinetic behavior of petcoke. Reaction kinetics indicated that petcoke oxidation undergoes a parallel-consecutive reaction in which an oxidative decomposition took place in the first step producing different oxidized intermediates. The oxy-cracked petcoke was characterized by FTIR, XPS and NMR analyses. The oxy-cracked products were found to contain carboxylic, carbonyl, phenolic, and sulfonic functions. Moreover, the elemental analysis showed that most of the metals remained in the residue, suggesting that the proposed technique could be employed for petcoke demineralization.