Enhanced Hydrophobicity and Oleophilicity of Modified Activated Carbons Derived from Agro-Wastes Biomass for the Removal of Crude Oil from Aqueous Medium

Abstract

Crude oil spillage has tremendous environmental impacts and poses severe pollution problems worldwide due to the continuous activities and operations in the oil and gas sector. This has resulted in the urgent need for clean-up techniques such as the use of natural adsorbents which is considered a relatively low-cost, readily-available, efficient, eco-friendly, and easy-to-deploy mode of addressing oil spillage due to its high oil sorption capacity/efficiency, high oil selectivity, oleophilic, enduring, reusability and biodegradable properties. Empty palm fruit bunch and coconut coir were used as precursors to produce activated carbons for oil spill remediation. The influence of varying parameters was investigated using a batch experimental procedure resulting in the crude oil adsorption capacity increasing with a corresponding increase in contact time, initial oil concentration, temperature, agitation speed, and particle size but decreasing in adsorbent dosage. The combination of surface morphological modification and hydrophobicity enhancement resulted in significantly improved adsorption capacity for crude oil removal (2710.0 mg/g and 4859.5 mg/g for EPFBAC<SUB>LA</SUB> and CCAC<SUB>L.A</SUB> respectively), as evidenced by both FTIR and SEM analyses. The experimental isotherm data were analysed using various isotherm models and the best-fitted isotherm model was the Freundlich model with a correlation coefficient (R<sup>2 </sup>= 0.991 and R<sup>2 </sup>= 0.999) for EPFB<SUB>L.A</SUB> and CCAC<SUB>L.A</SUB> respectively. The kinetic behaviour of the adsorption process was best described by pseudo-second order with R<sup>2</sup> values of 0.970 and 0.999 for EPFBAC<SUB>LA</SUB> and CCAC<SUB>L.A</SUB> respectively while Boyd model revealed that the adsorption was controlled by an internal transport mechanism and film diffusion was the rate-limiting step. The crude oil adsorption was chemisorption and endothermic owing to the positive enthalpy values (ΔH<sup>o</sup> = 183.890 KJ/mol for EPFBAC<SUB>L.A </SUB>and ΔH<sup>o</sup> = 69.656 KJ/mol for CCAC<SUB>L.A</SUB>), the positive value of entropy suggested that the adsorption process was accompanied by an increase in the degree of randomness or disorder at the interface between the adsorbent and the adsorbate. A temperature rise led to a decline in Gibbs energy (ΔG<sup>o</sup>), suggesting that adsorption became more feasible and spontaneous at higher temperatures and the significant activation energies indicated the existence of a substantial energy barrier that must be overcome to initiate the reaction. The results showed the significant capability of the prepared adsorbents to be used as a low-cost, re-generable and eco-friendly adsorbent in oil spill clean-up and is recommended to exploit its usage on a large scale.