Bioremediation of real-time petroleum refining industry oily waste (PRIOW) is a major challenge due to the poor emulsification potential and oil sludge disintegration efficiency of conventional bioamphiphile molecules. The present study was focused on the design of a covalently engineered supramolecular bioamphiphile complex (SUBC) rich in hydrophobic amino acids for proficient emulsification of hydrocarbons followed by the concomitant degradation of total petroleum hydrocarbons (TPH) in PRIOW using the hydrocarbonoclastic microbial bio-formulation system. The synthesis of SUBC was carried out by pH regulated microbial biosynthesis process and the yield was obtained to be 450.8 mg/g of petroleum oil sludge. The FT-IR and XPS analyses of SUBC revealed the anchoring of hydrophilic moieties of monomeric bioamphiphilic molecules, resulting in the formation of SUBC via covalent interaction. The SUBC was found to be lipoprotein in nature. The maximum loading capacity of SUBC onto surface modified rice hull (SMRH) was achieved to be 45.25 mg/g SMRH at the optimized conditions using RSM-CCD design. The SUBC anchored SMRH was confirmed using SEM, FT-IR, XRD and TGA analyses. The adsorption isotherm models of SUBC onto SMRH were performed. The integrated approach of SUBC-SMRH and hydrocarbonoclastic microbial bio-formulation system, emulsified oil from PRIOW by 92.86 ± 2.26% within 24 h and degraded TPH by 89.25 ± 1.75% within 4 days at the optimum dosage ratio of SUBC-SMRH (0.25 g): PRIOW (1 g): mass of microbial-assisted biocarrier material (0.05 g). The TPH degradation was confirmed by SARA fractional analysis, FT-IR, ¹H NMR and GC-MS analyses. The study suggested that the application of covalently engineered SUBC has resulted in the accelerated degradation of real-time PRIOW in a very short duration without any secondary sludge generation. Thus, the SUBC integrated approach can be considered to effectively manage the hydrocarbon contaminants from petroleum refining industries under optimal conditions.

Industrialization and the rise in population have led to the larger utilization of resources which has become the supreme risk for the environment. Different types of pollutants enter the aquatic environment from various sources which create a threat for the aquatic organisms and humans. Many separation techniques like precipitation, adsorption, reactive distillation, ion exchange, electro dialysis, solvent extraction, and ultrafiltration are available, but these techniques have various limitations like the use of excessive and expensive chemicals, high energy requirement, sludge formation, requirement of utilities in large amount and so. The green emulsion liquid membrane (GELM) is an emerging and promising method that incorporates the traits of ELM for the removal of various pollutants, metal ions, acids, and so on. In the present scenario, much focus has been diverted towards the use of green solvents derived from vegetable and plant origin. These solvents are environmentally friendly and economically viable making the ELM process more reliable. The traditionally used petroleum-based solvents for ELM formation are expensive, toxic, volatile in nature, and are detrimental to the environment. The present study tries to address the recent advancement in the field of GELM. The different factors like concentration of surfactant, carrier, types of diluents, effect of volume ratio of external feed phase to emulsion, agitation speed, effect of internal aqueous phase concentration, and emulsification time play a substantial role in the removal of several pollutants from the aqueous streams through GELM have been discussed in detail. The statistical analysis of the operating variables as executed by different investigators is also mentioned.