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    A novel perspective on emulsion stabilization in steam crackers

    Year: 2017

    Journal: Colloid Surf. A-Physicochem. Eng. Asp., Volume 516, nov-05, page 48–62

    Authors: Pensini, Erica; Vleugels, Leo; Frissen, Martijn; Wadhwa, Kuldeep; van Lier, Roy; Kwakkenbos, Gerard

    Organizations: SABIC; ACES

    Keywords: Steam crackers; Emulsions; Solubility fractions; Rigidity; Interfacial films; SEM/EDX

    Fouling issues in steam crackers may arise due to a number of reasons, including emulsion formation in the quench water tower. Freeze-drying according to a protocol developed in-house was used to extract species potentially capable of stabilizing emulsions from process water sampled from a quench tower. Such species were subsequently fractionated into solubility classes: water soluble, and soluble in organic solvents (polar and apolar). Liquid chromatography/mass spectrometry analyses indicated differences in the chemical composition of these fractions, with molecules bigger and richer in oxygen in the fraction soluble in polar organic solvents compared to those detected in the water soluble fraction. Bottle tests demonstrated that the interfacial material soluble in polar organic solvents was the most effective in stabilizing water-in-gasoline and gasoline-in-water emulsions. When the water soluble fraction was added to these stable emulsions it acted as demulsifier, with the most marked effects observed at low pH. In the absence of the water soluble fraction emulsion stability was largely pH-independent. The role of electrostatic forces in emulsion stabilization was investigated by conducting zeta potential measurements. With the organic soluble fraction only added to the oil phase and at pH 5.5, emulsions were stable and the zeta potential was close to zero, proving that electrostatic forces did not play a role in stabilizing this system. With the water soluble fraction added to the water phase and at alkaline pH, emulsions were stable and the zeta potential was negative, suggesting that electrostatic stabilization mechanisms cannot be discounted in the presence of the water soluble fraction. Scanning Electron Microscopy (SEM)/Energy Dispersive X-Ray Spectroscopy (EDX) were used to probe the morphology and elemental composition of the Langmuir-Blodgett films extracted from the gasoline-water interface. SEM images highlighted the presence of particles at the gasoline-water interface, suggesting Pickering stabilization mechanisms. Dynamic interfacial tension measurements showed that the decrease of the interfacial tension measured for gasoline-water interfaces upon addition of interfacial material was relatively low and similar for all fractions, supporting this hypothesis. SEM/EDX data further reveal the strong correlation between interfacial film composition and emulsion stability, with high densities of particles containing sulfur and iron associated with significant emulsion stability. The compressional visco-elastic moduli of interfacial films were determined using a pulsating drop rheometer. Measurements were done at pH 5.5 and 8.5, with the individual solubility fractions added. Film rigidity was similar with all fractions, indicating that it did not dictate the differences in their stabilizing properties. (C) 2016 Elsevier B.V. All rights reserved.
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