Elucidating morphological effects in membrane mineral fouling using real-time particle imaging and impedance spectroscopy

Mineral fouling is a major hindrance to high recovery effluent nanofiltration, with calcium phosphate (Ca-P) and calcium carbonate (CaCO3) the most prevalent mineral foulants. In this study, we used a novel combination of real-time in-line microscopy, electrical impedance spectroscopy (EIS), post SEM analysis, and filtration metrics (water flux and rejection) to study mineral fouling mechanisms of Ca-P and CaCO3 salts in synthetic effluent nanofiltration. We used nanofiltration (NF) polyelectrolyte multilayer (PEM) membranes, prepared by static layer-by-layer (LbL) coating of a cationic polymer - polydiallyl dimethylammonium chloride, and anionic polymer - poly styrenesulfonate (six bi-layer) on a polyethersulfone (PES) ultrafiltration (UF) membrane. Increasing permeate recovery over filtration time was simulated through additions of CaCl2 with NaHCO3 or NaH2PO4/Na2HPO4. Using the novel combination of methods, we delineated the mechanisms governing fouling development with time for both CaCO3 and Ca-P. For CaCO3, a transition from heterogeneous precipitation on the membrane surface (scaling) to particulate fouling due to bulk precipitation was identified. For Ca-P, a transition from fouling by amorphous particles to fouling by crystalline particles was identified; and this phase-change was captured in real-time images using an in-line microscope. We also found that for similar precipitation potentials measured by weight, Ca-P fouling was more detrimental to water flux (86% decrease) compared to CaCO3 (20% decrease) due to the voluminous amorphous phase. We established in-line microscopy as a new useful method to study mineral fouling, as it gives invaluable information on the suspended particles in real-time. Combining it with EIS gives complementary information on mineral accumulation on the membrane surface. Insight from this study and further use of these methods can guide future strategies towards higher effluent recovery by membrane filtration.

Fouling and fouling mitigation of calcium compounds on heat exchangers by novel colloids and surface modifications

Fouling is the accumulation of unwanted materials on surfaces that causes detrimental effects on its function. The accumulated materials can be composed of living organisms (biofouling), nonliving substances (inorganic and/or organic), or a combination of both of them. Mineral fouling occurs when a process uses cooling water supersaturated with mineral salt crystals (i.e. hard water). Precipitation ensues on heat transfer surfaces whenever the inversely soluble dissolved calcium salt ions are exposed to high temperature. Mineral salts, dirt, waxes, biofilms, whey proteins, etc. are common deposits on the heat exchanger surfaces, and they create thermal resistance and increase pressure drop and maintenance costs of plants. Fouling of dissolved salts and its mitigation have been studied in detail by varying process parameters, surface materials, coatings on surfaces, additives, etc. by many researchers. In the present stage, researchers have considered polymeric additives, environmental friendly nanoparticles, natural fibers, and thermal conductive coatings (metallic and polymeric) in the study of mitigation of fouling. A better understanding of the problem and the mechanisms that lead to the accumulation of deposits on surfaces will provide opportunities to reduce or even eliminate the problem in certain situations. The present review study has focused on fouling phenomena, environment of fouling, heat exchanger fouling in design, and mitigation of fouling. The findings could support in developing the improved heat exchanger material surfaces, retain efficiency of the heat exchangers, and prolong their continuous operation.