Dual Nucleation and Growth Inhibitors of Mineral Scale

This present disclosure aims to describe a class of organic compounds with properties that are amenable to their use as inhibitors of mineral scale such as barite, calcite, and gypsum, among others. Crystallization of mineral scale components ubiquitously plagues industrial systems for water treatment, energy production, and manufacturing. Phosphate-based scale inhibitors such as diethylenetriamine penta(methylene phosphonic acid) (DETPMP) are often employed to control mineral scale formation. Despite its high potency, the environmental drawbacks prompt scientific and industrial communities to pursue high performance low-cost and eco-friendly chemicals to address scale formation. Among a wide diversity of organic compounds, polyprotic acids, especially alcohol-substituted carboxylates such as sodium citrate, have garnered tremendous attention. Citrate is one example of a key ingredient that is commonly blended with chelating agents and surfactants as formulations to address pipeline scale problems. The use of citrate as a scale inhibitor has been demonstrated for CaCO3 and CaSO4. For less soluble minerals, such as BaSO4 (barite), the efficacy of citrate is often limited due to its moderate interactions with barite crystal surfaces. This has motivated research into alternative molecules that function as crystallization inhibitors (resulting from modifier-crystal interactions) and/or sequestering agents that have a binding affinity for free Ba2+ cations. Herein, we report two new molecules, hydroxycitrate (HCA) and isocitrate (ICA), as examples of molecules possessing multiple carboxylates and multiple hydroxyl groups to facilitate their interactions with mineral surfaces and free cations in solution. Unique properties of HCA and ICA are their ability to inhibit both nucleation and growth of crystals. We also identified a unique mechanism for HCA surface inhibition whereby an appreciable concentration of HCA leads to the formation of a surface layer that blocks growth and prevents facile regrowth in the absence of the inhibitor. The efficacy of these molecules were evaluated by a combination of techniques that included bulk crystallization assays, kinetic studies of crystal growth (i.e. conductivity measurements and microfluidic assays), and atomic force microscopy to measure surface growth in real time. Collectively, these measurements reveal that HCA and ICA reduce the number of nuclei with increasing inhibitor concentrations, leading to the complete suppression of crystallization at threshold concentrations. Studies of crystal growth in the presence of HCA and ICA also reveal that the rate of growth is suppressed in the presence of both inhibitors. To mimic conditions of scale formation under flow, we used a microfluidic platform composed of gradient generator and multiple observation channels to collect time-resolved data of crystal growth in the presence of HCA and ICA. Our findings reveal the ability of growth inhibitors to suppress the advancement of facets, leading to complete arrest of growth at sufficient inhibitor concentrations. Few inhibitors have the ability to suppress nucleation. To gain more insight into this process, we used oblique illumination microscopy (OLM) to directly capture the process of cluster (or aggregate) formation, which often leads to the generation of nuclei. In a typical nucleation scenario, large amount of precipitates were observed within 5 min in the absence of inhibitors. In the presence of inhibitors (e.g. HCA and ICA), only a few clusters (with sizes 15 – 50 nm) were observed, indicating the ability of inhibitors to block the formation of clusters and nuclei. Analysis of in situ AFM measurements reveal a unique mode of action for HCA. It is well established that conventional molecular inhibitors tend to adsorb onto the active sites, e.g. kinks and steps of the crystal surface, to constrain the step movement as well as block the surface diffusion of the solute molecules. The introduction of growth solution containing HCA favors the rapid formation of islands on the (001) basal surface, thereby resulting a highly roughened interface. This process results in the deceleration of crystal growth and the complete arresting of layers. The newly formed rough layer consists of a large number of defects (potentially amorphous deposits) that frustrate the attachment of solutes, thereby hindering the growth of barite surfaces. Attempts to regenerate growth by the addition of supersaturated solutions in the absence of HCA were unsuccessful, indicating an irreversible inhibition of growth that is not commonly observed in reported examples of crystal growth inhibitors. From a manufacturing standpoint, HCA can be easily extracted from the natural plant such as garcinia cambogia which ensures its commercial viability as a potential antiscalant. Lastly, HCA has been suggested as one of the important ingredients of the over-the-counter supplements for weight control. This implies that the use and disposal of HCA-based chemicals will not cause hazardous consequence to the environment and human body which is beneficial for the development and marketing of HCA relevant products.

App TypeCase No.CountryPatent/Publication No.
InquireNon Provisional2019-059United States12,024,452