Deposits of calcium sulfate scale on the surfaces of industrial equipment in distillation facilities, reverse osmosis desalination plants, in oil and gas industries lead to significant clogging of pipes and membranes and to a serious increase in production costs. For the mitigation of scale formation, the wide spectrum of antiscalants is applied. The present work is dedicated to the study of calcium sulfate deposition from supersaturated aqueous solutions in the presence of polyacrylic antiscalant with fluorescent marker (naphthalimide fragment) PAA-F1, which provides traceability of the scale inhibitor and a better understanding of its efficacy. A paradoxical phenomenon is being described here. Antiscalant causes a change in the crystal phase from bassanite to gypsum, significantly reduces the amount of deposit, but does not reveal the presence of its molecules either at the kink, step, or at selected edge sites of deposited crystals. Contrary to the predictions of the theory, it either stays in the aqueous phase, or forms its own separate phase Ca-PAA-F1. It is demonstrated that the antiscalant does not block the surfaces of calcium sulfate nuclei or crystal surfaces, but rather the foreign particles of nanodust with particle sizes around 1 nm, naturally occurring in any aqueous solution. As a result, the number of calcium nucleation sites is reduced, and the rate of scale formation decreases without any apparent antiscalant–scale interaction. On the grounds of the current experiment, the substoichiometric effect of scale inhibition obtained an alternative, quite stoichiometric explanation.

Equipment scaling leads to reduced production efficiency in a wide range of industrial applications worldwide. Various antiscaling agents are currently commonly used to mitigate this problem. However, irrespective of their long and successful application in water treatment technologies, little is known about the mechanisms of scale inhibition, particularly the localization of scale inhibitors on scale deposits. The lack of such knowledge is a limiting factor in the development of applications for antiscalants. Meanwhile, fluorescent fragments integrated into scale inhibitor molecules have provided a successful solution to the problem. The focus of this study is, therefore, on the synthesis and investigation of a novel fluorescent antiscalant: (2-(6-morpholino-1,3-dioxo-1H-benzo[de]isoquinolin-2(3H)yl)ethylazanediyl)bis(methylenephosphonic acid) (ADMP-F) which is an analog of the commercial antiscalant: aminotris(methylenephosphonic acid) (ATMP). ADMP-F has been found to effectively control the precipitation of CaCO3 and CaSO4 in solution and is a promising tracer for organophosphonate scale inhibitors. ADMP-F was compared with two other fluorescent antiscalants—polyacrylate (PAA-F1) and bisphosphonate (HEDP-F)—and was found to be highly effective: PAA-F1 > ADMP-F >> HEDP-F (CaCO3) and PAA-F1 > ADMP-F > HEDP-F (CaSO4·2H2O). The visualization of the antiscalants on the deposits provides unique information on their location and reveals differences in the “antiscalant-deposit” interactions for scale inhibitors of different natures. For these reasons, a number of important refinements to the mechanisms of scale inhibition are proposed.

Calcium carbonate scaling in reverse osmosis (RO) desalination process is studied in the presence of two novel fluorescent-tagged scale inhibitors 1,8-naphthalimide-tagged polyacrylate (PAA-F1) and 1-hydroxy-7-(6-methoxy-1,3-dioxo-1H-benzo[de]isoquinolin-2(3H)-yl)heptane-1,1-diyl-bis(phosphonic acid) (HEDP-F) by fluorescent microscopy (FM) and scanning electron microscopy (SEM). Both antiscalants diminished the mean size of calcite crystals relative to the blank experiment. The behavior and localization of HEDP-F and PAA-F1 during calcite scale formation on membrane surface was found to be significantly different from the distribution in similar RO experiments with gypsum, reported earlier. In the former case, both antiscalants are concentrated exactly on the surface of calcium carbonate crystals, while in the latter one they form their own phases (Ca-HEDP-F and Ca-PAA-F1) and are not detected on gypsum scale. The difference is interpreted in terms of interplay between background calcium concentration and sparingly soluble calcium salts’ solubility. HEDP-F reveals slightly higher efficiency than PAA-F1 against calcite scale formation, while PAA-F exhibits a higher ability to change calcite morphology. It is demonstrated that there is a lack of correlation between antiscaling efficacy and ability of antiscalant to change calcium carbonate morphology in a particular case study. An application of fluorescent-tagged antiscalants in RO experiments provides a unique possibility to track the scale inhibitor molecules’ localization during calcite scale formation. Fluorescent-tagged antiscalants are presumed to become a very powerful tool in membrane scaling inhibition studies.

Membrane scaling is a serious problem in electrodialysis. A widely used technique for controlling scale deposition in water treatment technologies is the application of antiscalants (AS). The present study reports on gypsum scale inhibition in electrodialysis cell by the two novel ASs: fluorescent-tagged bisphosphonate 1-hydroxy-7-(6-methoxy-1,3-dioxo-1Hbenzo[de]isoquinolin-2(3H)-yl)heptane-1,1-diyl-bis(phosphonic acid), HEDP-F and fluorescein-tagged polyacrylate, PAA-F2 (molecular mass 4000 Da) monitored by chronopotentiometry and fluorescent microscopy. It was found that cation-exchange membrane MK-40 scaling is sufficiently reduced by both ASs, used in 10−6 mol·dm−3 concentrations. PAA-F2 at these concentrations was found to be more efficient than HEDP-F. At the same time, PAA-F2 reveals gypsum crystals’ habit modification, while HEDP-F does not noticeably affect the crystal form of the deposit. The strong auto-luminescence of MK-40 hampers visualization of both PAA-F2 and HEDP-F on the membrane surface. Nevertheless, PAA-F2 is proved to localize partly on the surface of gypsum crystals as a molecular adsorption layer, and to change their crystal habit. Crystal surface coverage by PAA-F2 appears to be nonuniform. Alternatively, HEDP-F localizes on the surface of a deposit tentatively in the form of [Ca-HEDP-F]. The proposed mechanisms of action are formulated and discussed. The application of antiscalants in electrodialysis for membrane scaling mitigation is demonstrated to be very promising.