Synthesis and properties of novel fluorescent‐tagged polyacrylate‐based scale inhibitors

Popov, Konstantin; Oshchepkov, Maxim; Kamagurov, Semen; Tkachenko, Sergey; Dikareva, Julia; Rudakova, Galina

doi:10.1002/app.45017

Cited by 35 publications

(43 citation statements)

References 31 publications

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“…PAA-F1 has definitely proved itself as an effective antiscalant in gypsum brine RO desalination, Figure 6. This was also confirmed earlier by the static experiment tests [36]. However, the visualization of PAA-F1 molecules indicates clearly that there is no definite interaction between antiscalant and gypsum along the brine RO treatment.…”

Section: Tentative Mechanism Of Gypsum Membrane Fouling Inhibition Bysupporting

confidence: 85%

“…Normally, the method sensitivity corresponds to the ppb level for both solid and liquid samples. For example, the detection limit of Rhodamine is in the range of 0.01 ppb in distilled water (25 mm cuvette) [35], and fluorescence quantum yield of our fluorescent inhibitor is quite close to Rhodamine [35,36]. Thus, localization of fluorescent inhibitor upon crystals/particles of scale is a valid approach.…”

Section: Tentative Mechanism Of Gypsum Membrane Fouling Inhibition Bymentioning

confidence: 78%

“…Antiscalant PAA-F1 ( Figure 1) was synthesized by our group as described elsewhere [36] along with its scale inhibition efficiency against gypsum scaling and its fluorescent properties. It has the mean molecular mass 4000 Da with c.a.…”

Section: Reagents Membrane Materials and Model Solutionsmentioning

confidence: 99%

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Gypsum Crystallization during Reverse Osmosis Desalination of Water with High Sulfate Content in Presence of a Novel Fluorescent-Tagged Polyacrylate

et al. 2020

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Gypsum scaling in reverse osmosis (RO) desalination process is studied in presence of a novel fluorescent 1,8-naphthalimide-tagged polyacrylate (PAA-F1) by fluorescent microscopy, scanning electron microscopy (SEM), dynamic light scattering (DLS) and a particle counter technique. A comparison of PAA-F1 with a previously reported fluorescent bisphosphonate HEDP-F revealed a better PAA-F1 efficacy, and a similar behavior of polyacrylate and bisphosphonate inhibitors under the same RO experimental conditions. Despite expectations, PAA-F1 does not interact with gypsum. For both reagents, it is found that scaling takes place in the bulk retentate phase via heterogeneous nucleation step. The background "nanodust" plays a key role as a gypsum nucleation center. Contrary to popular belief, an antiscalant interacts with "nanodust" particles, isolating them from calcium and sulfate ions sorption. Therefore, the number of gypsum nucleation centers is reduced, and in turn, the overall scaling rate is diminished. It is also shown that, the scale formation scenario changes from the bulk medium, in the beginning, to the sediment crystals growth on the membrane surface, at the end of the desalination process. It is demonstrated that the fluorescent-tagged antiscalants may become very powerful tools in membrane scaling inhibition studies.However, in spite of numerous relevant studies, some controversy regarding both the dominant scaling mechanism in particular situations and the mechanism of antiscalant activity still exists [12][13][14][15][16][17][18]. Recent reviews on scale formation control in RO technologies [6,19] mention two main hypothetic mechanisms of inhibition: (i) antiscalant molecules adsorb on the active growth sites at the crystal surface of sparingly soluble inorganic salt and retard nucleation and crystal growth by distorting its crystal structure; (ii) antiscalant molecules provide similar electrostatic charge, and thus, repulsion between particles prevents them from agglomeration.Nevertheless, our recent static [20,21] and RO [22] experiments operating gypsum as a model scale in presence of a novel fluorescent-tagged bisphosphonate antiscalant 1-hydroxy-7-(6-methoxy-1,3dioxo-1H-benzo[de]isoquinolin-2(3H)-yl)heptane-1,1-diyl-bis(phosphonic acid), HEDP-F (H 4 hedp-F) revealed a paradoxical effect: an antiscalant does not interact with gypsum at all, but provides nevertheless retardation of corresponding deposit formation. According to the classical crystallization theory [23], this is possible only in the case, when gypsum passes bulk heterogeneous nucleation, and exactly the "nanodust" plays the role of the solid phase template. Indeed, it is demonstrated that HEDP-F molecules being immersed into the stock solution (undersaturated against gypsum) occupy a significant part of "nanodust" crystallization centers and form there their own solid phase Ca 2 hedp-F·nH 2 O. However, polyacrylates are much less sensitive to calcium environment than phosphonates [20,21]. In this way, it was reasonable to study the trace...

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Section: Tentative Mechanism Of Gypsum Membrane Fouling Inhibition Bysupporting

confidence: 85%

Section: Tentative Mechanism Of Gypsum Membrane Fouling Inhibition Bymentioning

confidence: 78%

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Gypsum Crystallization during Reverse Osmosis Desalination of Water with High Sulfate Content in Presence of a Novel Fluorescent-Tagged Polyacrylate

et al. 2020

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“…HEDP‐F was tested for fluorescent activity and gypsum scale inhibition efficacy, following the National Association of Corrosion Engineers (NACE) Standard TM0374‐2007 . HEDP‐F is found to have emission and excitation spectra quite similar to those obtained for polyacrylate‐tagged 1,8‐naphtalimide (PAA‐F1),, Table , while its antiscaling efficacy relative to gypsum deposition was very close to that one of HEDP, Table .…”

Section: Methodsmentioning

confidence: 54%

Insight into the Mechanisms of Scale Inhibition: A Case Study of a Task‐Specific Fluorescent‐Tagged Scale Inhibitor Location on Gypsum Crystals

Oshchepkov

Kamagurov²,

Tkachenko

et al. 2019

ChemNanoMat

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Scaling in reverse osmosis facilities, boilers, heat exchangers, evaporation plants, and oilfield applications is a serious problem worldwide. In order to provide a new insight into the mechanism of the scale formation and inhibition, a novel fluorescent‐tagged bisphosphonate scale inhibitor 1‐hydroxy‐7‐(6‐methoxy‐1,3‐dioxo‐1H‐benzo[de]isoquinolin‐2(3H)‐yl)heptane‐1,1‐diyl‐di(phosphonic acid), (HEDP−F) was synthesized and used for fluorescent microscope visualization of gypsum crystal formation in supersaturated aqueous solutions. The visualization of HEDP−F location on gypsum crystals has demonstrated that the bisphosphonate molecules do not act as they are expected to do according to the current scale inhibition theory. At ambient temperature the gypsum macrocrystals are found to form, and then to grow without visible sorption of bisphosphonate on the crystal edges or any other gypsum crystal growth centers. A tentative nonconventional mechanism of scale inhibition in the bulk supersaturated aqueous solutions of gypsum is proposed.

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“…The first one belongs to the phosphonate group: 1-hydroxy-7-(6-methoxy-1,3-dioxo-1H-benzo[de]isoquinolin-2(3H)-yl)heptane-1,1-diyldi(phos-phonic acid), HEDP-F [19], while the second one represents a co-polymer of N-allyl-4-methoxy-1,8-naphtalimide with acrylic acid, PAA-F1 [20]. The barite scale formation process was monitored by fluorescence microscopy, scanning electron microscopy (SEM), light scattering technique (dynamic light scattering, DLS; Tyndall's effect, particle counter measurements) and turbidity measurements.…”

Section: Introductionmentioning

confidence: 99%

Barite crystallization in presence of novel fluorescent-tagged antiscalants

2019

Int. J. Corros. Scale Inhib.

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Formation of barite crystals in a bulk supersaturated aqueous solution at ambient temperature is studied in presence of two novel fluorescent-tagged antiscalants: a bisphosphonate 1-hydroxy-7-(6-methoxy-1,3-dioxo-1H-benzo[de]isoquinolin-2(3H)-yl)heptane-1,1-diyldi-(phosphonic acid), HEDP-F, and a co-polymer of N-allyl-4-methoxy-1,8-naphtalimide with acrylic acid, PAA-F1 by fluorescent microscopy, scanning electron microscopy (SEM), turbidimetry, dynamic light scattering (DLS) and a particle counter technique. Both scale inhibitors at a 20 mg·dm -3 dosage are found to be effective in supersaturated BaSO 4 solutions with saturation index (SI) 10 at 25°C (0.001 mol·dm -3 ). Herewith PAA-F1 reveals a higher efficacy than HEDP-F. At the same time a dramatic impact of foreign background "nanodust" particles on antiscalant efficacy is detected and interpreted in terms of barite nucleation. It is demonstrated, that barite nucleation takes place exclusively on "nanodust" particles as a bulk heterogeneous process. Thus an antiscalant molecule acts not so much as barite nuclei surface modifiers, but as the modifiers of "nanodust" particles. It is shown that inter alia the lower efficacy of HEDP-F relative to PAA-F1 is associated with insoluble barium salts formation by the former reagent (tentatively by Ba 2 HEDP-F·nH 2 O or BaH 2 HEDP-F·mH 2 O). Thus an efficacy evaluation may be strongly affected by the way of antiscalant introduction into the system. Being initially added to the barium brine both antisclants demonstrate greater difference in barite scale inhibition, than in the case of the sulfate brine. Both fluorescent-tagged reagents reveal perfectly an antiscalant location on barite crystals. Despite expectations they cover BaSO 4 crystal surface uniformly, and indicate no special concentration of antiscalant on crystal's kinks, edges etc. Thus the scale inhibitors affect rather the primary nucleation step of barite solid phase formation than the secondary one (macro-crystal growth phase).

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Synthesis and properties of novel fluorescent‐tagged polyacrylate‐based scale inhibitors

Cited by 35 publications

References 31 publications

Gypsum Crystallization during Reverse Osmosis Desalination of Water with High Sulfate Content in Presence of a Novel Fluorescent-Tagged Polyacrylate

Gypsum Crystallization during Reverse Osmosis Desalination of Water with High Sulfate Content in Presence of a Novel Fluorescent-Tagged Polyacrylate

Insight into the Mechanisms of Scale Inhibition: A Case Study of a Task‐Specific Fluorescent‐Tagged Scale Inhibitor Location on Gypsum Crystals

Barite crystallization in presence of novel fluorescent-tagged antiscalants

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