Searching for a universal scale inhibitor: A multi-scale approach towards inhibitor efficiency

Spinthaki, Argyro; Kamaratou, Michaela; Skordalou, Georgia; Petratos, George; Petrou, Irena; Tramaux, Axel; David, Ghislain; Demadis, Konstantinos D.

doi:10.1016/j.geothermics.2020.101954

Cited by 28 publications

(10 citation statements)

References 76 publications

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“…The solution turbidity provides a useful quantitative tool that can be used to evaluate the calcium tolerance of SIs. It has been also used successfully for mineral scale dispersion approaches to control scale deposition. , Our experiments revealed that short-alkyl chain-length aminoalkylphosphonate inhibitors (C1-D, C2-D, C3-D, C4-D, and C6-D) at low doses (100 and 1000 ppm) showed no turbidity due to the high solubility of the Ca–SI “complexes” formed. When high doses (10,000 and 50,000 ppm) of the SIs were used, medium to high turbidity values were observed due to dispersed Ca–SI “complexes”.…”

Section: Resultsmentioning

confidence: 83%

Systematic Molecular-Size Variants in Diphosphonate Inhibitors for Oilfield Scale Management

et al. 2023

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Organophosphorus-based scale inhibitors (SIs) have been widely used in the petroleum industry for several decades. Among them, aminomethylenephosphonates (possessing at least one −NH+–CH2–PO3H– moiety) have shown outstanding inhibition efficiency against carbonate and sulfate oilfield scales. However, one of the main drawbacks of aminomethylenephosphonate-based SIs with multiple phosphonate (−PO3H2) groups is their poor tolerance against high-calcium brines. In this work, the calcium tolerance of aminomethylenephosphonates was improved by reducing the number phosphonate groups in the inhibitor backbone to less than three and introducing a variable-length non-polar alkyl side chain while maintaining acceptable inhibitory efficiency levels. Hence, we synthesized a series of variable-length alkyl chain-based amino-di(methylenphosphonate) [(H2O3P–CH2)2–N–(X)] inhibitors, (X = methyl, ethyl, propyl, butyl, hexyl, octyl, and dodecyl). In addition, we also studied the role of the alkyl side-chain length in the diphosphonate structure backbone on the scale inhibitory activity. All newly synthesized aminomethylenediphosphonates were evaluated as SIs for calcium carbonate (calcite) and barium sulfate (barite) in brines based on the Heidrun oilfield using a high-pressure dynamic tube blocking rig at 100 °C and 80 bar. Furthermore, we investigated the calcium compatibility of all aminomethylenediphosphonate SIs at several levels of calcium stresses. The new aminoalkyldiphosphonate inhibitors possessing shorter alkyl chain lengths (X = methyl, ethyl, propyl, butyl, and hexyl) gave better calcite scale inhibition performance and outstanding calcium compatibility of up to 1000 ppm of Ca2+ compared to the commercial benchmark ATMP SI [amino-tris(methylenephosphonate)] and longer alkyl-chain diphosphonates, that is, octylamine-N,N-di(methylenephosphonate) (ODMP, C8-D) and dodecylamine-N,N-di(methylenephosphonate) (DDMP, C12-D). Moreover, we tested the thermal stability (at 130 °C for one week) of the best-performing additive (based on calcite inhibition and calcium tolerance performances), and it was found that methylamine-N,N-dimethylenephosphonate (MDMP, C1-D) was thermally stable under these harsh conditions without any loss of its inhibition performance. The Ca-C8-D “complex” was deliberately synthesized and structurally characterized. It appears that the major factor for its poor Ca tolerance is the tight packing of the octyl side-chain groups.

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Section: Resultsmentioning

confidence: 83%

Systematic Molecular-Size Variants in Diphosphonate Inhibitors for Oilfield Scale Management

et al. 2023

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“…With biodegradability and other advanced properties, they have been widely used in the petroleum industry as corrosion inhibitors, flocculants, and thickening agents [114][115][116]. Spinthaki et al [117,118] have prepared interrelated methacrylate-structured polymers, including the grafting of phosphonic acid (PHOS) to a methacrylate acid side-chain or with grafting of polyethylene glycol (PEG), as shown in Figure 8. These authors evaluated these polymeric scale inhibitors with eight different types of scales, including amorphous silica, carbonates, silicates, and sulfides.…”

Section: Grafted Copolymermentioning

confidence: 99%

“…Table 4 summarizes the key properties, including efficiency and toxicity of these phosphorusbased polymers. Grafted copolymer [117,118] Able to control multiple scales in any process field, in particular under harsh conditions;…”

Section: Other Terpolymermentioning

confidence: 99%

Review of Phosphorus-Based Polymers for Mineral Scale and Corrosion Control in Oilfield

Liu

Zhang

2022

Polymers

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Production chemistry is an important field in the petroleum industry to study the physicochemical changes in the production system and associated impact on production fluid flow from reservoir to topsides facilities. Mineral scale deposition and metal corrosion are among the top three water-related production chemistry threats in the petroleum industry, particularly for offshore deepwater and shale operations. Mineral scale deposition is mainly driven by local supersaturation due to operational condition change and/or mixing of incompatible waters. Corrosion, in contrast, is an electrochemical oxidation–reduction process with local cathodic and anodic reactions taking place on metal surfaces. Both mineral scaling and metal corrosion can lead to severe operational risk and financial loss. The most common engineering solution for oilfield scale and corrosion control is to deploy chemical inhibitors, including scale inhibitors and corrosion inhibitors. In the past few decades, various chemical inhibitors have been prepared and applied for scaling and corrosion control. Phosphorus-based polymers are an important class of chemical inhibitors commonly adopted in oilfield operations. Due to the versatile molecular structures of these chemicals, phosphorus-based polymeric inhibitors have the advantage of a higher calcium tolerance, a higher thermal stability, and a wider pH tolerance range compared with other types of inhibitors. However, there are limited review articles to cover these polymeric chemicals for oilfield scale and corrosion control. To address this gap, this review article systematically reviews the synthesis, laboratory testing, and field applications of various phosphorus-based polymeric inhibitors in the oil and gas industry. Future research directions in terms of optimizing inhibitor design are also discussed. The objective is to keep the readers abreast of the latest development in the synthesis and application of these materials and to bridge chemistry knowledge with oilfield scale and corrosion control practice.

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“…According to the development history, scale inhibitors are mainly experienced phosphonates, natural polymers, green scale inhibitors and polycarboxylic acids 4–6 . Among them, phosphonate scale inhibitors have been widely used and efficient in solving the problem of geothermal circulating water scaling 7,8 . However, it will seriously lead to eutrophication of water during use.…”

Section: Introductionmentioning

confidence: 99%

A carboxylate terpolymer as a scale inhibitor for geothermal hard water in recirculating systems

Chen

Qiao

et al. 2023

J of Applied Polymer Sci

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The inhibition efficiency of polycarboxylic acid will decrease due to the weak acidity of carboxyl group in high Ca 2+ geothermal circulating water. To solve this problem, we synthesized a novel carboxyl terpolymer (MA-AEO-7/SMAS/MA) with adipate polyoxyethylene ether maleate monoester (MA-AEO-7), sodium methacrylate sulfonate (SMAS) and maleic acid (MA). Its inhibition efficiency and mechanism were investigated at high Ca 2+ . The results indicated that the inhibition efficiency of MA-AEO-7/SMAS/MA was 96.84% for CaCO 3 at the monomeric ratio of 0.5:1:1 and a dosage of 12 mg L À1 . The X-ray diffraction and scanning electron microscope results of CaCO 3 scale showed that the presence of MA-AEO-7/SMAS/MA converted CaCO 3 calcite to vaterite with smaller particle size. The molecular dynamics and density functional theory calculations indicated that the increased solubility of MA-AEO-7/SMAS/MA and the carboxylic acidity in MA-AEO-7/SMAS/MA enhanced the Ca 2+ chelating properties. The electrostatic repulsion between the sulfonic acid groups made MA-AEO-7/SMAS/MA exhibit good dispersion properties. These findings explained why the inhibition efficiency of MA-AEO-7/SMAS/MA remained above 80% at Ca 2+ concentration of 1500 mg L À1 , exceeding the 30%-50% of the three commercial scale inhibitors.This study provides practical insight for the development of scale inhibitors suitable for high Ca 2+ geothermal circulating water.

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Searching for a universal scale inhibitor: A multi-scale approach towards inhibitor efficiency

Cited by 28 publications

References 76 publications

Systematic Molecular-Size Variants in Diphosphonate Inhibitors for Oilfield Scale Management

Systematic Molecular-Size Variants in Diphosphonate Inhibitors for Oilfield Scale Management

Review of Phosphorus-Based Polymers for Mineral Scale and Corrosion Control in Oilfield

A carboxylate terpolymer as a scale inhibitor for geothermal hard water in recirculating systems

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