A New Approach to Inhibitor Squeeze Design

Kan, A.T.; Fu, G.; Al-Thubaiti, M.; Xiao, J.; Tomson, M.B.

doi:10.2523/80230-ms

Cited by 7 publications

(11 citation statements)

References 4 publications

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“…Phosphonate chemicals show excellent scale inhibition performance, particularly in squeeze treatments. 14,15 They afforded remarkable retention and adsorption properties onto the formation rock and are easily monitored and detected. 16 In addition, polymer-based sulfonates have attracted significant attention as superior SIs in extremely high salinity reservoirs.…”

Section: Introductionmentioning

confidence: 99%

“…Phosphonate and sulfonate-based SIs are commonly applied for downhole and topside oilfield scale management. Phosphonate chemicals show excellent scale inhibition performance, particularly in squeeze treatments. , They afforded remarkable retention and adsorption properties onto the formation rock and are easily monitored and detected . In addition, polymer-based sulfonates have attracted significant attention as superior SIs in extremely high salinity reservoirs. , It was also found that introducing a few sulfonate moieties in the polymer structure improves its thermal stability, leading to a prolonged scale inhibition performance under harsh oilfield conditions…”

Section: Introductionmentioning

confidence: 99%

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Synthesis and Study of Modified Polyaspartic Acid Coupled Phosphonate and Sulfonate Moieties As Green Oilfield Scale Inhibitors

Mady

Rehman

Kelland

2021

Ind. Eng. Chem. Res.

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The petroleum industry has strived for several years to explore environmentally friendly scale inhibitors with no acute environmental impact. Well-known industrial biodegradable polyaspartic acid is widely used as a potent scale inhibitor (SI) against various inorganic scales in industrial circulating cooling water and topside petroleum applications. However, polyaspartic acid showed weak thermal stability at the petroleum reservoir temperatures. Here, we attempt to develop a new class of polyaspartic acid for squeeze treatment applications under harsh conditions. In this project, a series of modified polyaspartic acid, including pendant anionic functional moieties (phosphonate and sulfonate) were synthesized and investigated as new SIs to inhibit the calcium carbonate (calcite, CaCO3) and barium sulfate (barite, BaSO4) scales under oilfield conditions. These classes were synthesized via aminolysis of polysuccinimide with nucleophilic amine reagents under alkaline conditions. The products are polyaspartic acid-capped aminomethylene phosphonic acid (SI-2), polyaspartic acid-capped bisphosphonic acid (SI-3), polyaspartic acid-capped aminomethanesulfonic acid (SI-4), and polyaspartic acid-capped aminoethanesulfonic acid (SI-5), as well as in-house synthesized polyaspartic acid (SI-1). The scale inhibition activities of these compounds against carbonate and sulfate scales were determined using the dynamic scale loop test at 100 °C and 80 bar. Furthermore, the long-term thermal aging and calcium tolerance experiments were also investigated. It was found that polyaspartic-acid-capped aminomethylene phosphonic acid (SI-2) gave outstanding calcite scale inhibition performance and showed excellent thermal stability at 130 °C for 7 days compared to SI-1 and other modified SIs (SI-3-SI-5). This phosphonated polymer also exhibited superior calcium tolerance performance with Ca2+ ions up to 100 ppm, and moderate performance in the range of 1000–10 000 ppm calcium ions. This project highlights the success of designing and developing a new environmentally friendly calcite SI-based polyaspartic acid under harsh oilfield conditions.

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Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Synthesis and Study of Modified Polyaspartic Acid Coupled Phosphonate and Sulfonate Moieties As Green Oilfield Scale Inhibitors

Mady

Rehman

Kelland

2021

Ind. Eng. Chem. Res.

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“…Subsequently, a low solubility crystalline phase of calcium phosphonate with a stoichiometry of Ca3H4DTPMP was successfully made by Kan et al (Kan et al 1994) from the amorphous calcium phosphonate precipitates by a combined dialysis and filtration method. Following this observation, low solubility phase of calcium phosphonate precipitates were reported for other common phosphonate inhibitor such as, NTMP, and polyphosphinocarboxylic acid (PPCA) by the same approach (Xiao et al 2001;Kan et al 2003). Fogler and his co-worker (Browning and Fogler 1996;Pairat et al 1997) demonstrated different Ca-HEDP and Ca-ATMP precipitates by changing the pH and calcium-tophosphonate molar ratios.…”

Section: Introductionmentioning

confidence: 88%

Attchment/Release of Phosphonate to/from a CaCO Surface in Supersaturated Brines

Zhang¹,

Kan²,

Tomson³

2014

SPE International Oilfield Scale Conference and Exhibition

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One of the most intractable concerns when engineers try to reuse the produced water as frac fluid in the Bakken and some other shale plays is the scale formation caused by the incompatibility of produced water with additives in the frac fluids and with the formation. In order to obtain a more efficient scale treatment for a successful hydraulic fracing that handles the extraordinary amount of water with high supersaturation level, the better understanding of inhibitor retention and release in the production system is urgent.To explore the mechanism of attachment/release of phosphonate to/from a mineral surface, calcite supersaturated feed solutions with different diethylenetriamine penta (DTPMP) concentrations were introduced into the steel tubing that was internally pre-coated with a thin layer of CaCO 3 . It is unveiled that DTPMP attachment was dominated by the precipitation of calcium phosphonate solid once the solution is supersaturated with Ca 3 H 4 DTPMP (pKspϭ53.5), and the total amount of DTPMP attached on the calcite surface added up with the increasing supersaturation of Ca 3 H 4 DTPMP. The co-precipitation of CaCO 3 and Ca 3 H 4 DTPMP has facilitated the attachment of the inhibitor with the increase of supersaturation of CaCO 3 . The retained phosphonate was released from the surface with a steady and low level inhibitor concentration over extended period of time. Combining with the kinetics of calcium carbonate precipitation in the presence of inhibitor, a 1500 gram of calcium phosphonate precipitation can protect the scaling for about 100 days (100 bbl/day) when the saturation index of calcium carbonate (SI calcite ) is as high as 1.3.The results provide a better understanding of calcium-phosphonate-carbonate interaction, and show the phosphonate inhibitor can continuously accumulate on the carbonate and slowly dissolve. We anticipate this study can shed a light on how much inhibitor can be delivered to the unconventional reservoir as well as the theoretical limitation of inhibitor return in the flowback water.

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“…Others have reported on liquid inhibitor squeeze treatments. 5,6 Since a minimum residual value (for the sake of this exercise use 10 ppm as the point at which inhibition may start to diminish) is all that is necessary for scale protection, any residual in excess of that value is wasted. Thus the goal of any long term scale inhibitor exercise is to place an inhibitor into the formation such that the residual value starts low, i.e.…”

Section: Days Since Inhibitor Placement Scale Inhibitor Residual In Ppmmentioning

confidence: 99%

Long-Term Scale Inhibition Using a Solid Scale Inhibitor in a Fracture Fluid

Szymczak¹,

Brown²,

Noe³

et al. 2006

All Days

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TX 75083-3836, U.S.A., fax 01-972-952-9435. AbstractProlonged scale inhibition in excess of one year is a desirable benefit of oil and gas well formation squeeze treatments. Traditionally liquid inhibitors have given the requisite inhibitor residual for up to one year. Operators desire longer inhibition periods. This paper describes a new scale inhibitor technology that extends scale inhibition beyond one year.All of the components of a hydraulic fracturing package must be compatible to insure that the rheology of the fluid is not affected. The placement of a scale inhibitor onto a formation requires a suitable inhibitor that will adsorb to the mineral surfaces and return slowly with the produced water. Adding a solid scale inhibitor to a frac package required limited compatibility testing and reformulation in order to meet the fluid integrity and product effectiveness criteria. The scale inhibitor dosage was designed for a three-year life.The accepted method of monitoring the effectiveness of a scale inhibitor squeeze is through measuring the scale inhibitor residual in the produced water. Traditional liquid scale inhibitors give a high initial residual (>1000-ppm) and deplete to a minimal level (1-10 ppm) within a year. The solid inhibitor placed on the formation during the frac released a residual below 50 ppm at the first reading and has maintained an acceptable level for the life of the placement (as of this writing the residuals are still above the minimum level).Operators of offshore and remote area wells that are prone to scale deposition must undertake significant intervention measures to remediate scale deposition. 1 This new chemical technology extends the life of a scale inhibitor placement beyond the current expectations. The advancement of this technology will save operators money and encourage the development of properties that might be viewed unprofitable due to the high frequency and cost of intervention.

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A New Approach to Inhibitor Squeeze Design

Cited by 7 publications

References 4 publications

Synthesis and Study of Modified Polyaspartic Acid Coupled Phosphonate and Sulfonate Moieties As Green Oilfield Scale Inhibitors

Synthesis and Study of Modified Polyaspartic Acid Coupled Phosphonate and Sulfonate Moieties As Green Oilfield Scale Inhibitors

Attchment/Release of Phosphonate to/from a CaCO Surface in Supersaturated Brines

Long-Term Scale Inhibition Using a Solid Scale Inhibitor in a Fracture Fluid

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