Zirconium Crosslinkers: Understanding Performance Variations in Crosslinked Fracturing Fluids

Almubarak, Tariq; Ng, Jun Hong; Nasr‐El‐Din, Hisham A.; Almubarak, Majed; AlKhaldi, Mohammed

doi:10.4043/30381-ms

Cited by 14 publications

(21 citation statements)

References 47 publications

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“…Different ligands can create different zirconium crosslinkers with different performances, and they are shown in Figure 2 . 33 In the experiments, we used ready liquid with assumed 14% active content. The liquid Zr-crosslinker is added after the addition of GLDA.…”

Section: Methodsmentioning

confidence: 99%

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Rheological Study of Seawater-Based Fracturing Fluid Containing Polymer, Crosslinker, and Chelating Agent

et al. 2022

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Freshwater is usually used in hydraulic fracturing as it is less damaging to the formation and is compatible with the chemical additives. In recent years, seawater has been the subject of extensive research to reduce freshwater consumption. The study aims to optimize the rheology of seawater-based fracturing fluid with chemical additives that reduce the formation damage. The studied formulation consists of a polymer, a crosslinker, and a chelating agent to reduce seawater hardness. We used a standard industry rheometer to perform the rheology tests. By comparing five distinct grades [hydroxypropyl guar (HPG) and carboxymethyl hydroxypropyl guar (CMHPG)], we selected the guar derivative with the best rheological performance in seawater. Five different polymers (0.6 wt %) were hydrated with seawater and freshwater to select the suitable one. Then, the best performing polymer was chosen to be tested with (1.6, 4, and 8 wt %) N , N -dicarboxymethyl glutamic acid GLDA chelating agent and 1 wt % zirconium crosslinker. In the first part, the testing parameters were 120 °C temperature, 500 psi pressure, and 100 1/s shear rate. Then, the same formulations were tested at a ramped temperature between 25 and 120 °C. We observed that higher and more stable viscosity levels can be achieved by adding the GLDA after polymer hydration. In seawater, an instantaneous crosslinking occurs once the crosslinker is added even at room temperature, while in freshwater, the crosslinker is activated by ramping the temperature. We noted that, in the presence of a crosslinker, small changes in the chelating agent concentration have a considerable impact on the fluid rheology, as demonstrated in ramped temperature results. It is observed that the viscosities are higher and more persistent at lower concentrations of GLDA than at higher concentrations. The study shows the rheological response when different chemical additives are mixed in saline water for hydraulic fracturing applications.

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Section: Methodsmentioning

confidence: 99%

“…They are employed to prevent Zr oxides from precipitating and to restrict the development of Zr nanoparticles beyond what is required. Different ligands can create different zirconium crosslinkers with different performances, and they are shown in Figure . In the experiments, we used ready liquid with assumed 14% active content.…”

Section: Methodsmentioning

confidence: 99%

Rheological Study of Seawater-Based Fracturing Fluid Containing Polymer, Crosslinker, and Chelating Agent

et al. 2022

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“…Borates are immediate crosslinkers used to maintain viscosity stability at elevated temperatures; they generate borate-crosslinked guar derivative salt. Fracturing tasks employ delayed zirconium crosslinkers to transport proppants with little energy. ,,− …”

Section: Introductionmentioning

confidence: 99%

Individual Seawater Ions’ Impact on the Rheology of Crosslinked Polymers in the Presence of a Chelating Agent

et al. 2023

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Seawater (SW) has the potential to replace freshwater in hydraulic fracturing operations, which promotes sustainability. In this study, we investigated the influence of SW ions individually on a crosslinked polymer solution containing a chelating agent. The tested salts include calcium chloride, magnesium chloride, sodium chloride, and sodium sulfate. First, the concentrations of the delayed zirconium crosslinker, which is used to crosslink the carboxymethyl hydroxypropyl (CMHPG) polymer, and high-pH GLDA were optimized. The testing parameters for the crosslinker and chelating agent optimization experiments were a 70 °C temperature, a 500 psi pressure, and a 100 1/s shear rate. However, the temperature was raised to 120 °C representing harsh reservoir conditions. Results showed that sulfate had a significant effect on the rheology of the crosslinked CMHPG polymer. Unlike DI water, the viscosity of SW and individual ions increased when the crosslinker concentration was increased. In addition, the solution stability of magnesium chloride and DI water was improved. Adding a chelating agent at a low concentration improved the solution stability of magnesium chloride and DI water. These findings are critical for comprehending the rheology of produced water and SW-based fracturing fluids.

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“…To solve these issues, reagents such as propylene oxide and/or chloroacetic acid have been employed to modify guar gum, resulting in three guar-gum derivatives: hydroxypropyl guar gum (HPG), carboxymethyl guar gum (CMG), and carboxymethyl hydroxypropyl guar gum (CMHPG) . Borate cross-linked HPG and zirconium cross-linked CMHPG are two common guar-based, cross-linked gel-fracturing fluid systems that have been applied in different pH situations. − Carbon dioxide (CO 2 )-enhanced oil recovery (EOR) and storage techniques have broad applications in compacting reservoirs in China, such as the Changqing, Jidong, and Daqing peripheral oilfields. , CO 2 –water–rock reactions occur in the formation zone under high-temperature (HT)/high-pressure (HP) conditions, altering the pH of the formation environment; this pH can be as low as 3.5 . In this circumstance, the performance of the most utilized borate cross-linked HPG fracturing fluid system, which is gelled in an alkaline range (pH > 8.0), is restricted due to the incompatibility of the pH reaction conditions.…”

Section: Introductionmentioning

confidence: 99%

Development and Evaluation of an Acidic Shear-Tolerant Nanosheet-Enhanced Cross-Linked Gel System for Hydrofracturing

Zhang

Hou

2021

Energy Fuels

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Acidic fracturing fluids, such as zirconium cross-linked carboxymethyl hydroxypropyl guar gum (CMHPG), can not only adapt to formations treated with CO2 but also protect such formations from the damage that arises from the swelling and migration of clay particles during the hydrofracturing process. However, the shortcomings of uncontrollable viscosity growth and irreversible shear-thinning behavior limit the large-scale application of acidic fracturing fluids. In this work, a novel organic zirconium cross-linker was synthesized in the laboratory and applied under acidic conditions to control and delay cross-linking reactions. The ligands that were coordinated to the zirconium center were l-lactate and ethylene glycol. A CMHPG thickener was used at a low loading of 0.3% (approximately 25 pptg). Concentrated hydrochloric acid was utilized as a buffer to adjust the fracturing fluid pH to 3.0 for the majority of the tests and approximately simulate the pH attained in formations treated with CO2 under high-temperature (HT)/high-pressure (HP) conditions. Moreover, surface-functionalized metallic-phase (1T) molybdenum disulfide (MoS2) nanosheets were employed to improve the rheological performance of the zirconium cross-linked CMHPG fracturing fluid. l-Cysteine was utilized as a modification reagent. The morphologies, structures, and properties of the fabricated functionalized 1T-MoS2 (Cys-1T-MoS2) nanosheets were systematically characterized using transmission electron microscopy (TEM), scanning electron microscopy (SEM), Raman spectroscopy, X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), Fourier transform infrared spectroscopy (FTIR), and thermogravimetric analysis (TGA). The results of these characterization tests demonstrated the successful functionalization of the 1T-MoS2 nanosheets with l-cysteine. Then, the effects of this new nanosheet-enhanced zirconium cross-linked CMHPG fracturing fluid system with different cross-linker and nanosheet loadings on gelation performance were systematically assessed through the Sydansk bottle testing method combined with a rheometer under controlled-stress or controlled-rate modes. Microscopic observations and gel-breaking, regained-permeability, and proppant-settling tests were also carried out to further evaluate the fracturing fluid properties of this new system. The results indicated that the nanosheet-enhanced fracturing fluid had a desirable delayed cross-linking property. Compared with the blank fracturing fluid (without nanosheet enhancement), the nanosheet-enhanced fracturing fluid had a much better shear tolerance, shear recovery, and proppant carrying performance. Micrograph observations showed that an even and fine three-dimensional (3D) network structure formed within the nanosheet-enhanced fracturing fluid sample. Additionally, in contrast to the alkaline system, the acidic nanosheet-enhanced zirconium cross-linked CMHPG fracturing fluid system had much less formation damage induced by gel residues and clay swelling and dispersions.

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Zirconium Crosslinkers: Understanding Performance Variations in Crosslinked Fracturing Fluids

Cited by 14 publications

References 47 publications

Rheological Study of Seawater-Based Fracturing Fluid Containing Polymer, Crosslinker, and Chelating Agent

Rheological Study of Seawater-Based Fracturing Fluid Containing Polymer, Crosslinker, and Chelating Agent

Individual Seawater Ions’ Impact on the Rheology of Crosslinked Polymers in the Presence of a Chelating Agent

Development and Evaluation of an Acidic Shear-Tolerant Nanosheet-Enhanced Cross-Linked Gel System for Hydrofracturing

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