Polyelectrolyte Multilayered Nanoparticles as Nanocontainers for Enzyme Breakers During Hydraulic Fracturing Process

2021 ◽  
Author(s):  
Mubarak Muhammad Alhajeri ◽  
Jenn-Tai Liang ◽  
Reza Barati Ghahfarokhi

Abstract In this study, Layer-by-Layer (LbL) assembled polyelectrolyte multilayered nanoparticles were developed as a technique for targeted and controlled release of enzyme breakers. Polyelectrolyte multilayers (PEMs) were assembled by means of alternate electrostatic adsorption of polyanions and polycations using colloidal structure of polyelectrolyte complexes (PECs) as LbL building blocks. High enzyme concentrations were introduced into polyethyleneimine (PEI), a positively charged polyelectrolyte solution, to form an electrostatic PECs with dextran sulfate (DS), a negatively charged polyelectrolyte solution. Under the right concentrations and pH conditions, PEMs were assembled by alternating deposition of PEI with DS solutions at the colloidal structure of PEI-DS complexes. Stability and reproducibility of PEMs were tested over time. This work demonstrates the significance of PEMs as a technique for the targeted and controlled release of enzymes based on their high loading capacity, high capsulation efficiency, and extreme control over enzyme concentration. Entrapment efficiency (EE%) of polyelectrolyte multilayered nanoparticles were evaluated using concentration measurement methods as enzyme viscometric assays. Controlled release of enzyme entrapped within PEMs was sustained over longer time periods (> 18 hours) through reduction in viscosity, and elastic modulus of borate-crosslinked hydroxypropyl guar (HPG). Long-term fracture conductivity tests at 40℃ under closure stresses of 1,000, 2,000, and 4,000 psi revealed high fracture clean-up efficiency for fracturing fluid mixed with enzyme-loaded PEMs nanoparticles. The retained fracture conductivity improvement from 25% to 60% indicates the impact of controlled distribution of nanoparticles in the filter cake and along the entire fracture face as opposed to the randomly dispersed unentrapped enzyme. Retained fracture conductivity was found to be 34% for fluid systems containing conventional enzyme-loaded PECs. Additionally, enzyme-loaded PEMs demonstrated enhanced nanoparticle distribution, high loading and entrapment efficiency, and sustained release of the enzyme. This allows for the addition of higher enzyme concentrations without compromising the fluid properties during a treatment, thereby effectively degrading the concentrated residual gel to a greater extent. Fluid loss properties of polyelectrolyte multilayered nanoparticles were also studied under static conditions using a high-pressure fluid loss cell. A borate-crosslinked HPG mixed with nanoparticles was filtered against core plugs with similar permeabilities. The addition of multilayered nanoparticles into the fracturing fluid was observed to significantly improve the fluid- loss prevention effect. The spurt-loss coefficient values were also determined to cause lower filtrate volume than those with crosslinked base solutions. The PEI-DS complex bridging effects revealed a denser, colored filter cake indicating a relatively homogenous dispersion and properly sized particles in the filter cake.

1985 ◽  
Vol 25 (04) ◽  
pp. 482-490 ◽  
Author(s):  
Robert Ray McDaniel ◽  
Asoke Kumar Deysarkar ◽  
Michael Joseph Callanan ◽  
Charles A. Kohlhaas

Abstract A test apparatus is designed to carry out dynamic and static fluid-loss tests of fracturing fluids. This test apparatus simulates the pressure difference, temperature, rate of shear, duration of shear, and fluid-flow pattern expected under fracture conditions. For a typical crosslinked fracturing fluid, experimental results indicate that fluid loss values can be a function of temperature, pressure differential, rate of shear, and degree of non-Newtonian behavior of the fracturing fluid. A mathematical development demonstrates that the fracturing-fluid coefficient and filter-cake coefficient can be obtained only if the individual pressure drops can be measured during a typical fluid-loss test. Introduction In a hydraulic fracturing treatment, the development of fracture length and width is strongly dependent on a number of key fluid and formation parameters. One of the most important of these parameters is the rate at which the fracturing fluid leaks, off into the created fracture faces. This parameter, identified as fluid loss, also influences the time required for the fracture to heal after the stimulation treatment has been terminated. This in turn will influence the final distribution of proppant in the fracture and will dictate when the well can be reopened and the cleanup process started. Historically, tests to measure fluid loss have been carried out primarily under what is characterized as static conditions. In such tests, the fracturing fluid is forced through filter paper or through a thin core wafer under a pressure gradient, and the flow rate at the effluent side is determined. Of course, the use of filter paper cannot account for reservoir formation permeability and porosity; therefore, the fluid-loss characteristics derived from such tests should be viewed as only gross approximations. The static core-wafer test on the other hand, reflects to some extent the interaction of the formation and fracturing-fluid properties. However, one important fluid property is altogether ignored in such static core-wafer tests. This is the effect of shear rate in the fracture on the rheology (viscosity) of fracturing fluid and subsequent effects of viscosity on the fluid loss through the formation rock. In the past, several attempts were made to overcome the drawbacks of static core-wafer tests by adopting dynamic fluid-loss tests. Although these dynamic tests were a definite improvement over the static versions, each had drawbacks or limitations that could influence test results. In some of the studies, the shearing area was annular rather than planar as encountered in the fracture. In other cases, the fluid being tested did not experience a representative shear rate for a sufficiently long period of time. An additional problem arose because most studies were performed at moderate differential pressures and temperatures. The final drawback in several of the studies was that the fluid flow and leakoff patterns did not realistically simulate those occurring in the field. In the first part of this paper, we emphasize the design of a dynamic fluid-loss test apparatus that possesses none of these drawbacks. In the second part of the paper, test results with this apparatus are presented for three different fluid systems. These systems areglycerol, a non-wall-building Newtonian fluid,a polymer gel solution that is slightly wall-building and non-Newtonian, anda crosslinked fracturing system that is highly non-Newtonian in nature and possesses the ability to build a wall (filter cake) on the fracture face (see Table 1). The fluids were subjected to both static and dynamic test procedures. In the third part of the paper, results of experiments carried out with crosslinked fracturing fluid for different core lengths, pressure differences, temperatures, and shear rates are compared and the significance of the difference of fluid loss is emphasized. Experimental Equipment and Procedure The major components of the experimental apparatus shown in Fig. 1 are a fluid-loss cell, circulation pump, heat exchanger, system pressurization accumulators, and a fluid-loss recording device. The construction material throughout most of the system is 316 stainless steel. The fluid loss is measured through a cylindrical core sample, 1.5 in. [3.81 cm] in diameter, mounted in the fluid-loss cell. Heat-shrink tubing is fitted around the circumference of the core and a confining pressure is maintained to prevent channeling. Fracturing fluid is circulated through a rectangular channel across one end of the core. SPEJ P. 482^


2019 ◽  
Vol 71 ◽  
pp. 102986 ◽  
Author(s):  
Jiaxiang Xu ◽  
Yunhong Ding ◽  
Lifeng Yang ◽  
Zhe Liu ◽  
Rui Gao ◽  
...  

1985 ◽  
Vol 25 (05) ◽  
pp. 629-636 ◽  
Author(s):  
L.P. Roodhart

Abstract When filter-cake-building additives are used in fracturing fluids, the commonly applied static, 30-minute API filtration test is unsatisfactory, because in a dynamic situation (like fracturing) the formation of a thick filter cake will be inhibited by the shearing forces of the fracturing fluid. A dynamic, filter-cake-controlled, leakoff coefficient that is dependent on the shear rate and shear stress at the fracture face is, therefore, introduced. A test apparatus has been constructed in which the fluid leakoff is measured under conditions of temperature, rate of shear, duration of shear, and fluid-flow pattern as encountered under fracturing conditions. The effects of rock permeability, shear rate, and differential pressure on the permeability, shear rate, and differential pressure on the dynamic leakoff coefficient are presented for various, commonly used fracturing-fluid/fluid-loss-additive combinations. Introduction An important parameter in hydraulic fracturing design is the rate at which the fracturing fluid leaks into the formation. This parameter, known as fluid loss, not only determines the development of fracture length and width, but also governs the time required for a fracture to heal after the stimulation treatment has been terminated. The standard leakoff test is a static test, in which the effect of shear rate in the fracture on the viscosity of the fracturing fluid and on the filter-cake buildup is ignored. Dynamic vs. Static Tests The three stages in filter-cake buildup arespurt loss during initiation of the filter cake,buildup of filtercake thickness, during which time leakoff is proportional to the square root of time, andlimitation of filter-cake growth by erosion. In the standard API leakoff test, 1 the fracturing fluid, with or without leakoff additives, is forced through a disk of core material under a pressure differential of 1000 psi [7 MPa), and the flow rate of the filtrate is determined. In such a static test, the third stage-erosion of the filter cake-is absent. In a dynamic situation there is an equilibrium whereby flow along the filter cake limits the filter-cake thickness, and the leakoff rate becomes constant. The duration of each of these stages depends on the type of fluid, the type of additive, the rock permeability, and the test conditions. The differences between dynamic and static filtration tests are shown in Fig. 1, where the cumulative filtrate volume (measured in some experiments with the dynamic fluid-loss apparatus described below) is expressed as a function of time (Fig. la) and as a function of the square root of time (Fig. ]b), The shear rate at the surface of the disk is either static (O s -1 ), or 109 s -1 or 611 s -1. The curves indicate that the dynamic filtration velocities are higher than those measured in a static test and increase rapidly with increasing shear rate. This is in agreement with the observations made by Hall, who used an axially transfixed cylindrical core sample along which fracturing fluid was pumped, while the filtrate was collected from a bore through the center. Fig. la shows how the lines were drawn to fit the data: Vc = Vsp + A t + Bt, .........................(1) where Vc = cumulative volume per unit area, t = filtration time, Vsp= spurt loss, A = static leakoff component, andB = dynamic leakoff component. In static leakoff theory, B =0 and then A =2Cw, twice the static leakoff coefficient.-3 Each of the terms in Eq. 1 represents one of the stages in the leakoff process-spurt loss, buildup of filter cake, and erosion of filter cake. Analysis of the experimental data shows that the spurt loss, Vsp, and the static leakoff component, A, are independent of the shear rate, but the dynamic component, B, varies strongly with the shear rate (see Table 1). This means that, the higher the shear rate, the more the leakoff process is controlled by the third stage. process is controlled by the third stage. One model commonly used is based solely on square-root-of-time behavior with a constant spurt loss. Fig. 1 shows that little accuracy is lost by describing the leakoff with a single square-root-of-time equation: Vc = VsP + m t,...........................(2) where the dynamic leakoff coefficient. Cw = 1/2m, depends heavily on shear. and the spurt loss remains the same as in Eq. 1 and independent of the shear rate Table 2 shows that the error in C, that arises as a result of measuring under static conditions can be more than 100%. SPEJ P. 629


2020 ◽  
Vol 14 (3) ◽  
pp. 210-224
Author(s):  
Gayatri Patel ◽  
Bindu K.N. Yadav

Background: The purpose of this study was to formulate, characterize and in-vitro cytotoxicity of 5-Fluorouracil loaded controlled release nanoparticles for the treatment of skin cancer. The patents on nanoparticles (US8414926B1), (US61654404A), (WO2007150075A3) etc. helped in the selection polymers and method for the preparation of nanoparticles. Methods: In the present study nanoparticles were prepared by simple ionic gelation method using various concentrations of chitosan and sodium tripolyphosphate (TPP). Several process and formulation parameters were screened and optimized using 25-2 fractional factorial design. The prepared nanoparticles were evaluated for particle size, shape, charge, entrapment efficiency, crosslinking mechanism and drug release study. Results: The optimized 5-Fluorouracil loaded nanoparticle were found with particle size of of 320±2.1 nm, entrapment efficiency of 85.12%± 1.1% and Zeta potential of 29mv±1mv. Scanning electron microscopy and dynamic light scattering technique revealed spherical particles with uniform size. The invitro release profile showed controlled release up to 24 hr. Further study was carried using A375 basal cell carcinoma cell-line to elucidate the mechanism of its cytotoxicity by MTT assay. Conclusion: These results demonstrate that the possibility of delivering 5-Fluorouracil to skin with enhanced encapsulation efficiency indicating effectiveness of the formulation for treatment of basal cell carcinoma type of skin cancer.


Energies ◽  
2021 ◽  
Vol 14 (6) ◽  
pp. 1783
Author(s):  
Klaudia Wilk-Zajdel ◽  
Piotr Kasza ◽  
Mateusz Masłowski

In the case of fracturing of the reservoirs using fracturing fluids, the size of damage to the proppant conductivity caused by treatment fluids is significant, which greatly influence the effective execution of hydraulic fracturing operations. The fracturing fluid should be characterized by the minimum damage to the conductivity of a fracture filled with proppant. A laboratory research procedure has been developed to study the damage effect caused by foamed and non-foamed fracturing fluids in the fractures filled with proppant material. The paper discusses the results for high quality foamed guar-based linear gels, which is an innovative aspect of the work compared to the non-foamed frac described in most of the studies and simulations. The tests were performed for the fracturing fluid based on a linear polymer (HPG—hydroxypropyl guar, in liquid and powder form). The rheology of nitrogen foamed-based fracturing fluids (FF) with a quality of 70% was investigated. The quartz sand and ceramic light proppant LCP proppant was placed between two Ohio sandstone rock slabs and subjected to a given compressive stress of 4000–6000 psi, at a temperature of 60 °C for 5 h. A significant reduction in damage to the quartz proppant was observed for the foamed fluid compared to that damaged by the 7.5 L/m3 natural polymer-based non-foamed linear fluid. The damage was 72.3% for the non-foamed fluid and 31.5% for the 70% foamed fluid, which are superior to the guar gum non-foamed fracturing fluid system. For tests based on a polymer concentration of 4.88 g/L, the damage to the fracture conductivity by the non-foamed fluid was 64.8%, and 26.3% for the foamed fluid. These results lead to the conclusion that foamed fluids could damage the fracture filled with proppant much less during hydraulic fracturing treatment. At the same time, when using foamed fluids, the viscosity coefficient increases a few times compared to the use of non-foamed fluids, which is necessary for proppant carrying capacities and properly conducted stimulation treatment. The research results can be beneficial for optimizing the type and performance of fracturing fluid for hydraulic fracturing in tight gas formations.


2021 ◽  
Vol 38 (7) ◽  
pp. 2170013
Author(s):  
Ghizlane Choukrani ◽  
Jimena Álvarez Freile ◽  
Natasha Ustyanovska Avtenyuk ◽  
Wei Wan ◽  
Kerstin Zimmermann ◽  
...  

Molecules ◽  
2021 ◽  
Vol 26 (11) ◽  
pp. 3133
Author(s):  
Yuling Meng ◽  
Fei Zhao ◽  
Xianwei Jin ◽  
Yun Feng ◽  
Gangzheng Sun ◽  
...  

Fracturing fluids are being increasingly used for viscosity development and proppant transport during hydraulic fracturing operations. Furthermore, the breaker is an important additive in fracturing fluid to extensively degrade the polymer mass after fracturing operations, thereby maximizing fracture conductivity and minimizing residual damaging materials. In this study, the efficacy of different enzyme breakers was examined in alkaline and medium-temperature reservoirs. The parameters considered were the effect of the breaker on shear resistance performance and sand-suspending performance of the fracturing fluid, its damage to the reservoir after gel breaking, and its gel-breaking efficiency. The experimental results verified that mannanase II is an enzyme breaker with excellent gel-breaking performance at medium temperatures and alkaline conditions. In addition, mannanase II did not adversely affect the shear resistance performance and sand-suspending performance of the fracturing fluid during hydraulic fracturing. For the same gel-breaking result, the concentration of mannanase II used was only one fifth of other enzyme breakers (e.g., mannanase I, galactosidase, and amylase). Moreover, the amount of residue and the particle size of the residues generated were also significantly lower than those of the ammonium persulfate breaker. Finally, we also examined the viscosity-reducing capability of mannanase II under a wide range of temperatures (104–158 °F) and pH values (7–8.5) to recommend its best-use concentrations under different fracturing conditions. The mannanase has potential for applications in low-permeability oilfield development and to maximize long-term productivity from unconventional oilwells.


2020 ◽  
Vol 6 (1) ◽  
Author(s):  
Chukwuebuka H. Ozoude ◽  
Chukwuemeka P. Azubuike ◽  
Modupe O. Ologunagba ◽  
Sejoro S. Tonuewa ◽  
Cecilia I. Igwilo

Abstract Background Khaya gum is a bark exudate from Khaya senegalensis (Maliaecae) that has drug carrier potential. This study aimed to formulate and comparatively evaluate metformin-loaded microspheres using blends of khaya gum and sodium alginate. Khaya gum was extracted and subjected to preformulation studies using established protocols while three formulations (FA; FB and FC) of metformin (1% w/v)-loaded microspheres were prepared by the ionic gelation method using 5% zinc chloride solution as the cross-linker. The formulations contained 2% w/v blends of khaya gum and sodium alginate in the ratios of 2:3, 9:11, and 1:1, respectively. The microspheres were evaluated by scanning electron microscopy, Fourier transform-infrared spectroscopy, differential scanning calorimetry, entrapment efficiency, swelling index, and in vitro release studies. Results Yield of 28.48%, pH of 4.00 ± 0.05, moisture content (14.59% ± 0.50), and fair flow properties (Carr’s index 23.68 ± 1.91 and Hausner’s ratio 1.31 ± 0.03) of the khaya gum were obtained. FTIR analyses showed no significant interaction between pure metformin hydrochloride with excipients. Discrete spherical microspheres with sizes ranging from 1200 to 1420 μm were obtained. Drug entrapment efficiency of the microspheres ranged from 65.6 to 81.5%. The release of the drug from microspheres was sustained for the 9 h of the study as the cumulative release was 62% (FA), 73% (FB), and 80% (FC). The release kinetics followed Korsmeyer-Peppas model with super case-II transport mechanism. Conclusion Blends of Khaya senegalensis gum and sodium alginate are promising polymer combination for the preparation of controlled-release formulations. The blend of the khaya gum and sodium alginate produced microspheres with controlled release properties. However, the formulation containing 2:3 ratio of khaya gum and sodium alginate respectively produced microspheres with comparable controlled release profiles to the commercial brand metformin tablet.


Author(s):  
S. Sivaprasad ◽  
V. Alagarsamy ◽  
M. Prathibha Bharathi ◽  
P.V. Murali Krishna ◽  
K. Sandeeep Kanna

The main objective of the present study was to design a controlled release dosage form for an oral anti diabetic drug i.e. repaglinide employing polymers like eudragit s- 100. One of the other objective of this present study was to increase the biological half-life the drug by formulating into microspheres. The microspheres of repaglinide were prepared by solvent evaporation method by using eudragit s-100 and ethyl cellulose as polymers with different concentrations. Formulations (F1-F10) were prepared and evaluated for various micrometric properties and it was observed that though all the formulations were exhibited good flow properties, The F5 formulation exhibits higher in- vitro buoyancy time and entrapment efficiency which is considered for in- vitro and mucoadhesive studies. The FTIR results reveal that there was no interaction between the drug and the excipients. The in- vitro release profiles of F1-F5 indicated that all formulations showed controlled release over an extended period, with acceptable release kinetics. Among the all formulations F5 were considered as a promising candidate for sustain release of repaglinide.


Author(s):  
Farhana Sultan ◽  
Himansu Chopra ◽  
Gyanendra Kumar Sharma

Microsponge containing Luliconazole (LCZ) with different proportion of drug:polymer (Ethyl cellulose and Eudragit RS 100) were obtained efficiently using Quasi-emulsion solvent diffusion method. Luliconazole is an anti-fungal drug used for the topical delivery. The purpose of the microsponge formulation is to control the release of LCZ drug to the skin through Microsponge Delivery System (MDS) known to be the novel technique which overcome the maximum concentration of active ingredient, frequency doses, and skin irritation. The prepared microsponges were examined using drug content, % production yield, % entrapment efficiency and in-vitro drug release. The formulation were subjected to in-vitro drug release studies for 6 hr in which it was concluded that Ethyl cellulose microsponges formulated by drug:polymer (1:1) and Eudragit RS 100 microsponges formulated by drug:polymer (1:3) showed maximum controlled release i.e., Increase in drug:polymer ratio (1:1 to 1:9) increased the production yield and entrapment efficiency of microsponges using Ethyl cellulose with no significant effect for Eudragit RS 100.Therefore, both formulation F1 and F2 was dispersed in carbopol gel preparation for controlled delivery of LCZ to the skin. Various physical parameters like pH, spreadability, viscosity and in-vitro drug diffusion studies were evaluated for the prepared gel formulations. Microsponge gel formulation i.e., FG1 showed better results for controlled release of 89.40% as compared to FG2 i.e., 92.18% over the period of 12 hrs which is performed in Franz Diffusion Cell. On basis of in-vitro diffusion studies for LCZ gel formulation, microsponges using Ethyl cellulose (FG1) was found to be best for its controlled release of LCZ for 12 hrs and followed zero order kinetics. Hence, formulated LCZ loaded gel have potential to treat fungal infections i.e., tinea pedis, tinea cruris and tinea corporis.


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