Development of degradable pre-formed particle gel(DPPG)as temporary plugging agent for petroleum drilling and production

Temporary plugging agent(TPA)is widely used in many fields of petroleum reservoir drilling and production,such as temporary plugging while drilling and petroleum well stimulation by diverting in acidizing or fracturing operations.The commonly used TPA mainly includes hard particles,fibers,gels,and composite systems.However,current particles have many limitations in applications,such as insufficient plugging strength and slow degradation rate.In this paper,a degradable pre-formed particle gel(DPPG)was developed.Experimental results show that the DPPG has an excellent static swelling effect and self-degradation performance.With a decrease in the concentration of total monomers or cross-linker,the swelling volume of the synthesized DPPG gradually increases.However,the entire self-degradation time gradually decreases.The increase in 2-acrylamide-2-methylpropanesulfonic acid(AMPS)in the DPPG composition can significantly increase its swelling ratio and shorten the self-degradation time.Moreover,DPPG has excellent high-temperature resistance(150°C)and high-salinity resistance(200,000 mg/L NaCl).Core displacement results show that the DPPG has a perfect plugging effect in the porous media(the plugging pressure gradient was as high as 21.12 MPa),and the damage to the formation after degradation is incredibly minor.Therefore,the DPPG can be used as an up-and-coming TPA in oil fields.

Characteristics and displacement mechanisms of the dispersed particle gel soft heterogeneous compound flooding system

Considering high temperature and high salinity in the reservoirs, a dispersed particle gel soft heterogeneous compound(SHC) flooding system was prepared to improve the micro-profile control and displacement efficiency. The characteristics and displacement mechanisms of the system were investigated via core flow tests and visual simulation experiments. The SHC flooding system composed of DPG particles and surfactants was suitable for the reservoirs with the temperature of 80-110 °C and the salinity of 1×10~4-10×10~4 mg/L. The system presented good characteristics: low viscosity, weak negatively charged, temperature and salinity resistance, particles aggregation capacity, wettability alteration on oil wet surface, wettability weaken on water wet surface, and interfacial tension(IFT) still less than 1×10^(-1) mN/m after aging at high temperature. The SHC flooding system achieved the micro-profile control by entering formations deeply and the better performance was found in the formation with the higher permeability difference existing between the layers, which suggested that the flooding system was superior to the surfactants, DPG particles, and polymer/surfactant compound flooding systems. The system could effectively enhance the micro-profile control in porous media through four behaviors, including direct plugging, bridging, adsorption, and retention. Moreover, the surfactant in the system magnified the deep migration capability and oil displacement capacity of the SHC flooding system, and the impact was strengthened through the mechanisms of improved displacement capacity, synergistic emulsification, enhanced wettability alteration ability and coalescence of oil belts. The synergistic effect of the two components of SHC flooding system improved oil displacement efficiency and subsequently enhanced oil recovery.

Facile Preparation of PVA-AA/TiO2 Composite Gel Particles and Their Tunable Photo-catalytic Property for the Degradation of Methyl Orange

In the presence of titanium dioxide powder, cross-linking reaction between commercial polyvinyl alcohol(PVA)-based macromonomer and acrylic acid(AA) was initiated with potassium persulfate in an emulsifying system. As a result, PVA-AA/TiO2 composite gel particles were obtained. The morphology and composition of the particles were analyzed with scanning electron microscopy(SEM), energy scattering x-ray spectroscopy(EDS), Fourier infrared spectroscopy(FTIR), and thermogravimetric analysis(TGA). The analysis results confirmed that the particles were the expected ones. TiO2 was dispersed homogeneously within the spheroidal particles. Compared to the control gel, the composite gel particles not only contained Ti element but also showed higher thermal stability. In addition, the photo-catalytic behavior of the particles for the degradation of methyl orange contained in aqueous solution was examined. The particles exhibited photocatalytic characteristic for the degradation of the model dye, which could be modulated by simply varying the amount of cross-linking agent or TiO2. The photo-catalytic degradation percentage of methyl orange maintained at 91%-96% after using the particles three times, which indicated that TiO2 could played its role repeatedly via being fixated within polyvinyl alcohol-based gel.

Development of re-crosslinkable dispersed particle gels for conformance improvement in extremely high-temperature reservoirs

Micro-scale and nano-scale dispersed gel particles(DPG)are capable of deep migration in oil reservoirs due to their deformability,viscoelasticity,and suitable particle size.Therefore,it has been widely studied and applied in reservoir conformance control in recent years.However,for highly permeable channels,their plugging performance is still limited.In addition,conventional in situ cross-linked polymer gels(ISCPGs)have fast gelation time under extremely high-temperature conditions,which often causes problems such as difficulty in pumping.Therefore,a re-cross linkable dispersed particle gel(RDPG)system applied for conformance control in highly permeable channels of extremely high-temperature petroleum reservoirs was investigated.The particle size distribution,gelation time,gel strength,injection performance,and perfo rmance strength in po rous media were investigated using a laser particle size meter,the Sydansk bottle test method,rheometer,and core displacement experiments,respectively.Results show that the RDPG suspension can be stable for more than 6 months at room temperature with storage modulus G’much lower than 10 Pa.It can pass through the pore throat by elastic deformation effect and does not cause strong blockage.Moreover,it can undergo re-crosslinking reaction at 150℃to form a strong bulk gel.The gel strength G’of re-crosslinked RDPG can be as high as 69.3 Pa,which meets the strength requirement of conformance control.The RDPG suspension has the properties of easy injection,and it also has strong plugging,and high-temperature resistance after re-crosslinked in the core,which can be a very promising material for conformance improvement in extremely high-temperature reservoirs.

Hyper-Miniaturisation of Monodisperse Janus Hydrogel Beads with Magnetic Anisotropy Based on Coagulation of Fe₃O₄Nanoparticles

We describe a simple and robust technique for fabricating monodisperse Janus hydrogel beads with magnetic anisotropy smaller than the microchannel used to produce them.

Probing the effect of Young's modulus on the plugging performance of micro-nano-scale dispersed particle gels

The effect of mechanical strength of the dispersed particle gel(DPG)on its macro plugging performance is significant,however,little study has been reported.In this paper,DPG particles with different mechanical strengths were obtained by mechanical shearing of bulk gels prepared with different formula.Young’s moduli of DPG particles on the micro and nano scales were measured by atomic force microscope for the first time.The mapping relationship among the formula of bulk gel,the Young’s moduli of the DPG particles and the final plugging performance were established.The results showed that when the Young’s moduli of the DPG particles increased from 82 to 328 Pa,the plugging rate increased significantly from 91.46%to 97.10%due to the distinctly enhanced stacking density and strength at this range.While when the Young’s moduli of the DPG particles surpassed 328 Pa,the further increase of plugging rate with the Young’s moduli of the DPG particles became insignificant.These results indicated that the improvement of plugging rate was more efficient by adjusting the Young’s moduli of the DPG particles within certain ranges,providing guidance for improving the macroscopic application properties of DPG systems in reservoir heterogeneity regulation.

Experimental investigation on migration and retention mechanisms of elastic gel particles(EGPs)in pore-throats using multidimensional visualized models

Knowledge of migration and retention mechanisms of elastic gel particles(EGPs)in pore-throats is essential for the effective application of EGPs as a smart sweep improvement and profile control agent for enhanced oil recovery(EOR).The matching coefficient(defined as the ratio of particle size to pore-throat size)is used to investigate its influence on migration,retention and profile control performance of EGPs.A 1-D continuous pore-throat visualization model(PTVM),a 2-D heterogeneous PTVM and a 3-D heterogeneous core model were constructed and used to investigate pore-scale migration,retention and controlling mechanism of migration and retention characteristics on EGPs profile control.The results of the 1-D continuous PTVM indicated that while the matching coefficient was in the optimal range(i.e.,0.20-0.32),the EGPs could not only smoothly migrate to the deeper pore-throats,but also form stable retention in the pores to resist the erosion of injected water,which was conducive to the effective indepth profile control.The results of the 2-D heterogeneous PTVM verified that the sweep efficiency in low-permeability regions could be significantly improved by in-depth migration and stable retention of EGPs in the pore-throats with an optimal matching coefficient(0.29),which was much better than that in cases with a smaller matching coefficient(0.17)or an excessive matching coefficient(0.39).Moreover,the NMR displacement experiments of 3-D heterogeneous cores were carried out to simulate the EGPs profile control in actual reservoir porous media.Saturation images and T2 spectrum curves of crude oil showed that EOR in the low-permeability layer was highest(56.1%)using EGPs profile control with an optimal matching coefficient,attributing to the in-depth migration and stable retention of EGPs.

Degradable preformed particle gel as temporary plugging agent for low-temperature unconventional petroleum reservoirs:Effect of molecular weight of the cross-linking agent

The development of unconventional petroleum resources has gradually become an important succession for increasing oil production.However,the related engineers and researchers are paying more and more attention to the application of temporary plugging agents(TPAs)for their efficient development.TPAs can expand the stimulated reservoir volume(SRV)and facilitate the flow of oil and gas to the bottom of the well.Particle-gels used as temporary plugging agents have the characteristics of the simple injection process,good deformation,high plugging strength,and complete self-degradation performance,which have been widely applied in recent years.In this paper,five samples of DPPG polymerized by different molecular weights of cross-linking agents were prepared.In addition,infrared spectroscopy analysis,differential calorimetry scanning(DSC)analysis,static particle gel swelling and degradation performance evaluation experiments,and dynamic temporary plugging performance experiments in cores were conducted at 34°C.Results show that as the molecular weight of the cross-linking agent(at 0.01 g)in the DPPG molecule decreased from 1,000 to 200 Da,the fewer cross-linking sites of DPPG,the looser the microscopic three-dimensional mesh structure formed.The swelling ratio increased from 7 to 33 times.However,the complete degradation time increased from 40 to 210 min.Moreover,the DSC results confirmed that the higher the molecular weight of the cross-linking agent,the worse is chemical stability and the more prone it to self-degradation.DPPG samples had good temporary plugging performance in reservoir cores.DPPGs prepared by the cross-linking agent with smaller molecular weight has a stronger swelling ratio,higher gel strength,and greater plugging strength in the core permeabilities.Moreover,the degraded DPPG is less damaging to the cores.However,their slower degradation rates take a slightly longer times to reach complete degradation.The results of this paper can provide new ideas and a theoretical basis for the development of particle gel-type temporary plugging agents(TPA)with controllable degradation time in low-temperature reservoirs.It can help to expand the application range of existing DPPG reservoir conditions.

Sol-Gel Preparation of Graphite/TiO_2 Composite Particles and Their Electrorheological Effect

Graphite/TiO2 composite particles were obtained by sol-gel technique in this paper. The structure and characteristic of the composite particles are analyzed by XRD, SEM and TG-DTA. The electrorheological properties of the ER fluid containing the particles were measured by a Couette-type rheometer under shear rates of 1-136 s-1 and AC electric fields of 0-3 kV/mm. The experimental results show that the leaking current density of the ER fluid is higher than that of pure titanium dioxide particles dispersed in damping oil. The shear yield stress of the ER fluid increases with increasing electric field and exhibits a typical Bingham flow behavior. The suspension demonstrates an excellent ER performance (τ/τo=1200) compared with conventional ER fluids (τ/τ0 ≤500). The sedimentation of the ER fluid is improved obviously due to the coating effect of the particles.

Features of the motion of gel particles in a three-phase bubble column under foaming and non-foaming conditions

Features of the motion of gel particles in a three-phase bubble column with non-foaming and foaming gas–liquid systems,determined by using experiments of radioactive particle tracking(RPT),have been compared.The tracer used is a gel particle which resembles typical immobilized biocatalyst.The tracer trajectory is analyzed to extract relevant information for design purposes.The solid velocity field,turbulence parameters,dispersion coefficients,mixing times and flow transitions are determined and compared.The presence of foam significantly affects many quantified parameters,especially within the heterogeneous flow regime.The hydrodynamic stresses are reduced in the presence of foam,especially close to the disengagement.The dispersion coefficients also decrease,and the solid mixing time is only slightly affected by the presence of foam.Gas holdup,inferred both from RPT experiments and from gamma ray scanning,is higher for foaming systems and leads to a shift in the transition gas velocity towards higher values.

Characterization of self-assembled nano-phase silane-based particle coating

Self-assembled nano-phase silane-based particle coating was prepared through sol-gel technique.Tetramethoxysilane and 3-glycidoxypropyltrimethoxysilane were used as precursors for the self-assembled sol-gel coatings.The silane colloidal particle size was analyzed by laser particle size measurement.The results indicate that the particle size is in nano-scale and the diameter of particles deceases with increasing dilution times.Gel permeation chromatography proves that the relative molecular mass of macromolecule in a referenced sol solution is 1220-1240 amu.A simulation model was proposed to study the siloxane structure.Fourier transform infrared spectra of solution and film prove the disappearing of epoxy bond.The results of solid-state 13C and 29Si nuclear magnetic resonance experiments indicate the formation of Si-O-Si network.Potentiodynamic analysis shows that the self-assembled coating has excellent corrosion resistance.Salt fog tests prove that 2-methyl piperidine as inhibitor significantly improves the corrosion resistance of the self-assembled coating.

Incorporated Organic Modified Ag Nanoparticles in Ormocer

Ag nanoparticles coated trisodium citrate were incorporated in ormocer by sol-gel method. The doping concentration of Ag in ormocer is about 1.0% in weight. The HRTEM demonstrated that the particles disperse in ormocer, and the size of Ag nanoparticles is 5-10 nm. The absorption band of Ag nanoparticle at 410 nm was observed.

Microwave absorbing properties of La_(0.8)Ba_(0.2)MnO_3 nano-particles

La0.8Ba0.2MnO3 nano-particles were synthesized by sol-gel process, and the crystal structure and morphology were characterized by XRD and SEM, respectively. The complex permittivity and permeability were determined by microwave vector network analyzer in the frequency range of 2-18 GHz. The relationship between reflection coefficient and microwave frequency of La0.8Ba0.2 MnO3 was calculated based on measured data. The results show that the average diameter of La0.8Ba0.2MnO3 crystal powders is about 80 nm and the crystal structure is perovskite when being calcined at 800 ℃ for 2 h. The microwave absorbing peak is 13 dB at 6.7 GHz and the effective absorbing bandwidth above 10 dB reaches 1.8 GHz for the sample with the thickness of 2.6 mm. The microwave absorption can be attributed to both the dielectric loss and the magnetic loss from the loss tangents of the sample, but the former is greater than the latter.

Effect of Substitution of Al for Fe on Magnetic Properties and Particle Size of Ni-Co Nanoferrite

Nanocrystalline Al doped nickel-cobalt ferrite [Ni0.6Co0.4Fe2-xAlxO4 (x = 0.0, 0.1, 0.3, 0.5 and 0.7)] powders have been synthesized by sol-gel auto-ignition method and the effect of non-magnetic aluminum content on the nanosize particles and magnetic properties has been studied. The X-ray diffraction (XRD) revealed that the powders obtained are single phase with inverse spinel structure. The calculated grain size from XRD data have been verified using transmission electron microscopy (TEM). TEM photograph shows that the powders consist of nano meter sized grain. The size of nanoparticles decreases as the non magnetic Al content increases. Magnetic hysteresis loops were measured at room temperature with maximum applied magnetic field of 20 KOe. As aluminum content increases, the measured magnetic hysteresis curves became narrow and saturation magnetization (Ms), and coercive force (Hc) decreased. The reduction of magnetization with the increase of aluminum content is caused by non-magnetic Al3+ ions and weakened interaction between sub-lattices.

Structural and Magnetic Properties of Cr-Co Nanoferrite Particles

Nano-crystalline CrxCoFe2–xO4 (x = 0, 0.1, 0.2, 0.3, 0.4, 0.5) ferrites were synthesized by sol-gel method. The X-ray diffraction patterns of all the samples provide information about the existence of single phase spinel structure. The SEM and TEM micrographs show the uniform particle distribution and SAED pattern represents the polycrystalline nature of the resultant ferrite nano-particles. High purity of the sample is confirmed by energy dispersive X-ray analysis. The FTIR spectra show two strong absorption bands in the range of 600 - 400 cm–1, which confirm the presence of M-O stretching band in ferrites. The magnetic properties of the synthesized samples were investigated by using vibrating sample magnetometer at room temperature. According to VSM reports the main magnetic parameters like saturation magnetization (Ms), coercivity (Hc) were found to decrease with the substitution of Cr3+ content. Possible mechanisms which are responsible for the results are scrutinized minutely in this paper.

Study of deep transportation and plugging performance of deformable gel particles in porous media

Deformable gel particles(DGPs) possess the capability of deep profile control and flooding. However, the deep migration behavior and plugging mechanism along their path remain unclear. Breakage, an inevitable phenomenon during particle migration, significantly impacts the deep plugging effect. Due to the complexity of the process, few studies have been conducted on this subject. In this paper, we conducted DGP flow experiments using a physical model of a multi-point sandpack under various injection rates and particle sizes. Particle size and concentration tests were performed at each measurement point to investigate the transportation behavior of particles in the deep part of the reservoir. The residual resistance coefficient and concentration changes along the porous media were combined to analyze the plugging performance of DGPs. Furthermore, the particle breakage along their path was revealed by analyzing the changes in particle size along the way. A mathematical model of breakage and concentration changes along the path was established. The results showed that the passage after breakage is a significant migration behavior of particles in porous media. The particles were reduced to less than half of their initial size at the front of the porous media. Breakage is an essential reason for the continuous decreases in particle concentration, size, and residual resistance coefficient. However, the particles can remain in porous media after breakage and play a significant role in deep plugging. Higher injection rates or larger particle sizes resulted in faster breakage along the injection direction, higher degrees of breakage, and faster decreases in residual resistance coefficient along the path. These conditions also led to a weaker deep plugging ability. Smaller particles were more evenly retained along the path, but more particles flowed out of the porous media, resulting in a poor deep plugging effect. The particle size is a function of particle size before injection, transport distance, and different injection parameters(injection rate or the diameter ratio of DGP to throat). Likewise, the particle concentration is a function of initial concentration, transport distance, and different injection parameters. These models can be utilized to optimize particle injection parameters, thereby achieving the goal of fine-tuning oil displacement.

橡胶颗粒增强双网络结构堵水冻胶性能研究

目的研究橡胶颗粒增强双网络结构堵水冻胶性能,解决塔河油田为代表的缝洞型油藏在注水开发、注气开发过程中,出水、气窜现象频发的问题。方法选用丙烯酰胺/2-丙烯酰胺-2-甲基丙磺酸二元聚合物和疏水缔合聚合物为主剂,乌洛托品、间苯二酚和有机铬为交联剂,橡胶颗粒为增强剂制备了一种复合冻胶,详细考查了橡胶颗粒对冻胶基液黏度、成胶时间、成胶强度、耐稀释、耐温耐盐性能和封堵效果的影响规律。结果橡胶颗粒的加入,对冻胶基液黏度和成胶时间没有明显的改变,但对成胶强度、耐温耐盐性能和封堵效果具有明显提高作用。其中,橡胶颗粒质量分数为5%的增强冻胶的屈服应力达326.4 Pa,150℃下老化30天,脱水率仅为2.71%,对缝宽1 mm的裂缝岩心进行封堵,盐水突破压力梯度达到3.94 MPa/m。这表明,橡胶颗粒增强的双网络结构冻胶具有优异的封堵能力。结论该研究填补了塔河油田耐高温高盐堵水冻胶的技术空白,为塔河油田堵水技术发展提供了新的研究思路。

Sol-Gel与在位聚合联用制备分散良好的纳米杂化材料

采用 Sol- Gel法与在位聚合相结合的方法 ,使正硅酸乙酯在聚合物单体中进行水解、缩聚 ,然后再加入引发剂使单体聚合 ,制得了稳定分散的纳米粒子杂化的聚合物材料 ,该材料性能优良 ,具有很好的透明度。在保持树脂光学性能的前提下 ,材料的抗冲击性能有所改善。

Sol-Gel法制备球形UO_2陶瓷颗粒

以U3O8粉末为原料,采用外凝胶与内凝胶结合的sol-gel法,经过溶解制胶、凝胶成球、陈化、洗涤干燥、煅烧、还原烧结、筛选得到球形UO2陶瓷颗粒．采用该方法制备的陶瓷颗粒为面心立方结构,密度为理论密度的98．18％;基本不含杂质, O／U比为2．00,平均标准偏差为0．001;平均直径为498．1μm,标准偏差为14．7μm;球形度分布在1．00～1．10区间,平均值为1．04;平均畸形比为2．2×10-4,各项指标都达到设计要求．同时,研究分析了各参数的影响．