TBAB hydrate formation and growth in a microdevice under static and dynamic conditions

The natural gas hydrate has become one of the most promising future green energy sources on the earth.The natural gas hydrates mostly exist in the sediments with porous structure, so a solid understanding of the hydrate formation and growth processes in the porous medium is of significance for the exploitation of natural gas hydrate. The micro-packed bed device is one of the efficient microfluidic devices in the engineering field, but it has been rarely used for the hydrate-based research. In this study, a transparent micro-packed bed device filled with glass beads was developed to mimic the porous condition of sediments, and used to in-situ visualize the hydrate formation and growth habits in the pore spaces under both static and dynamic conditions. For the static experiment, two types of hydrate growth patterns in porous medium were observed and identified in the micro-packed bed device, which were the graincoating growth and pore-filling growth. For the dynamic condition, the hydrate formation, growth,distribution habits and hydrate blockage phenomena in the pore spaces were in-situ visually captured.The impacts of flowrate and subcooling on the pressure variation of the micro-packed bed and the duration of the hydrate growth under dynamic flow condition in pores were in-situ monitored and analyzed. The higher flowrate could result in the faster hydrate growth and more severe blockage in pores, but the effect of subcooling condition might be less significant at the high flowrate.

Restoration of reservoir diagenesis and hydrocarbon accumulation process by calcite in-situ U-Pb dating and fluid inclusion analysis: A case study on Cretaceous Qingshuihe Formation in Gaoquan Structure, southern Junggar Basin, NW China

The complexity of diagenesis and hydrocarbon accumulation in the deep reservoirs in southern Junggar Basin restricts hydrocarbon exploration in the lower reservoir assemblage. The lithofacies and diagenesis of reservoirs in the Cretaceous Qingshuihe Formation in the Gaoquan structure of the Sikeshu Sag, southern Junggar Basin were analyzed. On this basis, the thermal history was calibrated using calcite in-situ U-Pb dating and fluid inclusion analysis to depict the hydrocarbon accumulation process in the Gaoquan structure. The results show that the Qingshuihe reservoir experienced two phases of calcite cementation and three phases of hydrocarbon charging. The calcite cements are dated to be (122.1±6.4) Ma, (14.4±1.0) Ma - (14.2±0.3) Ma. The hydrocarbon charging events occurred at around 14.2-30.0 Ma (low-mature oil), 14.2 Ma (mature oil), and 2 Ma (high-mature gas). The latter two phases of hydrocarbon charging contributed dominantly to the formation of reservoir. Due to the S-N compressive thrust activity during the late Himalayan period since 2 Ma, the traps in the Gaoquan structure were reshaped, especially the effective traps which developed in the main reservoir-forming period were decreased significantly in scale, resulting in weak hydrocarbon shows in the middle-lower part of the structure. This indicates that the effective traps in key reservoir-forming period controlled hydrocarbon enrichment and distribution in the lower reservoir assemblage. Calcite U-Pb dating combined with fluid inclusion analysis can help effectively describe the complex diagenesis and hydrocarbon accumulation process in the central-west part of the basin.

In-situ hydrocarbon formation and accumulation mechanisms of micro- and nano-scale pore-fracture in Gulong shale, Songliao Basin, NE China

By conducting experimental analyses, including thermal pyrolysis, micro-/nano-CT, argon-ion polishing field emission scanning electron microscopy (FE-SEM), confocal laser scanning microscopy (CLSM), and two-dimensional nuclear magnetic resonance (2D NMR), the Gulong shale oil in the Songliao Basin was investigated with respect to formation model, pore structure and accumulation mechanism. First, in the Gulong shale, there are a large number of pico-algae, nano-algae and dinoflagellates, which were formed in brackish water environment and constituted the hydrogen-rich oil source materials of shale. Second, most of the oil-generating materials of the Qingshankou Formation shale exist in the form of organo-clay complex. During organic matter thermal evolution, clay minerals had double effects of suppression and catalytic hydrogenation, which expanded shale oil window and increased light hydrocarbon yield. Third, the formation of storage space in the Gulong Shale was related to dissolution and hydrocarbon generation. With the diagenesis, micro-/nano-pores increased, pore diameter decreased and more bedding fractures appeared, which jointly gave rise to the unique reservoir with dual media (i.e. nano-scale pores and micro-scale bedding fractures) in the Gulong shale. Fourth, the micro-/nano-scale oil storage unit in the Gulong shale exhibits independent oil/gas occurrence phase, and shows that all-size pores contain oils, which occur in condensate state in micropores or in oil-gas two phase (or liquid) state in macropores/mesopores. The understanding about Gulong shale oil formation and accumulation mechanism has theoretical and practical significance for advancing continental shale oil exploration in China.

In-situ observation of porosity formation during directional solidification of Al-Si casting alloys

In-situ observation of porosity formation during directional solidification of two Al-Si alloys (7%Si and 13%Si) was made by using of micro-focus X-ray imaging.In both alloys,small spherical pores initially form in the melt far away from the eutectic solid-liquid (S/L) interface and then grow and coagulate during solidification.Some pores can float and escape from the solidifying melt front at a relatively high velocity.At the end of solidification,the remaining pores maintain spherical morphology in the near eutectic alloy but become irregular in the hypoeutectic alloy.This is attributed to different solidification modes and aluminum dendrite interactions between the two alloys.The mechanism of the porosity formation is briefly discussed in this paper.

Characterization and in-situ formation mechanism of tungsten carbide reinforced Fe-based alloy coating by plasma cladding

The precursor carbonization method was first applied to prepare W–C compound powder to perform the in-situ synthesis of the WC phase in a Fe-based alloy coating. The in-situ formation mechanism during the cladding process is discussed in detail. The results reveal that fine and obtuse WC particles were successfully generated and distributed in Fe-based alloy coating via Fe/W–C compound powders. The WC particles were either surrounded by or were semi-enclosed in blocky M7C3 carbides. Moreover, net-like structures were confirmed as mixtures of M23C6 and α-Fe; these structures were transformed from M7C3. The coarse herringbone M6C carbides did not only derive from the decomposition of M7C3 but also partly originated from the chemical reaction at the α-Fe/M23C6 interface. During the cladding process, the phase evolution of the precipitated carbides was WC → M7C3 → M23C6 ＋ M6C.

Evolution features of in-situ permeability of low-maturity shale with the increasing temperature,Cretaceous Nenjiang Formation,northern Songliao Basin,NE China

Temperature-triaxial pressure permeability testing at the axial pressure of 8 MPa and confining pressure of 10 MPa,closed shale system pyrolysis experiment by electrical heating and scanning electron microscopy analysis are used to study the evolution mechanism of in-situ permeability in the direction parallel to bedding of low-maturity shale from Member 2(K_(2)n_(2))of Cretaceous Nenjiang Formation in northern Songliao Basin with mainly Type I kerogen under the effect of temperature.With the increasing temperature,the in-situ permeability presents a peak-valley-peak tendency.The lowest value of in-situ permeability occurs at 375℃.Under the same temperature,the in-situ permeability decreases with the increase of pore pressure.The in-situ permeability evolution of low-maturity shale can be divided into 5 stages:(1)From 25℃to 300℃,thermal cracking and dehydration of clay minerals improve the permeability.However,the value of permeability is less than 0.01×10^(-3)μm^(2).(2)From 300℃to 350℃,organic matter pyrolysis and hydrocarbon expulsion result in mineral intergranular pores and micron pore-fractures,these pores and fractures form an interconnected pore network at limited scale,improving the permeability.But the liquid hydrocarbon,with high content of viscous asphaltene,is more difficult to move under stress and more likely to retain in pores,causing slow rise of the permeability.(3)From 350℃to 375℃,pores are formed by organic matter pyrolysis,but the adsorption swelling of liquid hydrocarbon and additional expansion thermal stress constrained by surrounding stress compress the pore-fracture space,making liquid hydrocarbon difficult to expel and permeability reduce rapidly.(4)From 375℃to 450℃,the interconnected pore network between different mineral particles after organic matter conversion,enlarged pores and transformation of clay minerals promote the permeability to increase constantly even under stress constraints.(5)From 450℃to 500℃,the stable pore system and crossed fracture system in different bedding directions significantly enhance the permeability.The organic matter pyrolysis,pore-fracture structure and surrounding stress in the different stages are the key factors affecting the evolution of in-situ permeability.

Deep original information preservation by applying in-situ film formation technology during coring

Accurately obtaining the original information of an in-situ rock via coring is a significant guiding step for exploring and developing deep oil and gas resources.It is difficult for traditional coring technology and equipment to preserve the original information in deep rocks.This study develops a technology for insitu substance-preserved(ISP),moisture-preserved(IMP),and light-preserved(ILP)coring.This technology stores the original information in real time by forming a solid sealing film on the in-situ sample during coring.This study designed the ISP-IMP-ILP-Coring process and tool.In addition,an ISP-IMP-ILPCoring process simulation system was developed.The effects of temperature,pressure,and film thickness on the quality of the in-situ film were investigated by performing in-situ film-forming simulation experiments.A solid sealing film with a thickness of 2-3 mm can be formed;it completely covers the core sample and has uniform thickness.The film maintains good ISP-IMP-ILP properties and can protect the core sample in the in-situ environment steadily.This study verifies the feasibility of“film formation during coring”technology and provides strong support for the engineering application of ISP-IMP-ILPCoring technology.

Effects of Material Parameters on Stress Distribution in Casing-cement-formation(CCF)Multilayer Composite System

This work focus on the stress distribution of the casing-cement-formation(CCF)multilayer composite system,which is a borehole system with multiple casings and cement sheathes.Mostof the previous relevant studies are based on the traditional CCF system with the single casing and cement sheath,but these results are not adaptive to the CCF system multiple composite system.In this paper,the FEM numerical model of CCF multilayer composite system was constructed.Numerical simulations were calculated and compared with the system which consists of the single casing and cement sheath.Results show that the multilayer composite system possesses better performance.On this basis,the sensitivity analysis of main influence mechanical parameters such as in-situ stress,the elastic of cement sheathes and the elastic of formation are conducted.The cement sheath on the inside,namely cement sheath-1,is sensitive to its elastic modulus;meanwhile,the cement sheath on the outside,namely cement sheath-2,is not so sensitive to the elastic modulus of cement sheath-1.Cement sheath-1 and cement sheath-2 are all sensitive to the elastic modulus of cement sheath-2,and the mises stress of them has opposite trend to the elastic modulus of cement sheath-2.The proper values of elastic modulus of cement sheath-1 and cement sheath-2 are 5GPa and 5GPa to 30GPa,respectively.Under the in-situ stress ratio σh/σH=0.7,the maximum mises stress of cementsheath-1 and cement sheath-2 increase as the increase of σh,and they are nearly equal when σh=15GPa.This research can be helpful for the design and analysis of CCF multilayer composite system.

In-situ Formation of Spinel Fibers in MgO-C Refractory Matrixes

In-situ magnesia-rich spinel fiber was formed resulting from the addition of ferrocene into MgO-C refractory matrixes. The formation of in-situ spinel fiber was detected to start at 1300 ℃. The amount, diameter and length of the fibers increased with rising temperature. Ferrocene may have catalytic effects on the growth of the fibers in two aspects. First, the reaction between MgO and C and the decomposition of Al4C3 may be catalyzed at high temperature. Suitable concentration gaseous phase is then created for vapor-vapor reaction which could result in the in-situ formation of fibers. Second, Fe nanoparticle produced from ferrocene can act as catalytic droplets and catalyze the growth of the fibers. The fibers are formed via the vapor-liquid-solid and vapor-solid mechanisms. In terms of chemical thermodynamics, the partial pressure of CO and Mg（g） are found to play an important role in the in-situ fibers formation. Different concentration of vapors affects the size, amount and composition of the fibers at different temperatures. The mechanical properties of MgO-C brick was found to be improved by ferrocene addition.

MICROSTRUCTURE AND MECHANICAL PROPERTIES OF IN-SITU FORMATION FIBROUS POLYTYPE AlN COMPOSITE-MATERIAL

In-situ formation fibrous polytype AlN composite ceramic materials was prepared from AlN-Y_2O_3-SiO_2 system.In comparison with AlN ceramics,both bending strength and fracture toughness of the composite materials are much bettered.Microstructural observation revealed that a lot of epitaxial growth fibrous AlN polytype occurred in matrix.Y_2O_3 seems to act as a densifier for in-situ formation materials and as medium for growth of fibrous polytype.SiO_2 is the growth promoter for fibrous polytype.The occurrnce of fibrous polytype may increase the strength and toughness of AlN ceramic composite mateirals.

Direct observation of the CO_(2) formation and C–H consumption of carbon electrode in an aqueous neutral electrolyte supercapacitor by in-situ FTIR and Raman

Electrical double-layer capacitors(EDLCs)consist of energy storage devices that present high-power and moderate energy density.The electrolyte and electrode physicochemical properties are crucial for improving their overall energy storage capabilities.Therefore,the stability of the EDLCs’materials is the primary focus of this study.Since energy storage depends on the specific capacitance,and also on the square of the maximum capacitive cell voltage(UMCV).Thus,electrodes with high specific surface area(SSA)and electrolytes with excellent electrochemical stability are commonly reported in the literature.Aqueous electrolytes are safer and green devices compared to other organic-based solutions.On the other hand,their UMCVis reduced compared to other electrolytes(e.g.,organic-based and ionic liquids).In this sense,spanning the UMCVfor aqueous-based electrolytes is a’hot topic’research.Unfortunately,the lack of protocols to establish reliable UMCVvalues has culminated in the publishing of several conflicting results.Herein,we confirm that multiwalled carbon nanotubes(MWCNTs)housed in cells degrade and produce CO_(2) under abusive polarisation conditions.It is probed by employing electrochemical techniques,in-situ FTIR and in-situ Raman spectroscopies.From these considerations,the current study uses spectro-electrochemical techniques to support the correct determination of the electrode and electrolyte stability conditions as a function of the operating electrochemical parameters.

Study on determination method of in-situ stress using formation fracturing test and Kaiser effect method

A new method, which is based on formation fracturing test and Kaiser effect method, has been developed for confirming the oilfield in-situ stress in this paper. The new method has been used in a certain oilfield of China and the determined oilfield in-situ stresses is more accurate than that based on one single method.

In-situ Polymerization-modification Process and Foaming of Poly（ethylene terephthalate）

Most of traditional linear poly(ethylene terephthalate)(PET)resins of relatively low molecular mass and narrow molecular mass distribution have low melt strength at foaming temperatures,which are not enough to support and keep cells.An in-situ polymerization-modification process with esterification and polycondensation stages was performed in a 2 L batch stirred reactor using pyromellitic dianhydride(PMDA)or pentaerythritol(PENTA)as modifying monomers to obtain PETs with high melt strength.The influence of amounts of modifying monomers on the properties of modified PET was investigated.It was found that the selected modifying monomers could effectively introduce branched structures into the modified PETs and improve their melt strength.With increasing the amount of the modifying monomer,the melt strength of the modified PET increased.But when the amount of PENTA reached 0.35%or PMDA reached 0.9%,crosslinking phenomenon was observed in the modified PET.Supercritical carbon dioxide(ScCO2)was employed as physical foaming agent to evaluate the foaming ability of modified PETs.The modified PETs had good foaming properties at 14 MPa of CO2pressure with foaming temperature ranging from 265°C to 280°C.SEM micrographs demonstrated that both modified PET foams had homogeneous cellular structures,with cell diameter ranging from 35μm to 49μm for PENTA modified PETs and38μm to 57μm for PMDA modified ones.Correspondingly,the cell density had a range of 3.5×107cells·cm 3to 7×106cells·cm 3for the former and 2.8×107cells·cm 3to 5.8×106cells·cm 3for the latter.

Mechanistic insight into N_2O formation during NO reduction by NH_3 over Pd/CeO_2 catalyst in the absence of O_2

N2O is a major by-product emitted during low-temperature selective catalytic reduction of NO with NH3(NH3-SCR), which causes a series of serious environmental problems. A full understanding of the N2O formation mechanism is essential to suppress the N2O emission during the low-temperature NH3-SCR, and requires an intensive study of this heterogeneous catalysis process. In this study, we investigated the reaction between NH3 and NO over a Pd/CeO2 catalyst in the absence of O2, using X-ray photoelectron spectroscopy, NH3-temperature-programmed desorption, NO-temperature-programmed desorption, and in-situ Fourier-transform infrared spectroscopy. Our results indicate that the N2O formation mechanism is reaction-temperature-dependent. At temperatures below 250 ℃, the dissociation of HON, which is produced from the reaction between surface H· adatoms and adsorbed NO, is the key process for N2O formation. At temperatures above 250 ℃,the reaction between NO and surface N·, which is produced by NO dissociation, is the only route for N2O formation, and the dissociation of NO is the rate-determining step. Under optimal reaction conditions, a high performance with nearly 100% NO conversion and 100% N2 selectivity could be achieved. These results provide important information to clarify the mechanism of N2O formation and possible suppression of N2 O emission during low-temperature NH3-SCR.

Effect of temperature on formation and evolution of solid electrolyte in terphase on Si@Graphite@C anodes

Studies on the formati on and evolutio n of the solid electrolyte in terface(SEI)film under different ambient temperatures are important to understand the failure behavior of lithium-ion batteries(LIBs).Herein,in-situ electrochemical impedance spectroscopy(EIS)test is performed on the whole discharge process of Si@Graphite@C/Li cell at 0,25 and 55℃,respectively.Combining with scanning electron microscopy,transmission electron microscopy and X-ray photoelectron spectroscopy characterizations,it is found that the SEI film undergoes a complicated evolution process of pre-formation,self-improvement and gradual decay in succession at 25℃.Besides,due to the dissolution of organo-alkyl lithium at high temperature,the formed film is mainly composed of LiF,Li_(2)CO_(3) and other in organic salts,which helps to decrease the impedance.However,the electrolyte is consumed continuously on the new exposed in terface,leading to the degraded performance of the cell.Moreover,the dyn amic properties of Li^(+) ions are poor at low temperature,though the migration ability of Li^(+) ions in the solid phase can be improved as the cycle goes on.Therefore,the development and application of in-situ EIS tech no logy are expected to become an important means to explain the electrochemical performance of batteries.

Simulation of coupled THM process in surrounding rock mass of nuclear waste repository in argillaceous formation

To investigate and analyze the thermo-hydro-mechanical(THM) coupling phenomena of a surrounding rock mass in an argillaceous formation, a nuclear waste disposal concept in drifts was represented physically in an in-situ test way. A transversely isotropic model was employed to reproduce the whole test process numerically. Parameters of the rock mass were determined by laboratory and in-situ experiments. Based on the numerical simulation results and in-situ test data, the variation processes of pore water pressure, temperature and deformation of surrounding rock were analyzed. Both the measured data and numerical results reveal that the thermal perturbation is the principal driving force which leads to the variation of pore water pressure and deformations in the surrounding rock. The temperature, pore pressure and deformation of rock mass change rapidly at each initial heating stage with a constant heating power. The temperature field near the heater borehole is relatively steady in the subsequent stages of the heating phase. However, the pore pressure and deformation fields decrease gradually with temperature remaining unchanged condition. It also shows that a transversely isotropic model can reproduce the THM coupling effects generating in the near-field of a nuclear waste repository in an argillaceous formation.

龙凤山气田易漏井不承压泡沫水泥浆固井技术

中国石化龙凤山地区面临井温高、地层承压能力低、周期长、承压堵漏成本高等系列固井技术难题,导致固井周期长、费用高且固井质量无法保证等。为解决上述问题,在分析工区现有固井工艺的基础上,提出了不承压泡沫水泥浆固井设计思路,形成了龙凤山地区不承压泡沫水泥浆固井工艺,建立了泡沫水泥浆井内密度及恒密度注气固井计算方法与固井工艺;优选了发泡剂、降失水剂和早强剂等泡沫水泥浆关键外加剂,开发了新型低密度泡沫水泥浆体系,耐温性可达到120℃以上,泡沫半衰期大于420 s、水泥浆30 min失水32 mL、48 h强度13.3 MPa,各项性能均可满足中石化龙凤山气田高温、深井固井要求;形成了适合于龙凤山气田泡沫水泥浆固井技术。现场11口井应用表明,该项技术能够有效提高固井质量,避免了固井前承压、分级或尾管固井作业,平均节约承压堵漏周期7 d以上,经济效益显著。龙凤山气田泡沫水泥浆固井技术对解决中国石化其他工区深井、高温井固井漏失、承压堵漏等难题具有重要借鉴意义和可持续性推广价值。

盐水微滴/泡沫铜复合体系中甲烷水合物生成动力学研究

提高海水水合储气速率和储气密度对水合物技术规模化应用至关重要。将一定浓度的NaCl溶液与疏水性气相纳米二氧化硅高速搅拌分散成微米级盐水微滴。8.0 MPa、274.15 K条件下,利用不同硅含量的盐水微滴进行水合储甲烷实验,研究甲烷水合物生成动力学特性。结果表明,硅含量2.5%(质量分数)的盐水微滴分散性和储气性能最佳,储气量达141.01 cm^(3)·cm^(-3),储气速率达7.37 cm^(3)·cm^(-3)·min^(-1)。进一步将该硅含量盐水微滴填充至开孔泡沫铜中,构建盐水微滴/泡沫铜复合水合储气体系。研究发现,泡沫铜三维巢状金属骨架能显著加速水合反应热的转移,提高微滴水合储气性能。5.0~8.0 MPa下,相较于盐水微滴单一体系,复合体系水合储气量提高4.72%~21.70%,最大储气速率提高38.25%~110.58%。

油相对水相泡沫形成和稳定性的影响

油水混相泡沫在日用化妆品、化学工业、石油工业等领域有着广泛的应用,但是目前关于油水混相泡沫的报道多集中在探究表面活性剂、温度、pH、矿化度等外界因素对油水混相泡沫的稳定性的影响,对于油相种类和油相含量对水相泡沫的形成和稳定性影响机制缺乏系统研究。文章通过改变油相种类、油水体积比进行发泡实验,最后通过分析各泡沫体积、泡沫排液半衰期、泡沫的衰变速率、泡沫的微观粒径、油相的表面张力和油水界面张力来探究油相对水相泡沫的形成和稳定性影响机制。研究发现:随着油相碳链长度的增加水相泡沫的起泡性能下降;同时随着油相的表面张力增大,泡沫稳定性提高;油水体积比对水相泡沫的形成和稳定性有着重要的影响,在低油水体积比时,泡沫壁之间排列紧密,形成了大小不一的泡沫,且由于泡沫之间相互挤压,使其微观结构形貌杂乱无规则;随着油水体积比的升高泡沫粒径整体上变小,且大小变得越来越均匀,泡沫结构变得更加致密,使得泡沫更加稳定。

原位成纤PTFE对PP/CNT微孔注塑发泡材料电磁屏蔽性能的影响

采用聚丙烯(PP)为基体、以多壁碳纳米管(CNT)为碳纳米填料,制备二元复合泡孔材料PP/CNT,并且,当CNT含量为1%时,复合微孔材料泡孔质量及电磁屏蔽性能均较好。以聚四氟乙烯(PTFE)为原位成纤增强相,进行微孔注塑发泡成型,探究PP/CNT/PTFE三元复合微孔材料的电磁屏蔽性能,制备了力学性能较好、对电磁辐射吸收率较高的微发泡电磁屏蔽复合材料;研究了PTFE微纤含量对PP/CNT/PTFE三元复合微孔材料注塑发泡泡孔形貌及电磁屏蔽性能的影响规律;得到了该实验条件下PTFE的最佳添加量。结果表明,当PTFE含量为1%时,原位成纤效果较好,三元复合微孔材料的泡孔直径显著减小,电磁屏蔽性能从未添加PTFE时的12.6 dB提高至24.8 dB。