Simulation and visualization of the displacement between CO2 and formation fluids at pore-scale levels and its application to the recovery of shale gas

This article reports recent developments and advances in the simulation of the CO2-formation fluid displacement behaviour at the pore scale of subsurface porous media. Roughly, there are three effective visualization approaches to detect and observe the CO2-formation fluid displacement mechanism at the micro-scale, namely, magnetic resonance imaging, X-ray computed tomography and fabricated micromodels, but they are not capable of investigating the dis- placement process at the nano-scale. Though a lab-on-chip approach for the direct visualization of the fluid flow behaviour in nanoscale channels has been developed using an advanced epi-fluorescence microscopy method combined with a nanofluidic chip, it is still a qualitative analysis method. The lattice Boltzmann method （LBM） can simulate the CO2 displacement processes in a two-dimensional or three-dimensional （3D） pore structure, but until now, the CO2 displace- ment mechanisms had not been thoroughly investigated and the 3D pore structure of real rock had not been directly taken into account in the simulation of the CO2 displacement process. The status of research on the applications of CO2 displacement to enhance shale gas recovery is also analyzed in this paper. The coupling of molecular dynamics and LBM in tandem is proposed to simulate the CO2-shale gas displacement process based on the 3D digital model of shale obtained from focused ion beams and scanning electron microscopy.

Thermo-sensitive polymer nanospheres as a smart plugging agent for shale gas drilling operations

Emulsifier-free poly（methyl methacrylate-styrene） [P（MMA-St）] nanospheres with an average particle size of 100 nm were synthesized in an isopropyl alcoholwater medium by a solvothermal method. Then, through radical graft copolymerization of thermo-sensitive mono- mer N-isopropylacrylamide （NIPAm） and hydrophilic monomer acrylic acid （AA） onto the surface of P（MMA- St） nanospheres at 80 ℃, a series of thermo-sensitive polymer nanospheres, named SD-SEAL with different lower critical solution temperatures （LCST）, were prepared by adjusting the mole ratio of NIPAm to AA. The products were characterized by Fourier transform infrared spectroscopy, transmission electron microscopy, thermogravimetric analysis, particle size distribution, and specific surface area analysis. The temperature-sensitive behavior was studied by light transmittance tests, while the sealing performance was investigated by pressure transmission tests with Lungmachi Formation shales. The experimental results showed that the synthesized nanoparticles are sensitive to temperature and had apparent LCST values which increased with an increase in hydrophilic monomer AA. When the temperature was higher than its LCST value, SD- SEAL played a dual role of physical plugging and chemical inhibition, slowed down pressure transmission, and reduced shale permeability remarkably. The plugged layer of shale was changed to being hydrophobic, which greatly improved the shale stability

Study on Preparation and Electrical Properties of Ba_(1.03)Ce_(0.8)Eu_(0.2)O_(3-α) Solid Electrolyte

Ba_(1.03)Ce_(0.8)Eu_(0.2)O_(3-α) solid electrolyte with nonstoichiometric composition was prepared by high temperature solid-state reaction. Phase composition, surface and fracture morphologies of the specimen were characterized by using XRD and SEM, respectively. Ionic conduction was researched by gas concentration cell, the performance of hydrogen-air fuel cell was measured in the temperature range of 600～1000 ℃, and compared them with those of BaCe_(0.8)Eu_(0.2)O_(3-α) and Ba_(0.98)Ce_(0.8)Eu_(0.2)O_(3-α). The results indicate that Ba_(1.03)Ce_(0.8)Eu_(0.2)O_(3-α) is a single-phase perovskite-type orthorhombic system. It is a pure proton conductor in the temperature range of 600～1000 ℃ in hydrogen atmosphere, and its proton conduction is superior to that of BaCe_(0.8)Eu_(0.2)O_(3-α) and Ba_(0.98)Ce_(0.8)Eu_(0.2)O_(3-α). It is a mixed conductor of oxide ion and electron hole in oxygen atmosphere. At 1000 ℃, the performance of the fuel cell in which Ba_(1.03)Ce_(0.8)Eu_(0.2)O_(3-α) as electrolyte is higher than that of BaCe_(0.8)Eu_(0.2)O_(3-α) or Ba_(0.98)Ce_(0.8)Eu_(0.2)O_(3-α).

Formation damage mechanism and control strategy of the compound function of drilling fluid and fracturing fluid in shale reservoirs

For the analysis of the formation damage caused by the compound function of drilling fluid and fracturing fluid,the prediction method for dynamic invasion depth of drilling fluid is developed considering the fracture extension due to shale minerals erosion by oil-based drilling fluid.With the evaluation for the damage of natural and hydraulic fractures caused by mechanical properties weakening of shale fracture surface,fracture closure and rock powder blocking,the formation damage pattern is proposed with consideration of the compound effect of drilling fluid and fracturing fluid.The formation damage mechanism during drilling and completion process in shale reservoir is revealed,and the protection measures are raised.The drilling fluid can deeply invade into the shale formation through natural and induced fractures,erode shale minerals and weaken the mechanical properties of shale during the drilling process.In the process of hydraulic fracturing,the compound effect of drilling fluid and fracturing fluid further weakens the mechanical properties of shale,results in fracture closure and rock powder shedding,and thus induces stress-sensitive damage and solid blocking damage of natural/hydraulic fractures.The damage can yield significant conductivity decrease of fractures,and restrict the high and stable production of shale oil and gas wells.The measures of anti-collapse and anti-blocking to accelerate the drilling of reservoir section,forming chemical membrane to prevent the weakening of the mechanical properties of shale fracture surface,strengthening the plugging of shale fracture and reducing the invasion range of drilling fluid,optimizing fracturing fluid system to protect fracture conductivity are put forward for reservoir protection.

固相萃取-气相色谱-质谱法同时测定水中9种药品及个人护理用品

采用固相萃取-气相色谱-质谱联用技术，建立了水体中9种药品及个人护理用品（水杨酸、萘普生、布洛芬、对乙酰氨基酚、降固醇酸、三氯生、双氯酚酸、酮洛芬和双酚 A）的定量分析方法。水样品经稀盐酸调节至 pH =3后，采用 Oasis HLB 固相萃取小柱进行富集净化；选用三甲基氢氧化硫（ TMSH）为衍生化试剂，在常温条件下对目标物进行快速甲基化；以气相色谱-质谱法选择离子监测模式（GC-MS-SIM）进行检测，由2，4，5-涕丙酸为内标进行定量分析。本实验分别对固相萃取和衍生化等前处理条件进行了系统的研究。在优化的实验条件下，方法的回收率为50.7～115.4％，相对标准偏差均不高于10％，检出限为0.03～0.30μg / L，定量限为0．15～1．50μg / L。利用该方法对东莞市某农田灌溉水进行了分析，4种目标物在样品中有检出，最大质量浓度范围为0.176～0.998μg / L。结果表明该方法操作简便，灵敏可靠。

气相色谱-负化学源质谱联用法测定水产品及食用油中氟乐灵的残留量

建立了一种可用于水产品及食用油中氟乐灵残留量分析的分散型固相萃取-气相色谱-负化学离子源质谱方法。水产品及食用油经乙腈提取，4℃冷藏后，采用分散型固相萃取法净化，由气相色谱-负化学离子源质谱选择离子监测技术进行测定与确证，同位素内标法定量。在1～40μg / L 范围内氟乐灵农药的线性关系良好；方法定量限（LOQ）为0.02μg / kg；对鳗鱼、烤鳗、梭子蟹、小龙虾、猪油和橄榄油等6种复杂基质进行1.0、2.0和3.0μg / kg 等3个水平的添加回收试验，平均回收率均处于80％～100％之间，RSD≤10.3％；无干扰现象出现。该方法可作为水产品及食用油中氟乐灵残留检测的确证方法。

福建姜黄挥发油化学成分的HS-SPME-GC-MS分析

采用水蒸气蒸馏法提取福建姜黄挥发油,应用顶空固相微萃取进样结合气相色谱-串联质谱联用技术(HS-SPME-GC-MS)分析姜黄挥发油的化学成分。结果表明:姜黄挥发油含有量为7.2%(mL/g),从姜黄挥发油中共分出62个色谱峰,初步鉴定出了其中的51种化学成分,占总挥发油总量的98.41%。在鉴定的化合物中,主要为单萜类化合物和倍半萜类化合物,其中新发现一种主要成分为β-柏木烯,相对含量占比高达26.58%,这可作为福建姜黄挥发油的特征成分和主要品质指标。本研究结果将为福建姜黄植物药材的品质评价提供科学依据。

Study of fluid cell coarsening for CFD-DEM simulations of polydisperse gas–solid flows

Particle polydispersity is ubiquitous in industrial fluidized beds,which possesses a significant impact on hydrodynamics of gas-solid flow.Computational fluid dynamics-discrete element method(CFD-DEM)is promising to adequately simulate gas-solid flows with continuous particle size distribution(PSD)while it still suffers from high computational cost.Corresponding coarsening models are thereby desired.This work extends the coarse-grid model to polydisperse systems.Well-resolved simulations with different PSDs are processed through a filtering procedure to modify the gas-particle drag force in coarse-grid simulations.We reveal that the drag correction of individual particle exhibits a dependence on filtered solid volume fraction and filtered slip velocity for both monodisperse and polydisperse systems.Subsequently,the effect of particle size and surrounding PSD is quantified by the ratio of particle size to Sauter mean diameter.Drag correction models for systems with monodisperse and continuous PSD are developed.A priori analysis demonstrates that the developed models exhibit reliable prediction accuracy.

Hydrocarbon Charging and Accumulation Process of the Large Bozhong19-6 Condensate Gas Reservoirs in the Southwestern Bozhong Sub-Basin,Bohai Bay Basin,China

The Bozhong19-6(BZ19-6)condensate gas reservoirs,located in the southwestern Bozhong sub-basin,Bohai Bay Basin,China,were paleo-oil reservoirs in the geological past and have undergone at least three successive hydrocarbon charging events.The hydrocarbon migration and accumulation process of“early oil and late gas”has occurred in the current reservoirs.At the end of the sedimentation of the Guantao Formation(N_(1)g,∼12 Ma),the reservoirs began to fill with first stage low-moderate mature crude oil.At the late stage of the Lower Minghuazhen Formation(N_(1)ml)(∼6.7 Ma),the reservoirs were largely charged with second stage high mature crude oil.Since the deposition of the upper Minghuazhen Formation(N_(2)m^(u),∼5.1 Ma),the paleo-oil reservoirs were transformed into shallow Neogene reservoirs due to the reactivation of basement faults.From the late stage of the N_(2)m^(u)to the present day(∼2.8–0 Ma),the reservoirs were rapidly filled by natural gas within a short period.In addition,analysis of the formation of the reservoir bitumen and the conspicuous loss of the lower molecular weight n-alkanes in the crude oil reveal that the injection of a large amount of gas in the late stage caused gas flushing of the early charged oil.

Investigation on the application of reformed coke oven gas in direct reduction iron production with a mathematical model

To investigate the application of reformed coke oven gas （COG） in producing the direct reduction iron （DRI）, we simulated a countercurrent gas solid moving bed reactor in which the iron ore pellet was reduced by reformed COG. An ordinary differential equation （ODE） was set based on the unreacted shrinking core model considering both mass and energy balances of the reactor. The concentration and temperature profiles of all species within the reactor were obtained by solving the ODE sys tem. The solid conversion and gas utilization were studied by changing gas flow rate, solid flow rate, reactor length, and the ratio of O/CHa to guide the practical application of COG in DRI production. Model results showed that COG was suitable for the DRI production. In order to meet the requirement of the industrial production, the minimum gas flow rate was set as 130,000 Nm3/h, and the maximum production was 90 t/h. The reactor length and the mole ratio x（O）： x（CH4） were depended on the actual industrial situations.

A New Hybrid Stress Element with Fluid

In the process of shale gas exploitation,there exits two difficult problems:one is the real numerical simulation of a tremendous number of holes in actual shale;the other is the fluid–solid coupling problem involved in holes,where the difficulty of transition at the interface between the Eulerian grid and the Lagrangian grid becomes the most important.In response to these two problems,this paper establishes an element model with both fluid and solid.At the fluid–solid interface,the equilibrium condition of the surface force is introduced to obtain the modified complementary energy functional,and a new hybrid stress element with fluid is derived.The comparison of the simulation results with those of the ordinary commercial finite element software verifies the effectiveness and efficiency of this element,and proves its applicability in the problem of shale with numerous holes.Furthermore,this element can be extended to general problems of solid with fluid in.