四川盆地海相页岩气富集条件及勘探开发有利区

历经十余年探索实践,四川盆地海相页岩气勘探取得了一系列进展,锁定五峰组—龙马溪组为最有利产层,提出了一批页岩气富集高产理论,形成了集地质评价、开发优化、优快钻井、体积压裂、工厂化作业、清洁开发等为一体的勘探开发技术,探明了万亿立方米级储量的页岩气大气田。时值中国页岩气勘探发展的重要节点,回顾四川盆地海相页岩气勘探开发历程、梳理五峰组—龙马溪组页岩气在地质条件与富集规律上的成果认识、展望四川盆地海相页岩气勘探的重点接替领域,对推进盆地海相页岩气的勘探开发有积极意义。(1)四川盆地海相页岩气勘探开发经历了4个阶段：评层选区找目标阶段;浅层至中—深层先导试验阶段;浅层至中—深层示范区建设阶段;浅层至中—深层上产、深层评价、常压页岩气评价、立体开发评价、超深层和新层系探索阶段。(2)四川盆地五峰组—龙马溪组的沉积条件优越,深水陆棚相高有机质含量页岩呈连续稳定分布;页岩气主要赋存在有机孔隙中,页岩储层在纵向上集中发育,连续厚度大;川南地区和川东南涪陵区块的构造相对简单,气源持续补给、远离古/今剥蚀区和大型断裂逸散区是页岩气富集保存的有利区;目前,五峰组—龙马溪组的页岩气资源量为33.19×10<...     

水平井压裂微地震监测成果的不对称性分析

为了分析水平井压裂微地震监测成果的不对称性,为客观评价压裂效果提供依据,文中综合应用微地震监测、三维地震、录井以及压裂数据,紧密结合精细地质研究、工程设计,系统分析了54口水平井压裂的微地震监测成果,总结了导致水平井压裂微地震监测成果不对称的因素,取得如下认识：(1)导致水平井压裂微地震监测成果不对称的因素主要包括工程因素、地质因素以及完钻井分布等三个方面,其中地质因素具体包括天然裂缝、断层、岩性变化、地应力等;(2)天然裂缝、缝长距离内的完钻井会诱导压裂裂缝转向,并沿着裂缝集中发育区和完钻井周围延伸,在水平井两侧形成不对称的微地震事件分布;(3)断层对压裂裂缝具有诱导和屏蔽作用,压裂裂缝沿着断面延伸,微地震监测事件呈面状分布,压裂裂缝无法延伸至断层另一侧,形成远离水平井的单侧分布;(4)纵向隔夹层、横向的岩性变化会对压裂裂缝的延伸起控制和封隔作用,在很大程度上抑制了压裂裂缝延伸甚至无法形成裂缝,形成微地震事件在横向和纵向的不对称性;(5)当水平井与最大主应力方向不垂直时,微地震事件分布与水平段存在夹角,形成角度不对称。     

海上新区油气勘探突破典型案例分析及启示

随着陆地勘探程度越来越高,获得大发现的难度越来越大,油气勘探向海域拓展是大势所趋,加快海域新区突破、实现资源有序接替,具有十分重要的战略意义。重点剖析了渤海湾盆地秦皇岛32-6油田、黎凡特盆地塔马尔气田两个海域大发现的勘探历程,梳理每个勘探阶段的指导思想、部署思路及做法,探讨制约突破发现的因素及推动勘探突破的地质认识转变和思想革新。研究显示,盲目跟风追热点、未找到适合的理论指导制约了渤海湾油田发现;客观分析成藏特征,转变思路,以新近系为主要目的层,以生烃凹陷包围的隆起区及其倾没带为主要勘探方向,推动了秦皇岛32-6油田大发现。黎凡特盆地塔马尔气田的发现则归因于储层物源和低成熟生物气的新认识及较高的勘探投入。研究认为,摸清成藏规律是推动大发现的内在动因,尤其是深海前沿领域勘探;关键成藏要素的颠覆性认识是突破关键,保证持续稳定的勘探投入是推动海域新区突破的前提条件。     

Pervaporation via silicon-based membranes: Correlation and prediction of performance in pervaporation and gas permeation

Pervaporation (PV) is a membrane technology that holds great promise for industrial applications. To better understand the PV mechanism, PV dehydrations of various types of organic solvents (methanol, ethanol, iso-propanol, tert-butanol, and acetone) were performed on five types of organosilica and two types of silicon carbide-based membranes, all with different pore sizes. Water permeance was dependent on the types of organic aqueous solutions, which suggested that organic solvents penetrated the pores and hindered the permeation of water. In addition, water permeance of various types of membranes in PV was well correlated with hydrogen permeance in single-gas permeation. Furthermore, a clear correlation was obtained between the permeance ratio in PV and that in single-gas permeation, which was confirmed via the modified-gas translation model. These correlations make it possible to use single-gas permeation properties to predict PV performance.     

Kinetics simulation of propylene epoxidation over different Ti species in TS-1

A thorough experimental investigation on the kinetic behavior of liquid-phase propylene epoxidation over TS-1 and tetrapropylammonium hydroxide (TPAOH) treated TS-1 catalysts was conducted in a fixed-bed reactor. The amounts of different coordinated Ti species in the catalysts were quantified by spectroscopies, and their catalytic performances of the epoxidation and alcoholysis of propylene oxide were measured by kinetic modeling. The study shows that the TPAOH treatment converted some of the tetrahedrally coordinated Ti to octahedrally coordinated Ti, and both species were active for the epoxidation and alcoholysis. The superior catalytic performance observed over the TPAOH treated TS-1 is due to two factors, the increased percentage of active sites, and reduced energy barrier for epoxidation on the octahedrally coordinated Ti. In addition, as the H₂O₂ conversion increases, the adsorption equilibrium constant of propylene oxide plays a more decisive role than the activation energy for the selectivity of propylene glycol monomethyl ethers.     

Optimized sintering behavior and microwave dielectric properties of Ca1+2xSnSi2x+yO3+6x+2y by composition modulation

Ca_1+2xSnSi_2x+yO_3+6x+2y (0.1 ≤ x ≤ 0.9; 0.1 ≤ y ≤ 0.9) microwave dielectric ceramics were prepared through traditional solid-state reaction sintered at 1450°C–1500°C for 5 hours. The Ca₃SnSi₂O₉ second phase replaced the SnO₂ second phase of the Ca_1+2xSnSi_2xO_3+6x (x = 0, y = 0) ceramics by controlling the ratio of Ca:Sn:Si. The cracks of CaSnO₃ (x = 0, y = 0) ceramic were inhibited, the microwave dielectric properties were optimized by introducing the Ca₃SnSi₂O₉ second phase, and the CaSnO₃-Ca₃SnSi₂O₉ mixture system existed at (0.1 ≤ x ≤ 0.9, y = 0). The CaSnSiO₅ phase with positive τ_f value was related to the Si-rich in CaSnSi_yO_3+2y (x = 0; 0.1 ≤ y ≤ 0.9), and the coexistence of three and four phases was obtained at CaSnSi_yO_3+2y (0.1 ≤ y ≤ 0.9) ceramics. The CaSnSiO₅ phase appeared at CaSnSi_yO_3+2y (0.3 ≤ y ≤ 0.9) ceramics. The CaSnSi_yO_3+2y (y = 0.8) ceramic with 49.2 wt% CaSnSiO₅ phase exhibited excellent microwave dielectric properties: ε_r = 11.06, Q × f = 57,500 GHz (at 11.5 GHz), and τ_f = +8.1 ppm/°C.     

Oxidation behavior and mechanism of aluminum oxynitride (AlON) at elevated temperatures

The oxidation behavior and mechanism of aluminum oxynitride (AlON) powder exposed to air at elevated temperatures between 800°C and 1300°C was investigated by X-ray diffractometry (XRD), scanning electron microscope (SEM), electron spin resonance (ESR), nuclear magnetic resonance (NMR), and simultaneous thermogravimetry, differential thermal analysis, and mass spectrometry techniques (TG-DTA-MS). The weight of AlON gradually increases to a maximum value at 1150°C and then decreases with further heating. Meanwhile, AlON powder undergoes chemical changes, as evidenced by lattice expansion, and turns eventually into alumina. ESR spectra reveal the occurrence of lone pair electrons in the oxidized products and the intensity of corresponding resonance signal increases before disappearing with the increase in temperature. Combined with the results of NMR and TG-DTA-MS, the measured data suggest that Al-N in [AlO₃N] tetrahedron and [AlO₅N] octahedron are gradually oxidized into Al-O-N group with lone pair electrons, which causes continuous weight gain and lattice expansion. Further oxidation at higher temperatures results in alumina and N₂.     

Tuning fermi level and band gap in Li4Ti5O12 by doping and vacancy for ultrafast Li+ insertion/extraction

Li₄T_i5O₁₂ (LTO) attracts great interest due to the “zero strain” during cycles but the poor electronic and ionic conductivity critically impede the practical application. Herein, we report a synergy strategy of tuning localized electrons to shift Fermi level and band gap by Mg/Zr co-doping and oxygen vacancy incorporation, which significantly improves Li⁺ and electronic transport. More importantly, the intrinsic synergistic mechanism has been revealed by neutron diffraction, X-ray absorption spectra, and first-principles calculations. The “elastic effect” of lattice induced by Mg/Zr co-doping allows LTO to accommodate more oxygen vacancies to a certain degree without a severe lattice distortion, which largely improves the electronic conductivity. Mg/Zr co-doping and oxygen vacancy incorporation effectively enhanced the dynamic characteristics of LTO electrode, achieving the excellent rate performance (90 mAh/g at 20C) and cycle stability (96.9% after 500 cycles at 10C). First-principles calculations confirm Fermi level shifts to the conduction band, and the band gap becomes narrowed due to the synergistic modulation, and the intrinsic mechanism of the enhanced electronic and Li-ion conductivity is clarified. This study offers some insights into achieving the fast Li⁺ insertion/extraction by tuning the crystal and electronic structure with lattice doping and oxygen vacancy engineering.     

Polyethylenimine-modified sugarcane bagasse cellulose as an effective adsorbent for removing Cu(II) from aqueous solution

Polyethylenimine-modified sugarcane bagasse cellulose (SBCMP), as a new adsorbent, was synthesized by the reaction of polyethylenimine (PEI) with sugarcane bagasse cellulose and glutaraldehyde. The adsorption of Cu(II) by SBCMP was pH-dependent, and the higher removal efficiency of Cu(II) appeared in the range of pH 3.0–6.0. The adsorption isothermal data fitted well with the Langmuir model, and the maximum adsorption capacity of SBCMP was up to 107.5 mg/g. The adsorption kinetics was best described by the pseudo-second-order kinetic. The adsorption of Cu(II) by SBCMP was unfavorable at high temperatures, and thermodynamic analyses implied that the adsorption of Cu(II) by SBCMP was an exothermic reaction. Fourier transform infrared spectroscopy (FT-IR) combined with X-ray photoelectron spectroscopy (XPS) revealed that Cu(II) adsorption on SBCMP mainly controlled by the nitrogen atoms of  NH group in PEI. The results of regeneration cycles showed that SBCMP was suitable for reuse in the adsorption of Cu(II) from aqueous solution. These experimental results suggested that SBCMP is expected to be a new biomass adsorbent with high efficiency in removing Cu(II) from wastewater.